CN109679610B - Solid foam drainage agent with pH value response, preparation method and application - Google Patents
Solid foam drainage agent with pH value response, preparation method and application Download PDFInfo
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- CN109679610B CN109679610B CN201710969511.8A CN201710969511A CN109679610B CN 109679610 B CN109679610 B CN 109679610B CN 201710969511 A CN201710969511 A CN 201710969511A CN 109679610 B CN109679610 B CN 109679610B
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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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Abstract
The invention relates to a solid foam drainage agent with pH value response, 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 performance in an acidic environment is poor, and the problems of production reduction and even spray stopping of a high-temperature and high-salt ultra-deep gas well caused by liquid accumulation and difficulty in filling of a liquid foam discharging agent cannot be solved. The solid foam drainage agent responding to the pH value comprises the following components in parts by mass: 1)1 part of a long-chain polyamine compound; 2) 0.05-1000 parts of solid filler; 3) 0-0.5 parts of adhesive; the long-chain polyamine compound has a molecular general formula shown in a formula (1); the solid filler is at least one of carbonate, bicarbonate, sulfate, phosphate, borate, metal halide, urea, biuret and the like; the adhesive is at least one of dextrin, epoxy resin and the like, better solves the problem 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 solid foam drainage agent, a preparation method and application thereof, in particular to a solid foam drainage agent with pH value response, 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 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
The invention aims to solve the technical problems that the existing foam drainage agent has poor high-temperature resistance in an acid environment, cannot solve the problems of yield reduction and even spray stopping caused by liquid accumulation of a high-temperature ultra-deep gas well and difficulty in filling a liquid foam drainage agent, and provides a solid foam drainage agent with pH value response.
The second technical problem to be solved by the present invention is to provide a method for preparing a solid foam drainage agent with pH value response corresponding to the solution of the first technical problem. The present invention is also directed to a solid foam drainage agent having a pH response corresponding to one of the above-mentioned problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a solid foam drainage agent responding to a pH value comprises the following components in parts by mass:
(1)1 part of a long-chain polyamine compound;
(2) 0.05-1000 parts of solid filler;
(3) 0-0.5 parts of adhesive;
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、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;
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)bCH3One kind of (1).
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.
In the above technical solution, the solid filler is preferably at least one of carbonate, bicarbonate, sulfate, phosphate, borate, metal halide, formate, acetate, tartaric acid and salts, citric acid and salts, phthalic acid and salts, gallic acid and salts, urea, biuret, and the like; more preferably at least one of sodium carbonate, sodium bicarbonate, sodium borate, sodium chloride, sodium acetate, tartaric acid, sodium tartrate, citric acid, sodium citrate, potassium phthalate, urea and biuret.
In the above technical solution, the binder is preferably at least one of dextrin, epoxy resin, polyacrylamide, starch, cellulose, polyethylene glycol, and the like; further preferably at least one of polyacrylamide, starch and polyethylene glycol.
In the technical scheme, the mass ratio of the long-chain polyamine compound, the solid filler and the adhesive in the solid foam drainage agent is 1: (0.1-200): (0.01-0.1).
The key active ingredient of the solid foam-remover composition of the present invention is (1), and the long-chain polyamine compound, the solid filler and the binder may be mixed in a desired ratio, and preferably obtained by the following technical scheme for solving the second technical problem.
To solve the second technical problem, the invention adopts the following technical scheme: a method for preparing a pH-responsive solid foam drainage agent as set forth above to solve one of the problems, 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 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 the content of the first and second substances,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 the reaction temperature of 50-120 ℃ for 3-20 hours to generate a long-chain polyamine compound shown in the structural formula (1); the ionizing agent is selected from XR9Y1Or X R'9Y′1At least one of; the base is selected from alkali metal hydroxide or alkali metal alkoxide; y is1And Y'1Is SO3M1Or COON1，M1And N1Is an alkali metal, and X is chlorine, bromine or iodine;
(2) and (2) uniformly mixing the long-chain polyamine compound synthesized in the step (1), the solid filler and the adhesive according to the required mass parts, and then pressing and forming to prepare the solid foam drainage agent.
In the above technical solution, the solid foam drainage agent may be in the shape of a rod or a ball.
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～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 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 pH value response solid 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 solid foam water-discharging agent with the pH value response in the technical scheme in drainage and gas production of the acidic high-temperature high-salinity ultra-deep gas well.
In the above technical scheme, the application of the solid foam drainage agent responsive to the pH value is not particularly limited, and those skilled in the art can apply the solid foam drainage agent according to the existing drainage and gas production 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 salinity 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 solid foam drainage agent with pH value response, a preparation method and application thereof in drainage 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 molecules contain heteroatoms 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 the temperature of 150-200 ℃.
The key effective component (1) of the foam scrubbing agent, the solid filler and the adhesive have good compatibility, and the formed solid composition does not influence the foam scrubbing performance of the solid composition.
The content or concentration of the foam scrubbing agent in the invention refers to the content or concentration of the molecular general formula (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, the foaming height of the solid foam drainage agent with 0.02-0.15% pH value response reaches 171mm before and after high-temperature aging in 0-200,000 mg/L salinity saline, 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 acid environment, so that a better technical effect is achieved.
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 FS01
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+ms3＝20，r1+r2+mr3＝3，R2＝R3＝R4H), yield 96.2%.
d. Long-chain polyamine polyether compounds1(R1＝C18H35，m＝5，s1+s2+m*s3＝20，r1+r2+m*r3＝3，R2＝R3＝R4H)177.4 g (0.1 mol) of sodium hydroxide 8.0 g (0.2 mol), sodium 3-chloro-2-hydroxypropanesulfonate 29.5 g (0.15 mol) and 300 ml of toluene/benzene (v/v ═ 1) were mixed in a four-neck flask equipped with mechanical stirrer, thermometer and reflux condenser, heated to 90 ℃ and reacted for 7 hoursThen (c) is performed. Evaporating the solvent to obtain the long-chain polyamine polyether compound1(R1＝C18H35Sodium hydroxypropanesulfonate (R1 + R2+5R3 ═ 3), m ═ 5, s1+ s2+5s3 ═ 20, and R1+ R2+5R3 ═ 32、R3、R4One of them is CH2CH(OH)CH2SO3Na, remainder H).
e. Long-chain polyamine polyether compound1(R1＝C18H35Sodium hydroxypropanesulfonate (R1 + R2+5R3 ═ 3), m ═ 5, s1+ s2+5s3 ═ 20, and R1+ R2+5R3 ═ 32、R3、R4One of them is CH2CH(OH)CH2SO3Na and the balance of H), 120 g of potassium citrate, 100 g of urea and 30 g of biuret are uniformly mixed, 30 g of 1 percent polyacrylamide aqueous solution is added, and the mixture is pressed into a rod shape to prepare the foam drainage rod FS 01.
(2) FS01 was dissolved in deionized water, 100,000mg/L, 200,000mg/L NaCl water, respectively, to make 0.3 wt% foam-drain mother liquor.
The performances of foaming power, foam stability, liquid carrying capacity and the like of the FS01 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 when the FS01 performance was measured, pH was adjusted to 7 and 4 with hydrochloric acid to simulate neutral and acid gas environments, and the results are shown in table 2.
[ example 3 ]
The same as [ example 1 ] except that a long-chain polyamine polyether compound is used1(R1＝C18H35Sodium hydroxypropanesulfonate (R1 + R2+5R3 ═ 3), m ═ 5, s1+ s2+5s3 ═ 20, and R1+ R2+5R3 ═ 32、R3、R4One of them is CH2CH(OH)CH2SO3Na and the balance H)120 g, sodium sulfate 100 g, potassium carbonate 100 g and urea 70 g are mixed evenly, 10 percent polyethylene glycol 60 g is added to mixAfter the polymerization, the mixture was pressed into a stick to obtain a foam drainage stick FS02, and the results are shown in Table 3.
[ example 4 ]
(1) Preparation of foam discharging agent FS 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. 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 the long-chain polyamine polyether compound2(R1＝C16H33，m＝2，s1+s2+2s3＝3，r1+r2+2r3＝2，R2＝R3＝R4H), yield 97.6%.
d. Long-chain polyamine polyether compounds2(R1＝C16H33，m＝2，s1+s2+ms3＝3，r1+r2+mr3＝2，R2＝R3＝R4H)58.9 g (0.1 mol) with 57 g (0.11 mol) of sodium methoxide, 13.4 g (0.11 mol) of 1, 3-propanesultone and 100 ml of cyclopentanone are mixed in a four-neck flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, after the addition, the temperature is raised to reflux reaction for 5 hours, the solvent is evaporated, and ammonia water is added to obtain the long-chain polyamine polyether compound2(R1＝C16H33Ammonium propanesulfonate (R1 + R2+2R3 ═ 2, s1+ s2+2s3 ═ 3, R1+ R2+2R3 ═ 2)2、R3、R4One of them is CH2CH2CH2SO3NH4And the balance is H).
e. Long-chain polyamine polyether compound2(R1＝C16H33Ammonium propanesulfonate (R1 + R2+2R3 ═ 2, s1+ s2+2s3 ═ 3, R1+ R2+2R3 ═ 2)2、R3、R4One of them is CH2CH2CH2SO3NH4And the balance of H)120 g, sodium tartrate 100 g, sodium chloride 70 g and urea 30 g, and adding 10% cellulose aqueous solution 30 g, mixing and pressing into a rod shape to obtain the foam drainage rod FS 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 4.
[ example 5 ]
The same as [ example 4 ] except that in the measurement of FS03 performance, pH was adjusted to 7 and 4 with hydrochloric acid to simulate neutral and acidic gas environments, and aged at 150 ℃ for 72 hours, the results are shown in table 5.
[ example 6 ]
The same as [ example 4 ], except that a long-chain polyamine polyether compound is used2(R1＝C16H33Ammonium propanesulfonate (R1 + R2+2R3 ═ 2, s1+ s2+2s3 ═ 3, R1+ R2+2R3 ═ 2)2、R3、R4One of them is CH2CH2CH2SO3NH4And the balance of H)120 g, sodium tartrate 100 g, sodium bicarbonate 70 g and sodium borate 30 g, and then adding 5% starch aqueous solution 30 g, mixing and pressing into a stick shape to obtain a foam drainage stick FS04, wherein the results are shown in Table 6.
[ example 7 ]
(1) Preparation of foam discharging agent FS 05:
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 compound3(R1＝C22H45，m＝1，s1+s2+s3＝12，r1+r2+r3＝0，R2＝R3＝R4H), yield 98.1%.
d. Long-chain polyamine polyether compounds3(R1＝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 to obtain long-chain polyamine polyetherCompound (I)3(R1＝C22H45Sodium acetate (R) of 1, s1+ s2+ s 3-12, R1+ R2+ R3-02、R3、R4One of them is CH2COOK and the rest is H).
e. Long-chain polyamine polyether compound3(R1＝C22H45Potassium acetate (R) of m 1, s1+ s2+ s 3-12, R1+ R2+ R3-02、R3、R4One of them is CH2COOK and the balance H), 120 g of sodium sulfate, 150 g of sodium tartrate, 100 g of sodium tartrate and 20 g of potassium chloride, adding 60 g of 10% polyethylene glycol, mixing, pressing into a rod shape, and preparing the foam drainage rod FS 05.
(2) The same as [ example 1 ] except that the aging was carried out at 200 ℃ for 24 hours, the results are shown in Table 7.
[ example 8 ]
The same as [ example 7 ] except that in the measurement of FS05 performance, pH was adjusted to 7 and 4 with hydrochloric acid to simulate neutral and acidic gas environments, and aging was performed at 200 ℃ for 24 hours, and the results are shown in table 8.
[ example 9 ]
The same as [ example 7 ], except that a long-chain polyamine polyether compound is used3(R1＝C22H45Potassium acetate (R) of m 1, s1+ s2+ s 3-12, R1+ R2+ R3-02、R3、R4One of them is CH2COOK and the balance of H), 120 g of sodium sulfate, 100 g of sodium sulfate, 50 g of potassium carbonate, 30 g of sodium borate and 30 g of biuret, adding 30 g of 5% dextrin water solution, mixing, pressing into a rod shape, and obtaining the foam drainage rod FS06, wherein the results are shown in Table 9.
[ example 10 ]
(1) Preparation of foam discharging agent FS 07:
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) under stirring, reacting at the reaction temperature of 120-160 ℃ for 8 hours, and collecting methanol generated by the reaction to obtain the required acylAmine 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 the solvent to obtain the long-chain polyamine polyether compound4(R1＝C20H31Sodium ethanesulfonate (R) of m 1, s1+ s2+ s 30, R1+ R2+ R3 92、R3、R4One of them is CH2CH2SO3Na，The balance being H).
e. Long-chain polyamine polyether compound4(R1＝C20H31M is 1, s1+ s2+ s3 is 0, r1+ r2+ r3 is 9), potassium phthalate 50 g and biuret 100 g are mixed with 5% polyethylene glycol solution 30 g and then pressed into a rod shape, thus obtaining the foam drainage rod FS 07.
(2) The results are shown in Table 10, as in example 1.
[ example 11 ]
The same as [ example 10 ] except that when the FS07 performance 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 11.
[ example 12 ]
The same as [ example 10 ] except that a long-chain polyamine polyether compound is used4(R1＝C20H31M 1, s1+ s2+ s3 is 0, r1+ r2+ r3 is 9), 120 g of sodium ethanesulfonate, 100 g of potassium citrate, 50 g of urea, 30 g of potassium carbonate and 60 g of sodium acetate are uniformly mixed, 30 g of a 1% polyacrylamide aqueous solution is added, the mixture is mixed and then pressed into a stick shape, and a foam drainage stick FS08 is prepared, and the results are shown in Table 12.
[ COMPARATIVE EXAMPLE 1 ]
The same as [ example 1 ], except that C is used17H33CO(NHCH2CH2)5NH2Substituted long-chain polyamine polyether compounds1(R1＝C18H35Sodium hydroxypropanesulfonate (R1 + R2+5R3 ═ 3), m ═ 5, s1+ s2+5s3 ═ 20, and R1+ R2+5R3 ═ 32、R3、R4One of them is CH2CH(OH)CH2SO3Na, balance H) produced foam drainage stick FS09 with simulated water of 100,000mg/LNaCl, the results of which are shown in Table 13.
[ COMPARATIVE EXAMPLE 2 ]
The same as in comparative example 1, except that when the FS09 performance was measured, pH was adjusted to 7 and 4 with hydrochloric acid to simulate neutral and acid gas environments, and the results are shown in table 14.
[ COMPARATIVE EXAMPLE 3 ]
The same as [ example 4 ], except thatC15H31CO(NHCH2CH2)2NH2Substituted long-chain polyamine polyether compounds2(R1＝C16H33Ammonium propanesulfonate (R1 + R2+2R3 ═ 2, s1+ s2+2s3 ═ 3, R1+ R2+2R3 ═ 2)2、R3、R4One of them is CH2CH2CH2SO3NH4And the remainder H) produced foam drainage stick FS10 with simulated water of 100,000mg/LNaCl, the results of which are shown in Table 13.
[ COMPARATIVE EXAMPLE 4 ]
The same as [ example 7 ], except that C is used21H43CONHCH2CH2NH2Substituted long-chain polyamine polyether compounds3(R1＝C22H45Potassium acetate (R) of m 1, s1+ s2+ s 3-12, R1+ R2+ R3-02、R3、R4One of them is CH2COOK, remainder H) produced foam drainage sticks FS11 with simulated water of 100,000mg/LNaCl, the results are shown in Table 13.
[ COMPARATIVE EXAMPLE 5 ]
The same as [ example 10 ], except that C is used19H29CONHCH2CH2NH2Substituted long-chain polyamine polyether compounds4(R1＝C20H31M 1, s1+ s2+ s 3-0, r1+ r2+ r 3-9) was used to make foam drainage bars FS12 with simulated water of 100,000mg/LNaCl, the results are shown in table 13.
[ COMPARATIVE EXAMPLE 6 ]
The same as in comparative example 5, except that the FS12 performance was measured, the pH was adjusted to 2 with hydrochloric acid to simulate a high acid gas containing atmosphere, and the results are shown in Table 14.
[ COMPARATIVE EXAMPLE 7 ]
The same as comparative example 1 except that oleyl alcohol polyoxyethylene ether hydroxypropyl sodium sulfonate C was used18H35O(C2H4O)3CH2CH(OH)CH2SO3Na (F09) substituted long-chain polyamine polyether compound1(R1＝C18H35，m＝5，s1+s2+5s3＝20，r1+r2+5r3＝3) Sodium hydroxypropanesulfonate (R)2、R3、R4One of them is CH2CH(OH)CH2SO3Na, balance H) produced foam drainage stick FS13 with simulated water of 100,000mg/LNaCl, the results of which are shown in Table 13.
The same as comparative example 2 except that oleyl alcohol polyoxyethylene ether hydroxypropyl sodium sulfonate C was used18H35O(C2H4O)3CH2CH(OH)CH2SO3Na (F09) substituted long-chain polyamine polyether compound1(R1＝C18H35Sodium hydroxypropanesulfonate (R1 + R2+5R3 ═ 3), m ═ 5, s1+ s2+5s3 ═ 20, and R1+ R2+5R3 ═ 32、R3、R4One of them is CH2CH(OH)CH2SO3Na, balance H) produced foam drainage stick FS13 with simulated water of 100,000mg/LNaCl, the results of which are shown in Table 14.
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
TABLE 14
Claims (11)
1. The solid foam drainage agent comprises the following components in parts by weight:
(1)1 part of a long-chain polyamine compound;
(2) 0.05-1000 parts of solid filler;
(3) 0-0.5 parts of adhesive;
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、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 solid foam drainage agent of claim 1, wherein R is1Is C8～C24Hydrocarbyl or substituted hydrocarbyl; r2、R3、R4Independently selected from H, CH2COOM、(CH2)3SO3M or CH2(CHOH)CH2SO3One of M is not H at the same time; 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.
3. The solid foam drainage agent of claim 2, wherein M is hydrogen, an alkali metal, or a compound of formula NR5(R6(R7)(R8) One of the groups shown, R5、R6、R7、R8Independently 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.
4. The solid foam drainage agent of claim 1, wherein the solid filler is at least one of carbonate, bicarbonate, sulfate, phosphate, borate, metal halide, formate, acetate, tartaric acid and salts, citric acid and salts, phthalic acid and salts, gallic acid and salts, urea, biuret; the adhesive is at least one of dextrin, epoxy resin, polyacrylamide, starch, cellulose and polyethylene glycol.
5. The solid foam drainage agent of claim 4, wherein the solid filler is at least one of sodium carbonate, sodium bicarbonate, sodium borate, sodium chloride, sodium acetate, tartaric acid, sodium tartrate, citric acid, sodium citrate, potassium phthalate, urea, biuret; the adhesive is at least one of polyacrylamide, starch and polyethylene glycol.
6. The solid foam drainage agent according to claim 1, wherein the mass ratio of the long-chain polyamine compound, the solid filler and the binder is 1: (0.1-200): (0.01-0.1).
7. The method for preparing the solid foam drainage agent according to any one 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 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 1-5, 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 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)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 the reaction temperature of 50-120 ℃ for 3-20 hours to generate a long-chain polyamine compound shown in the structural formula (1); the ionizing agent is selected from XR9Y1Or X R'9Y′1At least one of; the base is selected from alkali metal hydroxide or alkali metal alkoxide; y is1And Y'1Is SO3M1Or COON1，M1And N1Is an alkali metal, and X is chlorine, bromine or iodine;
(2) and (2) uniformly mixing the long-chain polyamine compound synthesized in the step (1), the solid filler and the adhesive according to the required mass parts, and then pressing and forming to prepare the solid foam drainage agent.
8. The method of claim 7, 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.
9. The method of claim 7, wherein the step H is performed in the step b-Y+Is LiAlH4、LiAlH(OEt)3Or NaBH4Wherein the aprotic solvent is at least one of diethyl ether, tetrahydrofuran and dioxane.
10. The method of claim 7, wherein the long-chain polyamine polyether intermediate of step d: ionizing agent: the molar ratio of the alkali is 1 to (1-2) to (1-4), and the solvent is selected from C3～C8Ketone and C6～C9At least one aromatic hydrocarbon of (1).
11. The application of the solid foam drainage agent as claimed in any one of claims 1 to 6 in drainage and gas production of acidic high-temperature high-salt ultra-deep gas wells.
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