CN109679614B

CN109679614B - Method for water drainage and gas recovery by adopting high-temperature-resistant acid-resistant solid foam drainage agent

Info

Publication number: CN109679614B
Application number: CN201710969689.2A
Authority: CN
Inventors: 沈之芹; 吴春芳; 翟晓东; 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: CN109679614A

Abstract

The invention relates to a drainage method by adopting a high-temperature-resistant and acid-resistant solid foam drainage agentThe method of gas mainly solves 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 adopts the following steps: 1) mixing the solid foam drainage agent composition with water to obtain a foam drainage agent solution; 2) fully contacting a foam drainage agent solution or a mixed solution of the foam drainage agent solution and oil with gas to form a foam fluid, and displacing water or an oil-water mixture in the foam drainage agent solution; wherein the solid foam discharging agent composition comprises: the technical scheme of 1 part of polyamine surfactant shown in the formula (1), 0.05-1000 parts of solid filler and 0-0.5 part of adhesive well solves the problem and can be used for drainage and gas production of acidic high-temperature high-salt ultra-deep gas wells.

Description

Method for water drainage and gas recovery by adopting high-temperature-resistant acid-resistant solid foam drainage agent

Technical Field

The invention relates to a method for drainage and gas recovery by adopting a solid foam drainage agent, in particular to a method for drainage and gas recovery by adopting a high-temperature-resistant and acid-resistant solid foam drainage agent.

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 solid 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 of a liquid foam drainage agent, and provides a method for drainage and gas recovery by adopting the solid foam drainage agent.

In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: the method for drainage and gas production by adopting the solid foam drainage agent comprises the following steps:

(1) mixing the solid foam drainage agent composition with water to obtain a foam drainage agent solution;

(2) fully contacting a foam drainage agent solution or a mixed solution of the foam drainage agent solution and oil with gas to form a foam fluid, and displacing water or an oil-water mixture in the foam drainage agent solution;

the solid foam drainage agent comprises the following components in parts by weight:

1)1 part of polyamine surfactant;

2) 0.05-1000 parts of solid filler;

3) 0-0.5 parts of adhesive;

wherein the polyamine surfactant 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、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,s2 is R₅Y₁ ^-、R₆Y₂ ^-The number of the substituents, t1 ═ s1 ═ 0 or 1, t2 ═ s2 ═ 0 or 1; the gas is at least one of air, nitrogen, methane or natural gas, and may or may not contain H₂S or CO₂An acid gas; the oil is at least one of kerosene, crude oil or condensate oil.

In the above technical scheme, R₁Preferably C₈～C₂₄Hydrocarbyl or substituted hydrocarbyl.

In the above technical scheme, R₂、R₃、R₄Is 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.

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, Y₁、Y₂Independently 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 solid filler is preferably at least one of inorganic oxysalt, metal halide, organic carboxylic acid and salt thereof, urea, and biuret; the adhesive is at least one of dextrin, epoxy resin, polyacrylamide, starch, cellulose, polyethylene glycol and the like; further preferably, the inorganic oxysalt is carbonate, bicarbonate, sulfate, phosphate, borate, the organic carboxylic acid and the salt thereof is formate, acetate, tartaric acid and the salt thereof, citric acid and the salt thereof, phthalic acid and the salt thereof, gallic acid and the salt thereof; still more preferably: the solid filler is 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; the binder is preferably at least one of polyacrylamide, starch and polyethylene glycol. In the technical scheme, the mass ratio of the polyamine surfactant, the solid filler and the adhesive in the solid foam drainage agent is 1: (0.1-200): (0.01-0.1).

In the above technical solution, the gas is preferably at least one of nitrogen, methane or natural gas.

In the above technical scheme, H in the gas₂S and CO₂The content of (b) is preferably 15 to 35%.

In the above technical solution, the oil is preferably at least one of kerosene and condensate.

The key effective component of the solid foam discharging agent composition is 1), and the solid foam discharging agent composition can be obtained by mixing the polyamine surfactant, the solid filler and the adhesive according to the required proportion, and is preferably obtained by the following technical scheme.

In the above technical solution, the preparation method of the high temperature resistant and acid resistant solid foam drainage agent preferably includes the following steps:

(1) preparation of polyamine surfactants

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 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 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 R₆ Y₂N, 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) and (2) uniformly mixing the polyamine surfactant synthesized in the step (1), 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.

In the above-described aspect, the solid foam drainage agent composition may have a shape of a bar, a ball, or the like.

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 solution, the mole ratio of the tertiary amine nonionic surfactant to the ionizing agent in step d is preferably 1: (1-1.5).

In the above technical scheme, the solvent in the step d is preferably selected from C₃～C₈Ketone and C₆～C₉At least one aromatic hydrocarbon of (a), e.g. at least one member of the group consisting of acetone, butanone, pentanone, benzene, toluene or xylene, trimethylbenzene, ethylbenzene and diethylbenzeneOne kind of the medicine.

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 solid foam drainage agent has good compatibility, and can also contain other treating agents commonly used in the field.

In the technical scheme, the application environment of the method for water drainage and gas production by using the solid foam drainage agent is not particularly limited, for example, but not limited to, the method is preferably used for acidic high-temperature high-salt ultra-deep gas wells and high-temperature acid gas-containing gas reservoirs, for example, the formation temperature is 150-200 ℃, the total salinity of formation 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 solid foam drainage agent to the maximum extent. The invention relates to a method for drainage and gas recovery by adopting a high-temperature-resistant and acid-resistant solid foam drainage agent.

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.

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.

The method for liquid drainage and gas production can also comprise methods such as gas lift, mechanical pumping and the like commonly used in the field.

The invention adopts the measurement of foaming, foam stabilizing and liquid carrying performances of the foam drainage agent to evaluate the foam drainage performance, and evaluates the high temperature resistance of the foam drainage agent by comparing the foaming, foam stabilizing and liquid carrying performances before and after high-temperature aging, wherein the specific evaluation method comprises the following steps:

(1) foam row performance

The initial foaming height of the foam drainage agent and the foaming height after a certain period of time were measured by a Roche foam tester (ROSS-Miles method) to evaluate the foaming ability and foam stabilizing ability. Continuously introducing gas with a certain flow rate into the foam water discharging agent solution or the mixed solution of the foam water discharging agent solution and the oil to form foam, measuring the amount of liquid (water, oil and water) carried out by the foam after a certain time, calculating the liquid carrying rate, and evaluating the liquid carrying capacity of the foam water discharging agent solution.

(2) High temperature resistance

And (3) after the foam drainage agent solution is aged at high temperature by adopting a pressure-resistant and acid-resistant aging device, measuring the foam drainage performance and the high-temperature resistance again.

By adopting the liquid drainage and gas production method, 0.02-0.15% of solid foam water discharging agent is in 0-200,000 mg/L salinity brine, when no kerosene is contained, the foaming height reaches 169mm before and after high-temperature aging, the liquid carrying rate reaches 91.8%, 0.15% of solid foam water discharging agent is in 100,000mg/L salinity brine, when 10-30 wt% of kerosene is contained, the foaming height reaches 152mm, the liquid carrying rate reaches 88.7%, the liquid discharging and gas production method has excellent temperature resistance, salt tolerance and oil resistance in an acid environment, and better technical effects are obtained.

Drawings

FIG. 1 is a schematic view showing a flow of measuring the amount of liquid carried by a foam drainage agent. Wherein, 1 is a constant temperature water bath, 2 is a measuring cup, 3 is circulating water, 4 is a foam collector, 5 is a foaming pipe, 6 is a test solution, 7 is a rotameter, and 8 is a gas cylinder.

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＝CH₃T 1-t 2-s 1-s 2-0) 120 g, 150 g of sodium sulfate, 50 g of sodium tartrate and 70 g of potassium chloride are mixed uniformly, 50 g of 10% polyethylene glycol is added, and the mixture is pressed into a stick shape to prepare the foam drainage stick 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 mother liquor was diluted to a predetermined concentration and introduced into a Roche foam meter, and the initial height of foaming and the height of foaming after 5 minutes of the foam discharging agent HFS01 were measured by the ROSS-Miles method, and the results are shown in Table 1.

4000mL/min of nitrogen was continuously introduced into the aqueous solution of the foam discharging agent HFS01, the amount of water carried over by the foam in 15 minutes was measured, and the liquid carrying rate was calculated, and the results are shown in Table 1. The liquid carrying amount measuring apparatus used is shown in FIG. 1. The experiment is carried out by adopting a pressure-resistant and acid-resistant aging device, the performances such as initial foaming height, foaming height after 5 minutes, liquid carrying rate after 15 minutes and the like are measured again after aging 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).

e. Reacting a polyamine compound1(R₁＝C₁₈H₃₅，m＝5，R₂＝R₃＝R₄＝CH₃T 1-t 2-s 1-s 2-0), 120 g of sodium hydroxypropanesulfonate, 150 g of sodium sulfate, 50 g of sodium tartrate and 70 g of potassium chloride are mixed uniformly, 50 g of 10% polyethylene glycol is added, and the mixture is pressed into a rod shape to prepare the foam drainage rod HFS 02.

(2) The same as [ example 1 ] except that the aging was carried out at 150 ℃ for 72 hours, the results are shown in Table 3.

[ example 4 ]

The same as [ example 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＝C₂H₅120 g of t 1-t 2-s 1-s 2-0), 120 g of sodium tartrate, 70 g of sodium chloride and 50 g of urea are uniformly mixed, 30 g of 10% cellulose aqueous solution is added to be mixed, and the mixture is 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 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).

e. Reacting a polyamine compound3(R₁＝C₂₂H₄₅，m＝1，R₂＝R₃＝R₄＝C₂H₄OH, t1 ═ t2 ═ s1 ═ s2 ═ 0), 120 g of potassium acetate product, 30 g of potassium phthalate, 30 g of sodium borate, 100 g of biuret, and 30 g of 5% polyethylene glycol solution were mixed and pressed into a stick, and the foam drainage stick HFS04 was obtained.

(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 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 DEG CKeeping the temperature for 1 hour after the hydrogen absorption is finished, and carrying out post-treatment to obtain the 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＝CH₃120 g of t 1-t 2-s 1-s 2-0), 100 g of potassium citrate, 100 g of urea, 30 g of potassium carbonate and 30 g of sodium acetate, adding 30 g of 1% polyacrylamide aqueous solution, mixing, pressing into a rod shape, and obtaining the foam drainage rod HFS 05.

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

[ example 10 ]

The same as [ example 10 ] 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 same as [ example 1 ] except that 10 wt% and 30 wt% of kerosene were added and the simulated water was 100,000mg/LNaCl in order to measure the properties of HFS01 to HFS05, the results are shown in Table 11.

[ example 12 ]

The same as in example 2, except that hydrogen sulfide and carbon dioxide acid gas were introduced into the gas when the amount of liquid carried was measured, the results are shown in Table 12.

[ COMPARATIVE EXAMPLE 1 ]

The same as [ example 1 ], except that C is used₁₇H₃₃CO(NHCH₂CH₂)₅NH₂Substituted polyamine compounds1(R₁＝C₁₈H₃₅，m＝5，R₂＝R₃＝R₄＝CH₃T1 ═ t2 ═ s1 ═ s2 ═ 0), and the other additives were unchanged to give foam drainage bars HFS06 with simulated water of 100,000mg/LNaCl, the results are shown in table 13.

[ COMPARATIVE EXAMPLE 2 ]

The same as example 2 except thatIn that is represented by C₁₇H₃₃CO(NHCH₂CH₂)₅NH₂Substituted polyamine compounds1(R₁＝C₁₈H₃₅，m＝5，R₂＝R₃＝R₄＝CH₃T1 ═ t2 ═ s1 ═ s2 ═ 0), and the other additives were unchanged to give foam drainage bars HFS06 with simulated water of 100,000mg/LNaCl, the results are shown in table 14.

[ COMPARATIVE EXAMPLE 3 ]

The same as [ example 5 ], except that C is used₁₅H₃₁CO(NHCH₂CH₂)₂NH₂Substituted polyamine compounds2(R₁＝C₁₆H₃₃，m＝2，R₂＝R₃＝R₄＝C₂H₅T1 ═ t2 ═ s1 ═ s2 ═ 0), and the other additives were unchanged to give foam drainage bars HFS07 with simulated water of 100,000mg/LNaCl, the results are shown in table 13. [ COMPARATIVE EXAMPLE 4 ]

The same as [ example 6 ], except that C is used₁₅H₃₁CO(NHCH₂CH₂)₂NH₂Substituted polyamine compounds2(R₁＝C₁₆H₃₃，m＝2，R₂＝R₃＝R₄＝C₂H₅T1 ═ t2 ═ s1 ═ s2 ═ 0), and the other additives were unchanged to give foam drainage bars HFS07 with simulated water of 100,000mg/LNaCl, the results are shown in table 14.

[ COMPARATIVE EXAMPLE 5 ]

The same as [ example 7 ], except that C is used₂₁H₄₃CONHCH₂CH₂NH₂Substituted polyamine compounds3(R₁＝C₂₂H₄₅，m＝1，R₂＝R₃＝R₄＝C₂H₄OH, t1 ═ t2 ═ s1 ═ s2 ═ 0), other additives were unchanged to give foam drainage bars HFS08 with simulated water of 100,000mg/LNaCl, the results are shown in table 13.

[ COMPARATIVE EXAMPLE 6 ]

The same as [ example 8 ], except that C is used₂₁H₄₃CONHCH₂CH₂NH₂Substituted polyamine compounds3(R₁＝C₂₂H₄₅，m＝1，R₂＝R₃＝R₄＝C₂H₄OH, t1 ═ t2 ═ s1 ═ s2 ═ 0), other additives were unchanged to give foam drainage bars HFS08 with simulated water of 100,000mg/LNaCl, the results are shown in table 14.

[ COMPARATIVE EXAMPLE 7 ]

The same as [ example 9 ], except that C is used₁₉H₂₉CO(NHCH₂CH₂)₂NH₂Substituted polyamine compounds4(R₁＝C₂₀H₃₁，m＝2，，R₂＝R₃＝R₄＝CH₃T1 ═ t2 ═ s1 ═ s2 ═ 0), and the other additives were unchanged to give foam drainage bars HFS09 with simulated water of 100,000mg/LNaCl, the results are shown in table 13.

[ COMPARATIVE EXAMPLE 8 ]

The same as [ example 10 ], except that C is used₁₉H₂₉CO(NHCH₂CH₂)₂NH₂Substituted polyamine compounds4(R₁＝C₂₀H₃₁，m＝2，，R₂＝R₃＝R₄＝CH₃T1 ═ t2 ═ s1 ═ s2 ═ 0), and the other additives were unchanged to give foam drainage bars HFS09 with simulated water of 100,000mg/LNaCl, the results are shown in table 14.

[ COMPARATIVE EXAMPLE 9 ]

The same as [ example 1 ] except that the betaine C is oleamidopropyl carboxylate₁₇H₃₃CONH(CH₂)₃N⁺(CH₃)₂CH₂COO^-Substituted polyamine compounds1(R₁＝C₁₈H₃₅，m＝5，R₂＝R₃＝R₄＝CH₃T1 ═ t2 ═ s1 ═ s2 ═ 0), and the other additives were unchanged to give foam drainage stick HFL10, with simulated water at 100,000mg/LNaCl, and the results are shown in table 13.

[ COMPARATIVE EXAMPLE 10 ]

Same as [ example 2 ], butCharacterized in that the betaine C is oleamide propyl carboxylate₁₇H₃₃CONH(CH₂)₃N⁺(CH₃)₂CH₂COO^-Substituted polyamine compounds1(R₁＝C₁₈H₃₅，m＝5，R₂＝R₃＝R₄＝CH₃T 1-t 2-s 1-s 2-0), and the other additives were unchanged to prepare a foam drainage bar HFL10, 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

1. The method for drainage and gas production by adopting the solid foam drainage agent comprises the following steps:

1)1 part of polyamine surfactant;

2) 0.05-1000 parts of solid filler;

3) 0-0.5 parts of adhesive;

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 = any integer from 1 to 4, d = any integer from 0 to 3, e = 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 = any integer of 1-10; t1, t2 are positive charges, s1, s2 are R₅Y₁、R₆Y₂The number of substituents, t1= s1=0 or 1, t2= s2=0 or 1; the gas is at least one of air, nitrogen, methane or natural gas, with or without H₂S or CO₂An acid gas; the oil is at least one of kerosene, crude oil or condensate oil;

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

2. The method of water drainage and gas production using a solid foam drainage agent of claim 1, wherein R is R₁Is C₈～C₂₄Hydrocarbyl or substituted hydrocarbyl; r₂、R₃、R₄Is (CH)₂)_aOH or (CH)₂)_bCH₃A = any integer of 2-4, b = any integer of 0-4; c = any integer of 1-2, d = any integer of 0-1, e = any integer of 1-2; y is₁、Y₂Independently selected from COO^-、SO₃ ^-One of (1); m =1~ 5.

3. The method of drainage and gas production using a solid foam drainage agent according to claim 1, wherein the binder is at least one of dextrin, epoxy resin, polyacrylamide, starch, cellulose, polyethylene glycol, and the like.

4. The method of water drainage and gas production using the solid foam drainage agent of claim 3, wherein the inorganic oxysalt is at least one of carbonate, bicarbonate, sulfate, phosphate, and borate.

5. The method for water drainage and gas production using the solid foam drainage agent according to claim 3, wherein the organic carboxylic acid and the salt thereof is at least one of formate, acetate, tartaric acid and the salt thereof, citric acid and the salt thereof, phthalic acid and the salt thereof, and gallic acid and the salt thereof.

6. The method of drainage and gas production using a solid foam drainage agent according to claim 3, 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, and biuret.

7. The method of claim 3, wherein the binder is at least one of polyacrylamide, starch, and polyethylene glycol.

8. The method for drainage and gas production by using the solid foam drainage agent according to claim 1, wherein the mass ratio of the polyamine surfactant, the solid filler and the adhesive is 1: (0.1-200): (0.01-0.1).

9. The method for draining water and producing gas by using the solid foam drainage agent according to any one of claims 1 to 8, wherein the preparation method of the solid foam drainage agent comprises 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 =1 to 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 the monohalogenated hydrocarbon-sodium hydroxide method, the aldehyde acid oxidation method, or by the use of a packageA process for the catalytic hydrogenation of an aldehyde 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 s1= t1= s2= t2=0 in a molecular general formula shown in a formula (1), and then 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：H₂The molar ratio of (A) to (3-20): (5-40);

or further obtaining the zwitterionic surfactant with at least one of s1= t1 and s2= t2 in the molecular general formula shown in the formula (1) as 1 through the reaction of the step d:

d. quaternization reaction:

and c, mixing the tertiary amine nonionic surfactant and the ionizing reagent obtained in the step c, wherein the molar ratio of s1= t1= s2= t2=0 is 1: (1-5) reacting in a short carbon chain alcohol aqueous solution at the 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 the 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;

10. The method for producing water and gas by draining water with solid foam drainage agent according to claim 9, wherein R in step a₀COOR’、 H(NHCH₂CH₂)_mNH₂The molar ratio of the catalyst is 1 (1-1.3) to 0-0.1, and the catalyst is selected from sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonateOne of them is less.

11. The method for producing water and gas by draining water with solid foam drainage agent according to claim 9, wherein the step b is H^-Y⁺Is LiAlH₄、LiAlH(OEt)₃Or NaBH₄Wherein the aprotic solvent is at least one of diethyl ether, tetrahydrofuran and dioxane.

12. The method for water drainage and gas production by using the solid foam drainage agent according to claim 9, wherein the metal catalyst in the step C is one selected from the group consisting 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; 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.

13. The method of water drainage and gas production using a solid foam drainage agent of claim 1, wherein the gas is at least one of nitrogen, methane or natural gas, H₂S and CO₂The content of (A) is 15-35%; the oil is at least one of kerosene or condensate oil.

14. The method for drainage and gas production by using the solid foam drainage agent according to any one of claims 1 to 8, characterized in that the method is applied under the following conditions: the formation temperature is 150-200 ℃, the total salinity of formation brine is 500-200000 mg/L, H₂S and CO₂The content of (A) is 0-35%.