CN109679621B

CN109679621B - High-temperature-resistant high-salt solid foam drainage agent, and preparation method and application thereof

Info

Publication number: CN109679621B
Application number: CN201710970093.4A
Authority: CN
Inventors: 沈之芹; 李应成; 裘鋆; 李斌
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2017-10-18
Filing date: 2017-10-18
Publication date: 2021-05-11
Anticipated expiration: 2037-10-18
Also published as: CN109679621A

Abstract

The invention relates to high-temperature-resistant high-salt solid foam drainageThe agent, the preparation method and the application mainly solve the problem that the prior foam water discharging agent contains H₂S、CO₂The high-temperature and high-salt resistance performance in an acidic environment is poor, and the problems of yield reduction, even spray stopping and difficult filling of the liquid foam discharging agent 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)1 part of polyamine surfactant; 2) 0.01-100 parts of cosurfactant; 3) 0.05-1000 parts of solid filler; 4) 0-0.5 parts of adhesive; wherein the polyamine surfactant has a general molecular formula shown in formula 1); the cosurfactant has at least one of the molecular general formula shown in the formula 2) or the molecular general formula shown in the formula 3), better solves the problem, and can be used for drainage gas recovery of acidic high-temperature high-salt ultra-deep gas wells.

Description

High-temperature-resistant high-salt solid foam drainage agent, and preparation method and application thereof

Technical Field

The invention relates to a solid foam drainage agent, a preparation method and application thereof, in particular to a high-temperature-resistant high-salt solid 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 water discharging 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 of a liquid foam water discharging agent, and provides a high-temperature and high-salt resistant solid foam water discharging agent which is applied to a high-temperature deep well, has very excellent temperature resistance under an acid 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 and high salt resistant solid foam drainage agent corresponding to the first technical problem.

The invention also provides an application of the high-temperature and high-salt resistant solid foam drainage agent corresponding to the solution of the technical problem.

In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: the solid foam drainage agent comprises the following components in parts by mass:

1)1 part of polyamine surfactant;

2) 0.01-100 parts of cosurfactant;

3) 0.05-1000 parts of solid filler;

4) 0-0.5 parts of adhesive;

wherein, the molecular general formula of the polyamine surfactant is shown as a 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 ^-、OSO₃ ^-One of (1); m is the number of the vinylamine fragments, and m is any integer of 1-10; t1 and t2 are positive charges, s1 and 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 cosurfactant is preferably at least one selected from a zwitterionic surfactant, a cationic surfactant and an anionic surfactant; the zwitterionic or cationic surfactant preferably has a general molecular formula shown in formula (2):

in the formula (2), R₇Is selected from C₄～C₃₂One of hydrocarbyl or substituted hydrocarbyl, R₈、R₉Independently selected from (CH)₂)_aOH、(CH₂)_bCH₃Or C₆H₅CH₂One of (1), R₁₀Is selected from (CH)₂)_aOH、(CH₂)_bCH₃、C₆H₅CH₂、(CH₂)_cOr (CH)₂)_c(CHOH)_d(CH₂)_eWherein a is any integer from 2 to 4, b is any integer from 0 to 5, c is any integer from 1 to 4, d is any integer from 0 to 3, and e is any integer from 1 to 4; n is the addition number of propoxy groups PO, and n is 0-15; p is the addition number of an ethoxy group EO, and p is 0-30; x^-Is selected from OH^-Halogen anion, HCO₃ ^-、NO₃ ^-、CH₃OSO₃ ^-、CH₃COO^-、COO^-、SO₃ ^-Or OSO₃ ^-One of (1);

the anionic surfactant has a general molecular formula shown in formula (3):

in the formula (3), R₁₁And R₁₂The sum is selected from C₃～C₃₁One of hydrocarbyl or substituted hydrocarbyl, M is selected from hydrogen, alkali metal or of the formula NR₁₃(R₁₄)(R₁₅)(R₁₆) At least one of the groups shown, R₁₃、R₁₄、R₁₅、R₁₆Is 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.

In the above technical scheme, R₁、R₇Independently is preferably 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, and b is preferably 0 to 2.

In the above technical scheme, R₅、R₆Independently is preferably (CH)₂)_cOr (CH)₂)_c(CHOH)_d(CH₂)_eOne kind of (1).

In the above-mentioned embodiments, c is preferably 1 or 2, d is preferably 0 or 1, and e is preferably 1 or 2.

In the above technical scheme, R₈、R₉Independently is preferably CH₃、C₂H₅、(CH₂)₂OH or C₆H₅CH₂One kind of (1).

In the above technical scheme, R₁₀Preferably CH₃、C₂H₅、(CH₂)₂OH or C₆H₅CH₂One of (1); or R₈X^-Preferably CH₂COO^-、(CH₂)₃SO₃ ^-、CH₂(CHOH)CH₂SO₃ ^-One kind of (1).

In the above technical scheme, R₁₁And R₁₂The sum is preferably C₇～C₂₃Hydrocarbyl or substituted hydrocarbyl.

In the above embodiments, M is independently preferably hydrogen, an alkali metal or a compound of formula NR₁₃(R₁₄)(R₁₅)(R₁₆) At least one of the groups shown.

In the above technical scheme, R₁₃、R₁₄、R₁₅、R₁₆Independently preferably H, (CH)₂)_aOH or(CH₂)_bCH₃One kind of (1).

In the above technical scheme, Y₁、Y₂Preferably COO^-Or SO₃ ^-One kind of (1).

In the above-mentioned technical means, m is preferably 1 to 5.

In the technical scheme, n is preferably 0-5; p is 0 to 5.

In the above technical solution, the solid filler is preferably at least one of inorganic oxysalt, metal halide, organic carboxylic acid and/or salt thereof, urea, biuret, and the like; further preferably, the inorganic oxysalt is a carbonate, a bicarbonate, a sulfate, a phosphate, a borate; the organic carboxylic acid and/or salt thereof is preferably formate, acetate, tartaric acid and/or salt thereof, citric acid and/or salt thereof, phthalic acid and/or salt thereof, gallic acid and/or salt thereof; still more preferably, 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, 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 polyamine surfactant, the cosurfactant, the solid filler and the adhesive in the solid foam drainage agent is preferably 1 to (0.1-10): (0.1-200): (0.01-0.1).

The high temperature and high salt resistant solid foam drainage agent of the present invention can be obtained by mixing the polyamine surfactant, the co-surfactant, the solid filler and the binder in a desired ratio, and is 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 the high temperature and high salt resistant solid foam drainage agent to solve one of the technical problems, comprising the following steps:

(1) preparation of polyamine surfactant:

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 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), and the polyamine surfactant is obtained; the short carbon chain alcohol is selected from C₁～C₅Hydrocarbyl or substituted hydrocarbylAn alcohol; 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 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, so as to obtain the polyamine surfactant; 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%;

(2) uniformly mixing the polyamine surfactant, the cosurfactant, the solid filler and the adhesive synthesized in the step (1) according to the required mass parts, and then pressing and molding to prepare the solid foam drainage

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 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 above technical scheme, the molar ratio of the tertiary amine nonionic surfactant to the ionizing agent in step d is 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 R₆Y₂Examples 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 high-salt 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 high-temperature-resistant high-salt solid foam water-discharging agent in the technical scheme in water discharging and gas production of a gas well.

In the above technical scheme, the application of the high temperature and high salt resistant solid foam drainage agent is not particularly limited, and those skilled in the art can use the high temperature and high salt resistant solid foam drainage agentThe method is applied according to the existing drainage gas production process technology, for example, but not limited to, the optimal selection of an acidic high-temperature high-salt ultra-deep gas well and a high-temperature acid gas-containing gas reservoir is carried out, the stratum temperature is 150-200 ℃, the total salinity of stratum brine is 500-200000 mg/L, and H is₂S and CO₂The content of (A) is 0-35%.

The polyamine surfactant 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 high-salt solid foam drainage agent, a preparation method and application thereof in drainage and gas production.

The thermal decomposition temperature of the polyamine surfactant prepared by the invention is 200 ℃ or above, the polyamine surfactant can not be hydrolyzed or can be hydrolyzed in trace amount in an acidic aqueous solution, and the polyamine surfactant 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 key effective components of the foam discharging agent, the solid filler and the adhesive have good compatibility, and the formed solid composition does not influence the foam discharging performance.

In the present invention, the content or concentration of the foam discharging agent refers to the total content or total concentration of the components 1) and 2) in the above 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 0.02-0.12% of the foam drainage agent is in 0-200,000 mg/L salinity brine and does not contain kerosene, the foaming height reaches 170mm before and after high-temperature aging, the liquid carrying rate reaches 93.9%, when 0.12% of the foam drainage agent is in 100,000mg/L salinity brine and contains 10-30 wt% of kerosene, the foaming height reaches 153mm, the liquid carrying rate reaches 88.5%, the foam drainage agent has excellent temperature resistance, salt resistance and oil resistance in an acid environment, and 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 HFS01

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＝CH₃，t1＝t2＝s1＝s2＝0)。

d. Reacting a polyamine compound1(R₁＝C₁₈H₃₅，m＝5，R₂＝R₃＝R₄＝CH₃T1 ═ t2 ═ s1 ═ s2 ═ 0) of 60 g of sodium hydroxypropanesulfonate product, C₁₆H₃₃SO₃Na 60 g, sodium sulfate 150 g, sodium tartrate 50 g and potassium chloride 70 g are evenly mixed, 10 percent of polyethylene glycol 50 g is added for mixing and then the mixture is pressed into a rod shape, thus obtaining the foam drainage rod HFS 01.

(2) HFS01 was dissolved in deionized water, 100,000mg/L, 200,000mg/L NaCl water, respectively, to make 0.3 wt% foam-remover stock solution.

The performances of foaming power, foam stability, liquid carrying capacity and the like of the HFS01 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 HFS01 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 hydroxyl groupsSodium propyl sulfonate product.

e. Reacting a polyamine compound1(R₁＝C₁₈H₃₅，m＝5，R₂＝R₃＝R₄＝CH₃50 g of sodium hydroxypropanesulfonate product t1 ═ t2 ═ s1 ═ s2 ═ 0), C₁₆H₃₃OC₂H₄N⁺(CH₃)₃Br^-40 g, C₁₆H₃₃SO₃K10 g, sodium sulfate 150 g, sodium tartrate 50 g and potassium chloride 70 g are evenly mixed, 10 percent of polyethylene glycol 50 g is added for mixing and then the mixture is pressed into a rod shape, thus obtaining the foam drainage rod HFS 02.

[ example 4 ]

The same as [ example 1 ] except that in the measurement of HFS02 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 4.

[ example 5 ]

(1) Preparation of foam discharging agent HFS 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＝C₂H₅，t1＝t2＝s1＝s2＝0)。

d. Reacting a polyamine compound2(R₁＝C₁₆H₃₃，m＝2，R₂＝R₃＝R₄＝C₂H₅T1 ═ t2 ═ s1 ═ s2 ═ 0)15 g, C₂₂H₄₅OC₂H₄N⁺(CH₂CH₂OH)₂(CH₃)CH₂COO^-90g internal olefin sulfonate IOS (C)_19～23)30 g of potassium phthalate, 30 g of sodium borate, 100 g of biuret and 30 g of 5 percent polyethylene glycol solution are mixed and pressed into a rod shape to prepare the foam drainage rod HFS 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 5.

[ example 6 ]

The same as [ example 5 ] except that in the measurement of HFS03 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 6.

[ example 7 ]

(1) Preparation of foam discharging agent HFS 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 behenic acid methyl ester 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 compoundSubstance 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).

e. Reacting a polyamine compound3(R₁＝C₂₂H₄₅，m＝1，R₂＝R₃＝R₄＝C₂H₄OH, t1 ═ t2 ═ s1 ═ s2 ═ 0), 90g of potassium acetate product, C₁₆H₃₃OC₂H₄N⁺(CH₃)₂CH₂COO^-20 g of potassium citrate, 50 g of potassium citrate, 200 g of urea, 20 g of potassium carbonate and 20 g of sodium acetate are uniformly mixed, 30 g of 1% polyacrylamide aqueous solution is added, and the mixture is pressed into a rod shape to prepare the foam drainage rod HFS 04.

(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 HFS04 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 8.

[ example 9 ]

(1) Preparation of foam discharging agent HFS 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 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 38.7 g (0.1 mol) of C at-10-5 DEG C₁₉H₂₉CO(NHCH₂CH₂)₂NH₂The 40 wt% dioxane solution is added dropwise and slowly heated to about 30 ℃ for reaction for 6 hoursThen (c) is performed. 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＝CH₃，t1＝t2＝s1＝s2＝0)。

d. Reacting a polyamine compound4(R₁＝C₂₀H₃₁，m＝2，，R₂＝R₃＝R₄＝CH₃T1 ═ t2 ═ s1 ═ s2 ═ 0)100 g, C₂₂H₄₅O(C₂H₄O)₂C₂H₄N⁺(CH₃)₂CH₂COO^-10 g of a-olefin sulfonate AOS (C)_14～18)5 g of potassium phthalate, 30 g of potassium phthalate, 50 g of sodium borate, 100 g of biuret and 30 g of 5 percent polyethylene glycol solution are mixed and pressed into a rod shape to prepare the foam drainage rod HFS 05.

(2) The results are shown in Table 9, as in example 1.

[ example 10 ]

The same as [ example 9 ] except that in the measurement of HFS05 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 10.

[ example 11 ]

The difference is that 10 wt% is added when the HFS 01-05 performances are measured, as in example 1, 30 wt% kerosene, simulated water 100,000mg/LNaCl, and the results are shown in Table 11.

[ COMPARATIVE EXAMPLE 1 ]

The same as [ example 1 ] except that polyamine compounds are used1(R₁＝C₁₈H₃₅，m＝5，R₂＝R₃＝R₄＝CH₃T1 ═ t2 ═ s1 ═ s2 ═ 0)100 g, C₁₆H₃₃SO₃K100 g substituted polyamine compounds1(R₁＝C₁₈H₃₅，m＝5，R₂＝R₃＝R₄＝CH₃T1 ═ t2 ═ s1 ═ s2 ═ 0)50 g, C₁₆H₃₃SO₃Na 50 g ", other additives unchanged, formed foam drainage bars HFS06 and HFS07, simulated water at 100,000mg/LNaCl, and the results are shown in Table 12.

[ COMPARATIVE EXAMPLE 2 ]

The same as [ example 3 ] except that polyamine compounds are used1(R₁＝C₁₈H₃₅，m＝5，R₂＝R₃＝R₄＝CH₃100 g of sodium hydroxypropanesulfonate product t1 ═ t2 ═ s1 ═ s2 ═ 0), C₁₆H₃₃OC₂H₄N⁺(CH₃)₃Br^-100 g of substituted polyamine compounds1(R₁＝C₁₈H₃₅，m＝5，R₂＝R₃＝R₄＝CH₃50 g of sodium hydroxypropanesulfonate product t1 ═ t2 ═ s1 ═ s2 ═ 0), C₁₆H₃₃OC₂H₄N⁺(CH₃)₃Br^-40 g, C₁₆H₃₃SO₃K10 g ", other additives were unchanged to form foam drainage bars HFS08 and HFS09 with simulated water of 100,000mg/LNaCl, and the results are shown in Table 12. [ COMPARATIVE EXAMPLE 3 ]

The same as [ example 5 ] except that polyamine compounds are used2(R₁＝C₁₆H₃₃，m＝2，R₂＝R₃＝R₄＝C₂H₅T1 ═ t2 ═ s1 ═ s2 ═ 0)135 g, C₂₂H₄₅OC₂H₄N⁺(CH₂CH₂OH)₂(CH₃)CH₂COO^-135 g internal olefin sulfonate IOS (C)_19～23)135 g of substituted polyamine compounds2(R₁＝C₁₆H₃₃，m＝2，R₂＝R₃＝R₄＝C₂H₅T1 ═ t2 ═ s1 ═ s2 ═ 0)15 g, C₂₂H₄₅OC₂H₄N⁺(CH₂CH₂OH)₂(CH₃)CH₂COO^-90g internal olefin sulfonate IOS (C)_19～23)30 g "of other additives, foam drainage bars HFS10, HFS11 and HFS12 were formed, with simulated water of 100,000mg/LNaCl, and the results are shown in Table 12.

[ COMPARATIVE EXAMPLE 4 ]

The same as [ example 7 ] except that polyamine compounds are used3(R₁＝C₂₂H₄₅，m＝1，R₂＝R₃＝R₄＝C₂H₄OH, t1 ═ t2 ═ s1 ═ s2 ═ 0), 110 g of potassium acetate product, C₁₆H₃₃OC₂H₄N⁺(CH₃)₂CH₂COO^-110 g substituted polyamine compound3(R₁＝C₂₂H₄₅，m＝1，R₂＝R₃＝R₄＝C₂H₄OH, t1 ═ t2 ═ s1 ═ s2 ═ 0), 90g of the potassium acetate product, C₁₆H₃₃OC₂H₄N⁺(CH₃)₂CH₂COO^-20 g ", other additives unchanged, foam drainage bars HFS13 and HFS14 were formed, with simulated water at 100,000mg/LNaCl, and the results are shown in Table 12.

[ COMPARATIVE EXAMPLE 5 ]

The same as [ example 9 ], except that C is added₂₂H₄₅O(C₂H₄O)₂C₂H₄N⁺(CH₃)₂CH₂COO^-115 g of a polyamine compound4(R₁＝C₂₀H₃₁，m＝2，R₂＝R₃＝R₄＝CH₃，t1＝t2＝s1＝s2 ═ 0)115 g, a-olefin sulfonate AOS (C)_14～18)115 g of substituted polyamine compounds4(R₁＝C₂₀H₃₁，m＝2，R₂＝R₃＝R₄＝CH₃T1 ═ t2 ═ s1 ═ s2 ═ 0)100 g, C₂₂H₄₅O(C₂H₄O)₂C₂H₄N⁺(CH₃)₂CH₂COO^-10 g of a-olefin sulfonate AOS (C)_14～18)5 g ", other additives unchanged, foam drainage bars HFS15, HFS16 and HFS17 were formed, with simulated water of 100,000mg/LNaCl, and the results are shown in Table 12.

[ COMPARATIVE EXAMPLE 6 ]

The same as [ example 1 ], except that "C" is used₁₇H₃₃CO(NHCH₂CH₂)₅NH₂50 g, C₁₆H₃₃SO₃Na 50 g 'substituted' polyamine compounds1(R₁＝C₁₈H₃₅，m＝5，R₂＝R₃＝R₄＝CH₃T1 ═ t2 ═ s1 ═ s2 ═ 0)50 g, C₁₆H₃₃SO₃Na 50 g ", other additives unchanged, formed foam drainage bar HFS18, simulated water at 100,000mg/LNaCl, and the results are shown in Table 12.

[ COMPARATIVE EXAMPLE 7 ]

The same as in comparative example 1, except that the 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 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

1. The solid foam drainage agent comprises the following components in parts by mass:

1)1 part of polyamine surfactant;

2) 0.01-100 parts of cosurfactant;

3) 0.05-1000 parts of solid filler;

4) 0-0.5 parts of adhesive;

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 ^-、Y₂ ^-Independently 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 and t2 are positive charges, s1 and s2 are R₅Y₁ ^-、R₆Y₂ ^-The number of the substituents, t1 ═ s1 ═ 0 or 1, t2 ═ s2 ═ 0 or 1;

the cosurfactant is at least one of a zwitterionic surfactant, a cationic surfactant and an anionic surfactant; the zwitterionic or cationic surfactant has a general molecular formula shown in formula (2):

in the formula (2), R₇Is selected from C₄～C₃₂One of hydrocarbyl or substituted hydrocarbyl, R₈、R₉Independently selected from (CH)₂)_aOH、(CH₂)_bCH₃Or C₆H₅CH₂One of (1), R₁₀Is selected from (CH)₂)_aOH、(CH₂)_bCH₃、C₆H₅CH₂、(CH₂)_cOr (CH)₂)_c(CHOH)_d(CH₂)_eWherein a is any integer from 2 to 4, b is any integer from 0 to 5, c is any integer from 1 to 4, d is any integer from 0 to 3, and e is any integer from 1 to 4; n is the addition number of propoxy groups PO, and n is 0-15; p is the addition number of an ethoxy group EO, and p is 0-30; x^-Is selected from OH^-Halogen anion, HCO₃-、NO₃ ^-、CH₃OSO₃ ^-、CH₃COO^-、COO^-、SO₃ ^-Or OSO₃ ^-One of (1);

the anionic surfactant has a general molecular formula shown in formula (3):

in the formula (3), R₁₁And R₁₂The sum is selected from C₃～C₃₁One of hydrocarbyl or substituted hydrocarbyl, M is selected from hydrogen, alkali metal or of the formula NR₁₃(R₁₄)(R₁₅)(R₁₆) At least one of the groupsA, R₁₃、R₁₄、R₁₅、R₁₆Is independently selected from H, (CH)₂)_aOH or (CH)₂)_bCH₃Wherein a is any integer of 2-4, b is any integer of 0-5;

the solid filler is at least one of inorganic oxysalt, metal halide, organic carboxylic acid and/or salt thereof, urea, biuret and the like.

2. The solid foam drainage agent of claim 1, wherein R is₁、R₇Is independently selected from C₈～C₂₄Hydrocarbyl or substituted hydrocarbyl; r₁₁And R₁₂The sum of C₇～C₂₃Hydrocarbyl or substituted hydrocarbyl; r₂、R₃、R₄Independently selected from (CH)₂)_aOH or (CH)₂)_bCH₃Wherein a is any integer from 2 to 4, and b is any integer from 0 to 4; r₅、R₆Independently selected from (CH)₂)_cOr (CH)₂)_c(CHOH)_d(CH₂)_eC is any integer of 1-2, d is any integer of 0-1, and e is any integer of 1-2; r₈、R₉Is independently selected from CH₃、C₂H₅、(CH₂)₂OH or C₆H₅CH₂One of (1); r₁₀Is CH₃、C₂H₅、(CH₂)₂OH、C₆H₅CH₂Or R is₁₀X^-Is CH₂COO^-、(CH₂)₃SO₃ ^-、CH₂(CHOH)CH₂SO₃ ^-One of (1); y is₁ ^-、Y₂ ^-Independently selected from COO^-、SO₃ ^-One of (1); m is 1 to 5, n is 0 to 5, and p is 0 to 5.

3. The solid foam drainage agent of claim 1, wherein the binder is at least one of dextrin, epoxy resin, polyacrylamide, starch, cellulose, polyethylene glycol.

4. The solid foam drainage agent of claim 1, wherein the inorganic oxysalt is a carbonate, bicarbonate, sulfate, phosphate, borate; the organic carboxylic acid and/or salt thereof is formate, acetate, tartaric acid and/or salt thereof, citric acid and/or salt thereof, phthalic acid and/or salt thereof, and gallic acid and/or salt thereof.

5. The solid foam drainage agent of claim 1, 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.

6. The solid foam drainage agent of claim 3, wherein the binder is at least one of polyacrylamide, starch, and polyethylene glycol.

7. The solid foam drainage agent according to claim 1, wherein the mass ratio of the polyamine surfactant, the cosurfactant, the solid filler and the binder is 1 to (0.1-10): (0.1-200): (0.01-0.1).

8. A method for preparing the solid foam drainage agent of any one of claims 1 to 7, comprising the steps of:

(1) preparation of polyamine surfactant:

a. amidation reaction:

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), and the polyamine surfactant is obtained; 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：H₂In a molar ratio of 1: (3-20): (5-40);

d. quaternization reaction:

step c yields s 1-t 1-s 2T 2-0 tertiary amine nonionic surfactant to ionizing agent in a molar ratio of 1: (1-5) reacting in a short carbon chain alcohol aqueous solution at 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, so as to obtain the polyamine surfactant; the ionizing agent is selected from XR₅Y₁M or XR₆ Y₂N, wherein M and N are independently selected from one of alkali metals, and X is one of chlorine, bromine or iodine;

(2) and (2) uniformly mixing the polyamine surfactant synthesized in the step (1), the cosurfactant, the solid filler and the adhesive according to the required parts by mass, and then pressing and forming to prepare the solid foam drainage agent.

9. The method for preparing a solid foam drainage agent according to claim 8, wherein R in the 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.

10. The method for preparing a solid foam drainage agent according to claim 8, 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.

11. The method for preparing a solid foam drainage agent according to claim 8, 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 (B) is 1 to (4-10) to (5-20); the tertiary amine nonionic surfactant in the 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.

12. Use of the solid foam drainage agent of any one of claims 1 to 7 in drainage and gas production of a gas well.