CN109679608B - High-temperature-resistant acid-resistant foam drainage agent, preparation method and application - Google Patents
High-temperature-resistant acid-resistant foam drainage agent, preparation method and application Download PDFInfo
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Abstract
The invention relates to a high-temperature-resistant acid-resistant foam drainage agent, a preparation method and application thereof, and mainly solves the problem that the existing foam drainage 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 comprises the following components in parts by mass: 1 part of polyamine surfactant and 0-10 parts of nano particles; wherein the polyamine surfactant is shown as a formula (1); r1Is selected from C4～C32One of hydrocarbyl or substituted hydrocarbyl, R2、R3、R4Is independently selected from C1～C5Hydrocarbyl or substituted hydrocarbyl radical, R5、R6Independently selected from (CH)2)cOr (CH)2)c(CHOH)d(CH2)eOne of (1); y is1、Y2Is selected from COO‑、SO3 ‑、OSO3 ‑The technical scheme 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 drainage agent, a preparation method and application thereof, in particular to a high-temperature-resistant acid-resistant foam drainage 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 under the acidic condition is a main factor for restricting the development of the foam drainage technology of the high-temperature ultra-deep gas well.
Disclosure of Invention
The invention aims to solve the technical problems that the existing foam drainage 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 high-temperature-resistant acid-resistant foam drainage agent which is applied to a high-temperature deep well, has very excellent temperature resistance under an acidic condition, and has strong liquid carrying, foaming and foam stabilizing properties.
The second technical problem to be solved by the present invention is to provide a method for preparing a high temperature resistant and acid resistant foam drainage agent corresponding to the first technical problem.
The third technical problem to be solved by the present invention is to provide an application of a high temperature resistant and acid resistant foam drainage agent corresponding to the solution of 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 comprises the following components in parts by weight:
1)1 part of polyamine surfactant;
2) 0-10 parts of nanoparticles;
wherein, the molecular general formula of the polyamine surfactant is shown as a formula (1):
R1is selected from C4～C32One of hydrocarbyl or substituted hydrocarbyl, R2、R3、R4Is independently selected from C1～C5Hydrocarbyl or substituted hydrocarbyl radical, R5、R6Independently selected from (CH)2)cOr (CH)2)c(CHOH)d(CH2)eC is any integer from 1 to 4, d is any integer from 0 to 3, and e is any integer from 1 to 4; y is1、Y2Independently selected from COO-、SO3 -、OSO3 -One of (1); m is the number of the vinylamine fragments, and m is any integer of 1-10; t1, t2 are positive charges, s1, s2 are R5Y1、R6Y2The number of the substituents t1 ═ s1 ═ 0 or 1, and t2 ═ s2 ═ 0 or 1.
In the above technical solution, the nanoparticles are preferably at least one of nano silica, nano calcium carbonate, and nano hectorite, and more preferably nano silica; and may be a solid or liquid sol.
In the above technical scheme, R1Preferably C8～C24Hydrocarbyl or substituted hydrocarbyl.
In the above technical scheme, R2、R3、R4Independently is preferably (CH)2)aOH or (CH)2)bCH3One kind of (1).
In the above-described embodiment, a is preferably 2 to 4, b is preferably 0 to 5, and b is more preferably 0 to 2.
Among the above-mentioned solutions, the preferred one isc1 or 2, d or 1, e or 1 or 2.
In the above technical scheme, Y1、Y2 -Independently is preferably COO-Or SO3 -One kind of (1).
In the above-mentioned technical means, m is preferably 1 to 5.
In the above technical solution, the mass ratio of the polyamine surfactant to the nanoparticles in the foam drainage agent is preferably 1: (0.02-0.2).
The polyamine surfactant (1) is the key active ingredient of the high-temperature resistant and acid-resistant foam drainage agent, and the polyamine surfactant can be supplied in various forms for transportation, storage or field 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 high temperature resistant and acid resistant foam drainage agent of the present invention may be obtained by mixing the polyamine surfactant and the nanoparticles in a desired ratio, and is preferably obtained by the following technical means for solving the second technical problem.
To solve the second technical problem, the invention adopts the following technical scheme: a method for preparing a high temperature resistant and acid resistant foam drainage agent to solve one of the above technical 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, 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)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 a metal compound, a metal alkyl compound, a metal amino compound;
c. alkylation reaction:
by using a monohalogenated hydrocarbon-sodium hydroxide process, an aldehyde acid oxidation process, or by using an aldehyde catalytic hydrogenation process comprising the steps of: the R synthesized in the step b0CH2(NHCH2CH2)mNH2R' CHO and H2In a short-chain alcohol solvent, a metal catalyst is used for reaction to obtain the compound shown in the formula (1), wherein s 1-t 1-s 2-t 2-0A tertiary amine nonionic surfactant; the short carbon chain alcohol is selected from C1～C5Hydrocarbyl or substituted hydrocarbyl alcohols; r' is selected from H, C1～C5One of hydrocarbyl or substituted hydrocarbyl; r0CH2(NHCH2CH2)mNH2：R”CHO：H2The molar ratio of (A) to (3-20): (5-40);
or further obtaining the zwitterionic surfactant with 1 in at least one of s 1-t 1 and s 2-t 2 in the molecular general formula shown in the formula (1) through a step d reaction:
d. quaternization reaction:
and c, mixing the tertiary amine nonionic surfactant and the ionizing reagent which are obtained in the step c and have the molar ratio of s1, t1, s2, t2 to 0 to obtain a mixture, wherein the molar ratio is 1: (1-5) reacting in a short carbon chain alcohol aqueous solution at a reaction temperature of 50-120 ℃ for 1-10 hours to generate a zwitterionic surfactant with at least one of s1 ═ t1 and s2 ═ t2 shown in formula (1) being 1; the ionizing agent is selected from XR5Y1M or X R6Y2N, wherein M and N are independently selected from one of alkali metals, and X is one of chlorine, bromine or iodine; the volume fraction of the short-carbon chain alcohol in the short-carbon chain alcohol aqueous solution is 0-100%;
e. and c, uniformly mixing the polyamine surfactant and the nanoparticles synthesized in the step c and/or the step d with water according to the required mass part to obtain the foam drainage agent.
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 solution, the metal catalyst in step C is preferably one of Rancy Ni or Pd/C, and more preferably Rancy Ni.
In the above technical solution, the short carbon chain alcohol in step c is preferably at least one of ethanol, propanol or isopropanol.
In the above technical solution, R' in step c is preferably H, CH3Or CH2One of OH.
In the above technical scheme, R in step c0CH2(NHCH2CH2)mNH2：R”CHO：H2The molar ratio of (a) to (4-10): 5 to 20.
In the technical scheme, the tertiary amine nonionic surfactant and the ionizing agent in the step d are mixed according to a molar ratio of 1: (1-1.5).
In the above technical scheme, the solvent in the step d is preferably selected from C3～C8Ketone and C6～C9For example, at least one of the group consisting of acetone, butanone, pentanone, benzene, toluene or xylene, trimethylbenzene, ethylbenzene and diethylbenzene.
In the above technical solution, the XR5Y1M or X R6 Y2Examples of N include, but are not limited to, alkali metal salts of chloroacetic acid, bromoacetic acid, 3-chloro-2-hydroxypropanesulfonic acid, and 2-chloroethanesulfonic acid.
The high-temperature-resistant acid-resistant foam drainage agent 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 high-temperature-resistant acid-resistant foam drainage agent in any one of the technical schemes in drainage and gas production of a gas well.
In the above technical scheme, the application of the foam drainage agent is not particularly limited, and a person skilled in the art can apply the foam drainage agent according to the existing drainage gas production process technology, for example, but not limited to, the foam drainage agent is preferably used for acidic high-temperature high-salt ultra-deep gas wells and high-temperature acidic gas-containing gas wellsReservoir, e.g., formation temperature of 150-200 deg.C, total salinity of formation brine of 500-200000 mg/L, H2S and CO2The content of (A) is 0-35%.
The 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 high-temperature-resistant acid-resistant foam drainage agent, a preparation method and application thereof in drainage and gas production.
The thermal decomposition temperature of the polyamine compound prepared by the invention is 200 ℃ or above, and the polyamine compound is not hydrolyzed or is hydrolyzed in a trace amount in an acidic aqueous solution, so that the polyamine compound has good temperature resistance; secondly, the molecules are provided with more hydrophilic groups, so that on one hand, the salt resistance is improved, on the other hand, the amount of bound water and bound water carried by the foaming agent is increased, 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 200 ℃.
The content or concentration of the foam discharging agent in the invention refers to the content or concentration of the component 1) in the technical scheme.
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, when 0.02-0.15% of the foam drainage agent is in 0-200,000 mg/L salinity brine and does not contain kerosene, the foaming height reaches 167mm before and after high-temperature aging, the liquid carrying rate reaches 91.5%, when 0.15% of the foam drainage agent is in 100,000mg/L salinity brine, the foaming height reaches 155mm when 30 wt% of the kerosene is contained, the liquid carrying rate reaches 86.3%, and the foam drainage agent has excellent temperature resistance, salt resistance and oil resistance in an acid environment, so that better technical effects are 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 HFL01
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. 192.8 g (0.4 mol) of C were added to a dry pressure reactor equipped with a stirring device17H33CH2(NHCH2CH2)5NH2200 g of isopropanol, 6 g of Rancy Ni and 109.2 g of formaldehyde (3.6 mol) are mixed, deoxygenated and then H is introduced2Reacting at 110-140 ℃ for reduction reaction, keeping the temperature for 1 hour after hydrogen absorption is finished, and performing post-treatment to obtain a polyamine compound1(R1＝C18H35，m＝5，R2＝R3＝R4＝CH3T1 ═ t2 ═ s1 ═ s2 ═ 0), is foam displacement agent HFL 01.
(2) HFL01 was dissolved in deionized water, 100,000mg/L, 200,000mg/L NaCl water, respectively, to make 0.3 wt% of the foam-expulsion-agent mother liquor.
The performances of foaming power, foam stability, liquid carrying capacity and the like of the HFL01 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.
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 in the measurement of HFL01 performance, pH was adjusted to 7, 4 and 2 with hydrochloric acid to simulate neutral and acidic gas environments, and the results are shown in table 2.
[ example 3 ]
The difference is as in [ example 1 ]:
d. polyamine compounds1(R1＝C18H35，m＝5，R2＝R3＝R4＝CH3T1 ═ t2 ═ s1 ═ s2 ═ 0)58.2 g (0.1 mol) were mixed with 29.5 g (0.15 mol) of sodium 3-chloro-2-hydroxypropanesulfonate and 100 ml of ethanol/water (v/v ═ 1) in a four-neck flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and heated to reflux for 5 hours. Evaporating the solvent, adding water to obtain polyamine compound1(R1＝C18H35，m＝5，R2＝R3＝R4＝CH3T1 ═ t2 ═ s1 ═ s2 ═ 0) of sodium hydroxypropanesulfonate as a foam remover HFL02, the results are shown in table 3.
[ example 4 ]
The same as [ example 3 ], except that the polyamine compound1(R1＝C18H35，m＝5，R2＝R3＝R4＝CH3Sodium hydroxypropanesulfonate product HFL02 and nanosilica (particle size 80nm) at t1 ═ t2 ═ s1 ═ s2 ═ 0) were formulated into 0.3 wt% foam drainage stock solutions in a 5:1 mass ratio, with simulated water at 100,000mg/LNaCl, and the results are shown in table 4.
[ example 5 ]
The oil resistance of a mixed system of HFL02, HFL02 and nanosilica (particle size 80nm) in a mass ratio of 5:1 was tested with the addition of 30 wt% kerosene, and the results are shown in Table 5, using simulated water of 100,000 mg/LNaCl.
[ example 6 ]
(1) Preparation of foam scrubbing agent HFL 03:
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. To a dry pressure reactor equipped with a stirring device was added 130.8 g (0.4 mol) of C15H31CH2(NHCH2CH2)2NH2150 g ethanol, 2 g Rancy Ni and 105.6 g acetaldehyde (2.4 mol) are mixed, deoxygenated and then H is introduced2Reacting at 110-140 ℃ for reduction reaction, keeping the temperature for 1 hour after hydrogen absorption is finished, and performing post-treatment to obtain a polyamine compound2(R1＝C16H33，m＝2，R2＝R3＝R4＝C2H5T1 ═ t2 ═ s1 ═ s2 ═ 0), is foam displacement agent HFL 03.
(2) The same as [ example 1 ] except that the aging was carried out at 150 ℃ for 72 hours, the results are shown in Table 6.
[ example 7 ]
The same as [ example 6 ] except that in the measurement of HFL03 performance, pH was adjusted to 7, 4 and 2 with hydrochloric acid to simulate neutral and acidic gas environments, and aged at 150 ℃ for 72 hours, the results are shown in Table 7.
[ example 8 ]
(1) Preparation of foam scrubbing agent HFL 04:
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. To a dry pressure reactor equipped with a stirring device 147.2 g (0.4 mol) of C were added21H43CH2NHCH2CH2NH2200 g of isopropanol, 3.5 g of Rancy Ni and 144.0 g of glycolaldehyde (2.4 mol) are mixed, deoxygenated and H is introduced2Reacting at 110-140 ℃ for reduction reaction, keeping the temperature for 1.5 hours after hydrogen absorption is finished, and performing post-treatment to obtain a polyamine compound3(R1＝C22H45，m＝1，R2＝R3＝R4＝C2H4OH，t1＝t2＝s1＝s2＝0)。
d. Polyamine compounds3(R1＝C22H45，m＝1，R2＝R3＝R4＝C2H4OH, t1 ═ t2 ═ s1 ═ s2 ═ 0)50 g (0.1 mol), 15.9 g (0.12 mol) of potassium chloroacetate and 100 ml of isopropanol/water (v/v ═ 0.2) were mixed in a four-neck flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and heated to reflux for 7 hours. Evaporating the solvent, adding water to obtain polyamine compound3(R1＝C22H45，m＝1，R2＝R3＝R4＝C2H4OH, t1 ═ t2 ═ s1 ═ s2 ═ 0) potassium acetate product as a foam remover HFL 04. Preparing 0.3 wt% of foam discharging agent mother liquor according to the mass ratio of HFL04 to nano silicon dioxide (particle size of 50nm) of 2: 1.
(2) The same as [ example 1 ] except that the aging was carried out at 200 ℃ for 24 hours, the results are shown in Table 8.
[ example 9 ]
The same as [ example 8 ] except that in the measurement of HFL04 performance, pH was adjusted to 7, 4 and 2 with hydrochloric acid to simulate neutral and acidic gas environments, and aging was carried out at 200 ℃ for 24 hours, the results are shown in Table 9.
[ example 10 ]
(1) Preparation of foam scrubbing agent HFL 05:
a. adding 56.7 g (0.55 mol) of diethylenetriamine 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 2) under stirring, reacting for 8 hours at the reaction temperature of 120-160 ℃, and simultaneously collecting methanol generated by the reaction to obtain the required amide compound C19H29CO(NHCH2CH2)2NH2The yield thereof was found to be 86.9%.
b. Removing water from three-neck flask device equipped with reflux condenser tube, dropping funnel and thermometerThen, 13.3 g (0.35 mol) of lithium aluminum hydride and 100 ml of dry dioxane are added, stirred, dispersed and mixed, and 38.7 g (0.1 mol) of C is added dropwise at-10 to 5 DEG C19H29CO(NHCH2CH2)2NH2The 40 wt% dioxane solution is added dropwise and slowly heated to about 30 ℃ for reaction for 6 hours. Carefully pouring the reaction liquid into ice water, and carrying out post-treatment to obtain a rosin polyamine compound C19H29CH2(NHCH2CH2)2NH2The yield thereof was found to be 75.8%.
c. To a dry pressure reactor equipped with a stirring device was added 149.2 g (0.4 mol) of C19H29CH2(NHCH2CH2)2NH2200 g of propanol, 7 g of Rancy Ni and 72.0 g of formaldehyde (2.4 mol) were mixed, deoxygenated and H was passed through2Carrying out reduction reaction at 120-140 ℃, keeping the temperature for 1 hour after hydrogen absorption is finished, and carrying out post-treatment to obtain a polyamine compound4(R1＝C20H31，m＝2，，R2＝R3＝R4＝CH3T1 ═ t2 ═ s1 ═ s2 ═ 0), is foam displacement agent HFL 05. Preparing 0.3 wt% of foam discharging agent mother liquor according to the mass ratio of HFL05 and nano silicon dioxide (particle size of 120nm) of 20: 1.
(2) The results are shown in Table 10, as in example 1.
[ example 11 ]
The same as [ example 10 ] except that in the measurement of HFL05 performance, pH was adjusted to 7, 4 and 2 with hydrochloric acid to simulate neutral and acidic gas environments, and the results are shown in table 11.
[ COMPARATIVE EXAMPLE 1 ]
The same as [ example 1 ], except that C is used17H33CO(NHCH2CH2)5NH2(HFL06) instead of HFL01, simulated water was 100,000mg/LNaCl, and the results are shown in Table 12.
[ COMPARATIVE EXAMPLE 2 ]
The same as [ example 2 ], except that C is used17H33CO(NHCH2CH2)5NH2(HFL06) alternative to HFL01, moduloThe water was 100,000mg/LNaCl and the results are shown in Table 13.
[ COMPARATIVE EXAMPLE 3 ]
The same as [ example 6 ], except that C is used15H31CO(NHCH2CH2)2NH2(HFL07) instead of HFL03, simulated water was 100,000mg/LNaCl, and the results are shown in Table 12.
[ COMPARATIVE EXAMPLE 4 ]
The same as [ example 7 ], except that C is used15H31CO(NHCH2CH2)2NH2(HFL07) instead of HFL03, simulated water was 100,000mg/LNaCl, and the results are shown in Table 13.
[ COMPARATIVE EXAMPLE 5 ]
The same as [ example 8 ], except that C is used21H43CONHCH2CH2NH2(HFL08) instead of HFL04, simulated water was 100,000mg/LNaCl, and the results are shown in Table 12.
[ COMPARATIVE EXAMPLE 6 ]
The difference is that C is21H43CONHCH2CH2NH2(HFL08) instead of HFL04, simulated water was 100,000mg/LNaCl, and the results are shown in Table 13.
[ COMPARATIVE EXAMPLE 7 ]
The same as [ example 10 ], except that C is used19H29CO(NHCH2CH2)2NH2(HFL09) instead of HFL05, simulated water was 100,000mg/LNaCl, and the results are shown in Table 12.
[ COMPARATIVE EXAMPLE 8 ]
The same as [ example 11 ], except that C is used19H29CO(NHCH2CH2)2NH2(HFL09) instead of HFL05, simulated water was 100,000mg/LNaCl, and the results are shown in Table 13.
[ COMPARATIVE EXAMPLE 9 ]
The same as comparative example 1 except that the betaine C is oleamidopropyl carboxylate17H33CONH(CH2)3N+(CH3)2CH2COO-(HFL10) instead of HFL01, simulated water was 100,000mg/LNaCl, and the results are shown in Table 12.
The same as comparative example 2 except that the betaine C is oleamidopropyl carboxylate17H33CONH(CH2)3N+(CH3)2CH2COO-(HFL10) instead of HFL01, simulated water was 100,000mg/LNaCl, and the results are shown in Table 13.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
TABLE 6
TABLE 7
TABLE 8
TABLE 9
Watch 10
TABLE 11
TABLE 12
Watch 13
Claims (10)
1. The foam water discharging agent comprises the following components in parts by weight:
1)1 part of polyamine surfactant;
2) 0-10 parts of nanoparticles;
wherein the polyamine surfactant is selected from at least one of the general molecular formulas shown in formula (1):
in the formula (1), R1Is selected from C4～C32One of hydrocarbyl or substituted hydrocarbyl, R2、R3、R4Is independently selected from C1～C5Hydrocarbyl or substituted hydrocarbyl radical, R5、R6Independently selected from (CH)2)cOr (CH)2)c(CHOH)d(CH2)eC is any integer from 1 to 4, d is any integer from 0 to 3, and e is any integer from 1 to 4; y is1、Y2Independently selected from COO, SO3、OSO3One of (1); m is the number of the vinylamine fragments, and m is any integer of 1-10; t1, t2 are positive charges, s1, s2 are R5Y1、R6Y2The number of the substituents t1 ═ s1 ═ 0 or 1, and t2 ═ s2 ═ 0 or 1.
2. The foam drainage agent according to claim 1, wherein R is1Is C8～C24Hydrocarbyl or substituted hydrocarbyl; r2、R3、R4Is (CH)2)aOH or (CH)2)bCH3Wherein a is any integer from 2 to 4, and b is any integer from 0 to 2; c is any integer from 1 to 2, d is any integer from 0 to 1, and e is any integer from 1 to 2; y is1、Y2Independently selected from COO, SO3One of (1); m is 1 to 5.
3. The foam drainage agent according to claim 1, wherein the nano-particles are one of nano-silica, nano-calcium carbonate and nano-hectorite.
4. The foam drainage agent according to claim 1, wherein the mass ratio of the polyamine surfactant to the nanoparticles is 1 (0.02-0.2).
5. A method for preparing the foam drainage agent of any one of claims 1 to 4, comprising the following steps:
a. amidation reaction:
r is to be0COOR' andH(NHCH2CH2)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, 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)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. alkylation reaction:
by using a monohalogenated hydrocarbon-sodium hydroxide process, an aldehyde acid oxidation process, or by using an aldehyde catalytic hydrogenation process comprising the steps of: the R synthesized in the step b0CH2(NHCH2CH2)mNH2R' CHO and H2In a short carbon chain alcohol solvent, a metal catalyst is adopted to react to obtain a tertiary amine nonionic surfactant with s 1-t 1-s 2-t 2-0 in a molecular general formula shown in a formula (1); the short carbon chain alcohol is selected from C1～C5Hydrocarbyl or substituted hydrocarbyl alcohols; r' is selected from H, C1～C5One of hydrocarbyl or substituted hydrocarbyl; r0CH2(NHCH2CH2)mNH2：R”CHO：H2The molar ratio of (A) to (3-20): (5-40);
or further obtaining the zwitterionic surfactant with 1 in at least one of s 1-t 1 and s 2-t 2 in the molecular general formula shown in the formula (1) through a step d reaction:
d. quaternization reaction:
and c, mixing the tertiary amine nonionic surfactant and the ionizing reagent which are obtained in the step c and have the molar ratio of s1, t1, s2, t2 to 0 to obtain a mixture, wherein the molar ratio is 1: (1-5) reacting in a short carbon chain alcohol aqueous solution at a reaction temperature of 50-120 ℃ for 1-10 hours to generate a zwitterionic surfactant with at least one of s1 ═ t1 and s2 ═ t2 shown in formula (1) being 1; the ionizing agent is selected from XR5Y1M or XR6Y2N, wherein M and N are independently selected from one of alkali metals, and X is one of chlorine, bromine or iodine; the volume fraction of the short-carbon chain alcohol in the short-carbon chain alcohol aqueous solution is 0-100%;
e. and c, uniformly mixing the polyamine surfactant and the nanoparticles synthesized in the step c and/or the step d with water according to the required mass part to obtain the foam drainage agent.
6. The method for preparing foam drainage agent according to claim 5, wherein R in step a 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.
7. The method for preparing the foam drainage agent according to claim 5, wherein the step b is performed by using H-Y+Is LiAlH4、LiAlH(OEt)3Or NaBH4Wherein the aprotic solvent is at least one of diethyl ether, tetrahydrofuran and dioxane.
8. The method for preparing a foam water discharging agent according to claim 5, wherein the metal catalyst in the step C is selected from one of Rancy Ni and Pd/C; the short carbon chain alcohol is selected from at least one of methanol, ethanol, propanol or isopropanol; r' is selected from H, CH3Or CH2One of OH; r0CH2(NHCH2CH2)mNH2：R”CHO：H2The molar ratio of (A) to (4-10): 5 to 20.
9. The method for preparing a foam drainage agent according to claim 5, wherein the tertiary amine nonionic surfactant of step d: the mol ratio of the ionizing reagent is 1: 1-1.5; the short carbon chain alcohol is selected from at least one of methanol, ethanol, propanol or isopropanol.
10. Use of the foam water drainage agent according to any one of claims 1 to 4 in drainage and gas production of a gas well.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280636A (en) * | 1997-12-05 | 2001-01-17 | 阿克佐诺贝尔公司 | Use of an alkoxy lated polyamine surfactant as a viscose spin bath additive |
| CN103289666A (en) * | 2013-06-04 | 2013-09-11 | 西南石油大学 | Automatic-defoaming foam discharging agent for gas well drainage and preparation method thereof |
| CN104774603A (en) * | 2015-04-28 | 2015-07-15 | 中国科学院理化技术研究所 | Stable foam system based on nano particles and Gemini surface active agents and preparation method thereof |
| CN104974730A (en) * | 2015-06-12 | 2015-10-14 | 中国石油天然气股份有限公司 | High temperature-resistant high-mineralization degree foam scrubbing agent and its preparation method and use |
| CN105199700A (en) * | 2015-10-13 | 2015-12-30 | 西南石油大学 | Oligomeric betanine type foam drainage agent and preparation method |
| WO2017031103A1 (en) * | 2015-08-18 | 2017-02-23 | Ecolab Usa Inc. | Fluoro-inorganics for acidification or neutralization of water systems |
| CN106590563A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Salt-tolerant drainage gas recovery foam scrubbing agent composition and preparation method and application thereof |
| CN106753304A (en) * | 2016-11-30 | 2017-05-31 | 四川锦盛油田技术服务有限公司 | A kind of gas well scale inhibition oil resistant type liquid foam water discharge agent and preparation method thereof |
-
2017
- 2017-10-18 CN CN201710969503.3A patent/CN109679608B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280636A (en) * | 1997-12-05 | 2001-01-17 | 阿克佐诺贝尔公司 | Use of an alkoxy lated polyamine surfactant as a viscose spin bath additive |
| CN103289666A (en) * | 2013-06-04 | 2013-09-11 | 西南石油大学 | Automatic-defoaming foam discharging agent for gas well drainage and preparation method thereof |
| CN104774603A (en) * | 2015-04-28 | 2015-07-15 | 中国科学院理化技术研究所 | Stable foam system based on nano particles and Gemini surface active agents and preparation method thereof |
| CN104974730A (en) * | 2015-06-12 | 2015-10-14 | 中国石油天然气股份有限公司 | High temperature-resistant high-mineralization degree foam scrubbing agent and its preparation method and use |
| WO2017031103A1 (en) * | 2015-08-18 | 2017-02-23 | Ecolab Usa Inc. | Fluoro-inorganics for acidification or neutralization of water systems |
| CN105199700A (en) * | 2015-10-13 | 2015-12-30 | 西南石油大学 | Oligomeric betanine type foam drainage agent and preparation method |
| CN106590563A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Salt-tolerant drainage gas recovery foam scrubbing agent composition and preparation method and application thereof |
| CN106753304A (en) * | 2016-11-30 | 2017-05-31 | 四川锦盛油田技术服务有限公司 | A kind of gas well scale inhibition oil resistant type liquid foam water discharge agent and preparation method thereof |
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