CN113528110A

CN113528110A - Foam drainage agent for exploitation of ancient sulfur-containing natural gas and preparation method thereof

Info

Publication number: CN113528110A
Application number: CN202110985010.5A
Authority: CN
Inventors: 孟楠; 邓明; 罗思宝; 杨青; 邓永智
Original assignee: Chengdu Sodium Magnesium Chemical Co ltd
Current assignee: Chengdu Sodium Magnesium Chemical Co ltd
Priority date: 2021-08-24
Filing date: 2021-08-24
Publication date: 2021-10-22
Anticipated expiration: 2041-08-24
Also published as: CN113528110B

Abstract

The invention discloses a foam drainage agent for exploitation of ancient sulfur-containing natural gas and a preparation method thereof; the foam scrubbing agent comprises the following components in percentage by mass: sulfonated AEO₃: 50-60% of lauramidopropyl betaine phosphate: 20-30% of coconut oil fatty acid monoethanolamide: 5-10% of oil soapberry essence: 5-10% of lignosulfonate: 1-4% and the balance of water; the preparation method of the foam scrubbing agent comprises the steps of firstly sulfonating AEO₃Adding the coconut oil fatty acid monoethanolamide, the soapberry essence, the lignosulfonate and the water into a reaction kettle in sequence, and mixing for the second time to obtain a foam water discharging agent; the invention provides a foam drainage agent with acid resistance, hypersalinity resistance and strong secondary foaming capacity, overcomes the defects of the prior art, and solves the technical problem of foam drainage of an ancient gas well.

Description

Foam drainage agent for exploitation of ancient sulfur-containing natural gas and preparation method thereof

Technical Field

The invention relates to the field of natural gas exploitation, in particular to a foam drainage agent for exploitation of ancient sulfur-containing natural gas and a preparation method thereof.

Background

The Ordosi basin underground ancient gas reservoir development enters an integrated pilot test stage from 2019 after evaluation of a vertical well and development of a horizontal well, annual contribution of yield is 1.89 million, and the yield accounts for 5.8%. 93 total wells, 89 production wells, 67 open wells (13 vertical wells and 54 horizontal wells) of ancient gas wells at 4 months in 2021, the open well rate is 74.2%, the production time rate is 96%, the average casing pressure is 7.39MPa, the pressure drop rate is 0.0021MPa/d, the single well yield is 0.97 ten thousand square/day, the liquid-gas ratio is 1.78 square/square, and the accumulated gas production is 10.1 hundred million square.

At present, the pressure and the yield of an ancient gas well are relatively high, 25 gas wells with foam drainage auxiliary liquid drainage are needed, and the number of the gas wells accounts for 37.3 percent of that of production wells. The existing foam row has the following problems:

firstly, because acid fracturing adopts acid fracturing fluid with lower pH, the flowback rate after gas testing is low, and the lower ancient bed contains H₂S, the whole produced liquid is acidic, foaming agents adopted by most of the ancient gas wells at present mainly comprise a composite foam discharging agent compounded by an anionic surfactant and a nonionic surfactant, the foaming performance is greatly influenced by pH, and the method is not suitable for drainage and gas production of the ancient gas wells.

And secondly, the ancient formation water and the ancient formation water have different characteristics, the mineralization degree is high and can reach 3000000mg/L, the formation water components and the fluid properties are different, and the highest mineralization resistance of the foam discharging agent for the current gas field is 200000mg/L, so that the foaming and liquid carrying capacity of the traditional foam discharging agent in the formation water is poor.

And thirdly, the old gas well adopts an underground throttler process, and after the foam discharging agent passes through a throttling air nozzle, a defoaming effect is generated, so that the foam discharging effect is influenced.

Disclosure of Invention

The invention aims to overcome the defects of the prior art, provides a foam drainage agent for the exploitation of ancient sulfur-containing natural gas, has strong foaming, foam stabilizing, secondary foaming and liquid carrying capacities in a high-salinity and acidic environment, and solves the technical problem of the foam drainage of ancient gas wells.

The purpose of the invention is realized by the following technical scheme:

a foam drainage agent for exploiting sulfur-containing natural gas in the ancient times comprises the following components in percentage by mass:

sulfonated AEO₃: 50-60% of lauramidopropyl betaine phosphate: 20-30% of coconut oil fatty acid monoethanolamide: 5-10% of oil soapberry essence: 5-10% of lignosulfonate: 1-4% and the balance of water.

Preferably, the paint consists of the following components in percentage by mass:

sulfonated AEO₃: 55%, lauramidopropyl phosphobetaine: 25%, coconut oil fatty acid monoethanolamide: 7% of soapberry essence: 7%, lignosulfonate: 3 percent of water and the balance of water.

Preferably, the sulfonated AEO₃Instead of containing sulfonated AEO₃Said mixture comprising sulfonated AEO₃The mixture of (a) was synthesized by the following method:

AEO (ethylene oxide)₃、HSO₃NH₂Adding the sulfonated AEO and a catalyst into a reaction kettle according to the mass ratio of 7: 2.5-3.5: 0.42-0.7, and fully reacting under a vacuum condition to obtain the sulfonated AEO₃A mixture of (a);

wherein the reaction temperature is 110-130 ℃, the stirring time is 1.5-3 h, and the stirring speed is 90-110 r/min.

Preferably, the AEO₃、HSO₃NH₂And the mass ratio of the catalyst is 7:3: 0.49.

Preferably, the sulfonation reaction temperature is 120 ℃, the stirring time is 2 hours, and the stirring speed is 100 r/min.

Preferably, the catalyst is dimethylformamide or urea.

The invention uses sulfonated AEO₃Sulfonated AEO with lauramidopropyl phosphobetaine as main agent₃The characteristics of the nonionic-anionic surfactant are reflected, and the foaming and liquid-carrying capacity is stronger under the condition of mineralization degree; baylaurelThe amidopropyl phosphobetaine shows the characteristics of an amphoteric surfactant, is insensitive to the pH value of formation water, and has strong foaming and liquid carrying capacities under the condition of low pH value. Because the invention is applied to a complex ancient sulfur-containing gas well formation water system, the mineralization degree of the formation water is high, the pH value is low, and the interference of condensate oil, methanol, corrosion inhibitor and other substances on the foam discharging agent also exists; coconut oil fatty acid monoethanolamide is introduced as a foaming aid, so that the structural stability of a bubble liquid film can be controlled, surfactant molecules are distributed in the bubble liquid film in order, and good elasticity and self-repairing capability are given to the foam; introducing soapberry essence as a foam stabilizer, embedding dialkyl chain sodium dicarboxylate anion groups on molecular soapberry and saponin plant essence molecular chains to obtain the soapberry essence, wherein the molecules of the soapberry essence have two hydrophilic groups with negative charges, the two hydrophilic groups generate a negative charge enhancement overlapping region, and the higher charge density greatly increases intermolecular attraction, so that a great dissolving effect is generated, molecular layers which are directionally arranged in an interface film are combined very tightly, the film strength is greatly enhanced, and foams are difficult to break; and then lignosulfonate is introduced as a foam regulator to regulate the water content of the foam, and substances with the size of the foam are controlled, so that large bubbles are changed into small bubbles, the foaming agent generates uniform, fine and stable foam substances, the obtained bubbles have low density and high strength, and the fluctuation of the water content of the foam is small.

The second purpose of the invention is to provide a preparation method of the foam drainage agent for the exploitation of the ancient sulfur-containing natural gas, which comprises the following steps:

first sulfonated AEO₃Adding the mixture and lauramidopropyl betaine phosphate into a reaction kettle, mixing for the first time, then sequentially adding the coconut oil fatty acid monoethanolamide, the soapberry essence, the lignosulfonate and the water into the reaction kettle, and mixing for the second time to obtain the foam water discharging agent.

Preferably, during the first mixing: the stirring speed is 120-180 r/min, and the stirring time is 1.8-2.2 h; in the second mixing process: the stirring speed is 120-180 r/min, the stirring time is 1.8-2.2 h, and the temperature in the preparation process is 38-42 ℃.

Preferably, during the first mixing: the stirring speed is 150r/min, and the stirring time is 2 h; in the second mixing process: the stirring speed is 150r/min, the stirring time is 2h, and the temperature in the preparation process is 40 ℃.

The invention has the beneficial effects that:

1. the invention fills the vacancy of the foam drainage agent of the ancient sulfur-containing natural gas well, and solves the technical problem of poor foaming performance under the conditions of high mineralization and low pH value.

2. The foam is fine and smooth, the diameter is small, the foam can quickly pass through the underground throttler, secondary foaming is realized at the rear end of the throttler, and the influence of the underground throttler on the performance of the foam discharging agent is overcome.

3. The invention provides a method for preparing sulfonated AEO₃The preparation process is simple, does not produce any pollution, and greatly improves the AEO₃And the prepared sulfonated AEO₃The mixture can reach extremely high conversion rate, and can reach extremely high purity requirement without independent purification; the antique foam-scrubbing agent prepared by using the raw material and AEO₃The performance of the antique foam-drain agent prepared from the raw materials has no obvious difference, and the antique foam-drain agent plays a great role in foaming, foam stabilization and liquid carrying rate of the foam-drain agent.

Drawings

FIG. 1 is a schematic flow diagram of the present invention;

FIG. 2 is a graph showing the effect of the ancient foam-scrubbing agent in the well X;

Detailed Description

The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited to the following.

First, an embodiment

As shown in figure 1, 50-60% of sulfonated AEO is added by mass percent₃Mixing with 20-30% of lauramidopropyl phosphobetaine for the first time, and then sequentially adding 5-10% of coconut fatty acid monoethanolamide, 5-10% of soapberry essence and 1-4% of woodAnd mixing the lignin sulfonate and water for the second time to prepare the foam water discharging agent. And finally, carrying out foaming, foam stabilizing, secondary foaming and liquid carrying capacity testing on the prepared foam drainage agent.

The specific implementation mode is as follows:

example 1

S1 containing sulfonated AEO₃Synthesis of the mixture of (a): AEO (ethylene oxide)₃、HSO₃NH₂Adding urea and urea into a reaction kettle according to the mass ratio of 7:2.5:0.42, and fully reacting under the vacuum condition to obtain the sulfonated AEO₃A mixture of (a);

wherein the reaction temperature is 120 ℃, the stirring time is 2h, and the stirring speed is 100 r/min;

s2: firstly, 55 percent of sulfonated AEO is added₃The mixture and 25% of lauramidopropyl betaine phosphate are added into a reaction kettle for the first mixing, then 7% of coconut monoethanolamide, 7% of sapindus mukorossi essence, 3% of lignosulfonate and 3% of water are sequentially added into the reaction kettle for the second mixing, and the foam water discharging agent is obtained.

Wherein, in the first mixing process: the stirring speed is 150r/min, and the stirring time is 2 h; in the second mixing process: the stirring speed is 150r/min, and the stirring time is 2 h; the temperature during the preparation was 40 ℃.

Example 2

S1 containing sulfonated AEO₃Synthesis of the mixture of (a): AEO (ethylene oxide)₃、HSO₃NH₂Adding urea and urea into a reaction kettle according to the mass ratio of 7:3:0.49, and fully reacting under the vacuum condition to obtain a mixture containing sulfonated AEO 3; wherein the reaction temperature is 120 ℃, the stirring time is 2h, and the stirring speed is 100 r/min;

s2: firstly, 55 percent of sulfonated AEO is added₃The mixture and 25% of lauramidopropyl phosphobetaine are added into a reaction kettle for the first mixing, then 7% of coconut monoethanolamide, 7% of sapindus mukorossi essence, 3% of lignosulfonate and 3% of water are added into the reaction kettle in sequence for the second mixingMixing the above materials, and making into foam water discharging agent.

Example 3

S1 containing sulfonated AEO₃Synthesis of the mixture of (a): AEO (ethylene oxide)₃、HSO₃NH₂Adding urea and urea into a reaction kettle according to the mass ratio of 7:3.5:0.7, and fully reacting under the vacuum condition to obtain the sulfonated AEO₃A mixture of (a); wherein the reaction temperature is 120 ℃, the stirring time is 2h, and the stirring speed is 100 r/min;

Example 4

S1 containing sulfonated AEO₃Synthesis of the mixture of (a): AEO (ethylene oxide)₃、HSO₃NH₂Adding the mixture and dimethylformamide into a reaction kettle according to the mass ratio of 7:3.5:0.7, and fully reacting under the vacuum condition to obtain a mixture containing sulfonated AEO 3;

wherein the reaction temperature is 110 ℃, the stirring time is 3h, and the stirring speed is 110 r/min;

s2: firstly, 55 percent of sulfonated AEO is added₃The mixture of (1) and 25% of lauramidopropyl phosphobetaine are added into a reaction kettle for first mixing, and then 7% of coconut monoethanolamide, 7% of sapindus essence, 3% of lignosulfonate and 3% of water are addedAnd sequentially adding the mixture into the reaction kettle, and mixing for the second time to obtain the foam water discharging agent.

Example 5

S1 containing sulfonated AEO₃Synthesis of the mixture of (a): AEO (ethylene oxide)₃、HSO₃NH₂Adding the mixture and dimethylformamide into a reaction kettle according to the mass ratio of 7:3.5:0.7, and fully reacting under the vacuum condition to obtain the sulfonated AEO₃A mixture of (a); wherein the reaction temperature is 120 ℃, the stirring time is 2h, and the stirring speed is 100 r/min;

Example 6

S1 containing sulfonated AEO₃Synthesis of the mixture of (a): AEO (ethylene oxide)₃、HSO₃NH₂Adding the mixture and dimethylformamide into a reaction kettle according to the mass ratio of 7:3.5:0.7, and fully reacting under the vacuum condition to obtain the sulfonated AEO₃A mixture of (a); wherein the reaction temperature is 130 ℃, the stirring time is 1.5h, and the stirring speed is 90 r/min;

s2: firstly, 55 percent of sulfonated AEO is added₃The mixture is added into a reaction kettle with 25 percent of lauramidopropyl phosphobetaine for the first mixing, and then 7 percent of coconut monoethanolamide, 7 percent of soapberry essence and 3 percent of wood are addedSequentially adding the lignin sulfonate and 3% of water into the reaction kettle, and mixing for the second time to obtain the foam water discharging agent.

Example 7

S1: containing sulfonated AEO₃Synthesis of the mixture of (a): AEO (ethylene oxide)₃、HSO₃NH₂Adding the mixture and dimethylformamide into a reaction kettle according to the mass ratio of 7:2.5:0.42, and fully reacting under the vacuum condition to obtain the sulfonated AEO₃A mixture of (a); wherein the reaction temperature is 110 ℃, the stirring time is 3h, and the stirring speed is 110 r/min;

s2, firstly, 50 percent of sulfonated AEO is added₃The mixture and 30% of lauramidopropyl betaine phosphate are added into a reaction kettle for the first mixing, then 10% of coconut monoethanolamide, 5% of sapindus mukorossi essence, 4% of lignosulfonate and 1% of water are sequentially added into the reaction kettle for the second mixing, and the foam water discharging agent is obtained.

Example 8

S1: containing sulfonated AEO₃Synthesis of the mixture of (a): AEO (ethylene oxide)₃、HSO₃NH₂Adding the mixture and dimethylformamide into a reaction kettle according to the mass ratio of 7:2.5:0.42, and fully reacting under the vacuum condition to obtain a mixture containing sulfonated AEO 3; wherein the reaction temperature is 110 ℃, the stirring time is 3h, and the stirring speed is 110 r/min;

s2: firstly, 55 percent of sulfonated AEO is added₃The mixture is added into a reaction kettle with 25 percent of lauramidopropyl phosphobetaine for the first mixing, and then 7 percent of coconut monoethanolamide and 7 percent of soapberry fruit are addedAnd adding the essence, 3% of lignosulfonate and 3% of water into the reaction kettle in sequence, and mixing for the second time to obtain the foam drainage agent.

Example 9

s2: according to the mass percentage, 60 percent of sulfonated AEO₃The mixture and 20% of lauramidopropyl betaine phosphate are added into a reaction kettle for the first mixing, then 5% of coconut monoethanolamide, 10% of sapindus mukorossi essence, 1% of lignosulfonate and 4% of water are sequentially added into the reaction kettle for the second mixing, and the foam water discharging agent is obtained.

Example 10

S1: containing sulfonated AEO₃Synthesis of the mixture of (a): AEO (ethylene oxide)₃、HSO₃NH₂Adding urea and urea into a reaction kettle according to the mass ratio of 7:3:0.49, and fully reacting under the vacuum condition to obtain the sulfonated AEO₃A mixture of (a); wherein the reaction temperature is 110 ℃, the stirring time is 2h, and the stirring speed is 110 r/min;

s2: firstly, 55 percent of sulfonated AEO is added₃The mixture of (1) and 25% lauramidopropyl phosphobetaine are added into a reaction kettle for the first mixing, and then 7% coconut oil fatty acid monoethanol acyl is addedAnd adding amine, 7% of soapberry essence, 3% of lignosulfonate and 3% of water into the reaction kettle in sequence, and mixing for the second time to obtain the foam drainage agent.

Wherein, in the first mixing process: the stirring speed is 120r/min, and the stirring time is 2.2 h; in the second mixing process: the stirring speed is 120r/min, and the stirring time is 2.2 h; the temperature during the preparation was 42 ℃.

Example 11

s2: adding 55% of mixture containing sulfonated AEO3 and 25% of lauramidopropyl phosphobetaine into a reaction kettle by mass percent for first mixing, then sequentially adding 7% of coconut monoethanolamide, 7% of sapindus essence, 3% of lignosulfonate and 3% of water into the reaction kettle for second mixing, and obtaining the foam water discharging agent.

Wherein, in the first mixing process: stirring at 180r/min for 1.8 h; in the second mixing process: stirring at 180r/min for 1.8 h; the temperature during the preparation was 38 ℃.

Example 12

S1: containing sulfonated AEO₃Synthesis of the mixture of (a): AEO (ethylene oxide)₃、HSO₃NH₂Adding urea and urea into a reaction kettle according to the mass ratio of 7:3:0.49, and fully reacting under the vacuum condition to obtain a mixture containing sulfonated AEO 3; wherein the reaction temperature is 110 ℃, the stirring time is 2h, and the stirring speed is 110 r/min;

s2: firstly, 55 percent of sulfonated AEO is added₃The mixture of (A) and 25% lauramidopropyl phosphobetaine are added into a reaction kettle for the first mixing, and then 7% coconut oil fatty acid monoethanolamide,And sequentially adding 7% of the sapindus mukorossi essence, 3% of the lignosulfonate and 3% of water into the reaction kettle, and mixing for the second time to obtain the foam drainage agent.

Example 13

Sulfonated AEO as described in this example₃Is sulfonated AEO prepared in any way and purified₃。

Firstly, according to mass percentage, sulfonated AEO₃Adding 30% of lauramidopropyl betaine phosphate into a reaction kettle, mixing for the first time, then sequentially adding 10% of coconut monoethanolamide, 5% of soapberry essence, 4% of lignosulfonate and 1% of water into the reaction kettle, and mixing for the second time to obtain the foam water discharging agent.

Example 14

Firstly, 55 percent of sulfonated AEO by mass₃Adding 25% of lauramidopropyl betaine phosphate into a reaction kettle, mixing for the first time, then adding 7% of coconut monoethanol amide, 7% of sapindus mukorossi essence, 3% of lignosulfonate and 3% of water into the reaction kettle in sequence, and mixing for the second time to obtain the foam water discharging agent.

Example 15

Firstly, 60 percent of sulfonated AEO is calculated by mass percent₃Adding 20% of lauramidopropyl betaine phosphate into a reaction kettle, mixing for the first time, then sequentially adding 5% of coconut monoethanolamide, 10% of soapberry essence, 1% of lignosulfonate and 4% of water into the reaction kettle, and mixing for the second time to obtain the foam water discharging agent.

Example 16

Example 17

Firstly, 55 percent of sulfonated AEO by mass₃Adding 25% of lauramidopropyl betaine phosphate into a reaction kettle, mixing for the first time, and then adding 7% of coconut monoethanol amide, 7% of Sapindus mukurossi essence, 3% of lignosulfonate and 3% of water in sequence for reactionAnd (5) mixing for the second time in the kettle to obtain the foam water discharging agent.

Example 18

Based on example 2, 55% of sulfonated AEO₃The mixture of (3) was replaced with 55% water and the other conditions were unchanged.

Example 19

On the basis of example 2, 25% of lauramidopropyl phosphobetaine was replaced by 25% of water, and the other conditions were unchanged.

Example 20

On the basis of example 2, 7% of coconut monoethanolamide was replaced by 7% of water, and the other conditions were not changed.

Example 21

On the basis of example 2, 7% of the oil soapberry essence is replaced by 7% of water, and other conditions are not changed.

Example 22

On the basis of example 2, 3% of lignosulfonate was replaced by 3% of water, the other conditions being unchanged.

And II, testing and analyzing data.

(I) containing sulfonated AEO₃The data and conditions during the synthesis of the mixture of (a).

1. The optimal data and conditions are selected through experiments.

The following are variables in the experiment

Sulfonation reagent: oleum, sulfur trioxide, chlorosulfonic acid, and sulfamic acid;

AEO₃the dosage relation of the sulfonating agent is as follows: AEO₃The mass ratio of the sulfonating agent to the water is arbitrary;

the kind of the catalyst: n-methyl pyrrolidone, p-toluenesulfonic acid, dimethylformamide, urea and sodium hypophosphite;

the dosage of the catalyst is as follows: AEO₃And catalysisThe agent is in any mass ratio;

reaction temperature: any temperature;

reaction time: at any time;

performing a plurality of experiments on the data and the conditions to finally obtain the optimal conditions, namely the optimal sulfonating reagent is sulfamic acid, and the optimal dosage of the sulfamic acid is AEO₃：HSO₃NH₂7: 3; the best catalyst is urea; the optimum catalyst dosage is AEO₃: urea is 1: 0.07; the optimal temperature is 120 ℃; the optimal reaction time is 2 h.

2. The following is a table of controls selected from the optimization experiments described above, i.e., when one of the variables is changed and the other variables are optimally selected, the changed variable is to the synthetic experiment or AEO₃The effect of conversion.

(1) Sulphonation reagent

TABLE 1-1 sulfonation reagents comparison Table

Sulfating reagent	Advantages and disadvantages of the invention
		Oleum	The waste acid produced in the production process is much, the salt content of the product is high, and the waste acid is rarely adopted
Sulfur trioxide	The reaction is fast, the conversion rate is high, but the hydrogen chloride is generated, so that the corrosion to equipment is serious
		Chlorosulfonic acid	The reaction is fastest, the product quality is good, but the process control is complex, and the investment is large
Sulfamic acid	Simple equipment, less investment and no "three wastes" pollution

Comprehensively considering the factors of production cost, environmental protection and the like, and preferably selecting sulfamic acid (HSO) from the comparison of the reagents₃NH₂) As a sulfonating agent. The reaction equation is as follows:

the mechanism of the above reaction is that sulfamic acid first forms S0₃And NH₃Then reacting with active hydroxyl:

sulfamic acid is a very mild sulfonating agent because of the low electropositivity on the sulfur atom and the reduced electrophilicity due to the electron donating property of the amino group in the sulfamic acid molecule.

(2) The kind and amount of catalyst

Selecting AEO₃：HSO₃NH₂: the catalyst was 7:3:0.49, reacted at 120 ℃ for 2h, and the conversion of the sulfation reaction was examined when different catalysts were added.

Tables 1-2 test of the Effect of catalyst types on conversion

Name of catalyst	Conversion (%)
		Without addition of catalyst	65.42
N-methyl pyrrolidone	77.45
		P-toluenesulfonic acid	78.66
Dimethyl formamide	86.14
		Urea element	90.72
Sodium hypophosphite	76.28

As is clear from tables 1-2, AEO was observed when dimethylformamide or urea was selected as the catalyst among the above catalysts₃The conversion rate is relatively high, the effect is good, but the urea has wide source and low price. Therefore, urea is preferred as a catalyst for sulfation.

② selection of AEO₃：HSO₃NH₂And (3) reacting for 2h at 120 ℃, and observing the conversion rate of the sulfation reaction when the urea dosage is different.

Tables 1-3 test of the Effect of catalyst usage on conversion

AEO₃: urea element	Conversion (%)
		l:0.01	53.35
l:0.05	69.32
		1:0.06	81.20
l:0.07	90.72
		l:0.1	91.15
l:0.2	91.35
		l:0.3	91.95
l:0.5	92.31

As can be seen from tables 1-3, when AEO₃: urea 1: 0.06-0.1, AEO₃The conversion rate is relatively high, and when excessive urea is used in the reaction, the conversion rate of the reaction is improved to a certain extent but the improvement range is not obvious, so that AEO₃The optimal use ratio of urea to urea is 1: 0.07.

(3) Amount of sulfamic acid used

AEO in the synthesis process₃The molar ratio to sulfamic acid is also an important factor affecting the conversion of the product. Selection of AEO₃: urea l 0.07, reacted at 120 deg.c for 2 hr and AEO examined₃The influence on the conversion of the sulfonation reaction at different ratios to sulfamic acid.

Tables 1-4 test of the Effect of the reaction raw Material feed ratio on the conversion

AEO₃：HSO₃NH₂	Conversion (%)
		7:2.0	78.27
7:2.5	83.32
		7:3.0	90.72
7:3.5	90.75
		7:4.0	91.20
7:4.5	91.79
		7:5.0	88.09

As can be seen from tables 1-4, when AEO₃：HSO₃NH₂When 7:2.5-3.5, AEO₃The conversion rate is relatively high, and when the excessive sulfamic acid is used in the reaction, although the conversion rate of the reaction can be improved to a certain extent, the improvement range is not obvious, so that AEO₃The optimal ratio of the feed to the sulfamic acid is 7:3.

(4) Determination of the reaction temperature

Selection of AEO₃：HSO₃NH₂: urea 7:3:0.49 and reaction time 2h, and the influence of different reaction temperatures on the product conversion rate is examined.

Tables 1-5 test of the Effect of reaction temperature on conversion

Reaction temperature (. degree.C.)	Conversion (%)
		l00	78.32
110	85.12
		120	90.72
130	91.20
		140	91.52

As can be seen from tables 1-5, when the reaction temperature is greater than 110 ℃, AEO₃Is greater than 80%; when the reaction temperature is more than 120 ℃, AEO₃The conversion of (a) is greater than 90%. But as the temperature continues to rise, AEO₃The conversion rate is not improved obviously. Therefore, AEO is performed at a temperature of 110 to 130 DEG C₃The conversion is relatively high and the optimum reaction temperature is 120 ℃.

(5) Determination of reaction time

Selection of AEO₃：HSO₃NH₂: urea 7:3:0.49 at 120 ℃ and the influence of different reaction times on the conversion of sulfation reaction was examined.

Tables 1-6 test of the Effect of reaction time on conversion

Reaction time (h)	Conversion (%)
		0.5	66.89
1.0	71.45
		1.5	82.65
2.0	90.72
		3.0	91.56
4.0	88.45
		5.0	82.87

As can be seen from tables 1 to 6, when the reaction time is 1.5 to 3 hours, AEO is obtained₃The conversion rate is relatively high and the conversion is carried out along with the reactionThe rate is improved quickly, when the reaction time is 2-3 h, the conversion rate is up to more than 90%, the conversion rate is not obviously improved along with the continuous reaction, and when the reaction time is more than 3h, because of AEO₃It is easily decomposed at high temperature and other side reactions occur, resulting in a decrease in conversion. Therefore, the optimum reaction time is 2 h.

(II) testing the performance of the foam drainage agent

1. Testing of foaming and liquid carrying Properties

(1) Testing indexes are as follows: foaming performance and liquid carrying rate

(2) Test method

a. Measurement of foaming and foam stabilizing Capacity (measured by Luo foam Meter)

Weighing 1.20g of the foam-exhausting agent prepared in the examples 1-22 and the conventional foam-exhausting agent in a 1000mL beaker respectively, adding a mineralization degree water sample to dilute to 400mL to obtain a sample solution to be detected with the foam-exhausting agent concentration of 0.003g/mL, and heating the sample solution to be detected in a constant-temperature water bath to 70 +/-1 ℃ for later use.

Preheating the Roche foam instrument in a constant-temperature water bath, keeping the temperature at 70 +/-1 ℃, transferring 50mL of sample liquid to be tested by using a 200mL transfer pipette, putting down the sample liquid along the tube wall of the Roche foam instrument to flush the tube wall, closing a valve at the lower end of the Roche foam instrument after the flush liquid flows out, then transferring 50mL of sample liquid to be tested, putting down along the tube wall of the Roche foam instrument to form a liquid level at the bottom, transferring 200mL of sample liquid to be tested by using the transfer pipette, putting the sample liquid to be tested at the central position of the upper end of the Roche foam instrument, vertically putting down aiming at the liquid level, immediately recording the rising height of foam in the Roche foam instrument after the sample liquid to be tested is put out, and obtaining the foaming capacity of the experimental sample. And recording the foam height after 5min, namely the foam stabilizing capacity of the experimental sample.

b. Test of liquid carrying capacity

Weighing 1.20g of the foam-drain agent prepared in the examples 1-22 and the conventional foam-drain agent in a 1000mL beaker respectively, adding a mineralization degree water sample to dilute to 400mL to obtain a sample solution to be detected with the foam-drain agent concentration of 0.003g/mL, and heating the sample solution to be detected in a constant-temperature water bath to 70 +/-1 ℃ for later use.

The constant-temperature water bath preheats the liquid carrying instrument and keeps the temperature at 70 +/-1 ℃, an inflator pump is started, 8L of gas is filled in every minute, preheated sample liquid to be tested (namely the total volume of the sample liquid) is poured into the constant-temperature liquid carrying instrument to foam the solution, the liquid collected by a liquid collector is taken out until no foam is taken out, the volume of the taken liquid is measured (the liquid carrying rate is the volume of the taken liquid/the total volume of the sample liquid multiplied by 100 percent), and the liquid carrying capacity of the experimental sample is obtained.

(3) Test results

Table 2-1: test results of foaming capacity, foam stabilizing capacity and liquid carrying rate of foam discharging agent

As can be seen from table 2-1, the foaming and liquid carrying abilities of the foam discharging agents prepared in examples 1 to 17 (i.e., the ancient foam discharging agents of the present invention) are hardly affected under the conditions of high salinity and low pH, wherein the foaming, foam stabilizing and liquid carrying abilities of the ancient foam discharging agents prepared in examples 2 and 14 are the best; the conventional foam scrubbing agent is reduced along with the reduction of the pH value of the mineralized water, and almost loses foaming and liquid carrying capacities particularly after the pH value is lower than 5; in addition, as can be seen from the foam detergents prepared in examples 18 to 22, the foam detergent prepared by reducing any component in the invention decreases with the decrease of the pH value of the mineralized water, and particularly, almost loses foaming and liquid carrying capacity after the pH value is lower than 5; comparison of examples 7 to 11 and examples 13 to 17 shows that purified sulfonated AEO is used₃The antique foam-drain agent prepared from the raw materials is prepared by the method comprising the sulfonated AEO₃The antique foam scrubbing agent prepared by taking the mixture as the raw material has more outstanding effects on foaming, foam stabilization and liquid carrying capacity, but the total capacities of the foaming agent and the liquid carrying agent are not greatly different, and the antique foam scrubbing agent containing sulfonated AEO can be embodied₃The superiority of the synthesis process of the mixture.

2. Secondary foaming Performance test

Preheating the Roche foam instrument in a constant-temperature water bath, keeping the temperature at 70 +/-1 ℃, transferring 50mL of sample liquid to be tested by using a 200mL transfer pipette, putting down the sample liquid along the tube wall of the Roche foam instrument to flush the tube wall, closing a valve at the lower end of the Roche foam instrument after the flush liquid flows out, then transferring 50mL of sample liquid to be tested, putting down along the tube wall of the Roche foam instrument to form a liquid level at the bottom, transferring 200mL of sample liquid to be tested by using the transfer pipette, putting the sample liquid to be tested at the central position of the upper end of the Roche foam instrument, vertically putting down by aiming at the liquid level, immediately recording the rising height of foam in the Roche foam instrument after the sample liquid is put out, and obtaining the foaming capacity of the experimental sample.

And (4) collecting all the liquid samples after the foaming capacity test, standing for 24 hours (contact with the defoaming agent is forbidden), and determining according to a foaming capacity test method to obtain the secondary foaming capacity of the experimental sample.

TABLE 2-2 foam remover Secondary foaming Capacity test results

As can be seen from Table 2-2, the conventional foam scrubbing agent has a secondary foaming capacity of less than 50mm under the conditions of high mineralization and low pH; the secondary foaming capacity of the ancient foam discharging agent prepared by the invention is hardly influenced and is higher than 150 mm; the secondary bubble capacity of the foam discharging agent prepared in the embodiment 18-22 is equivalent to that of the conventional foam discharging agent, and both the secondary bubble capacity and the conventional foam discharging agent are lower; as is clear from the comparison between examples 7 to 11 and examples 13 to 17, sulfonated AEO was used₃The mixture of (A) is used as raw material for preparing the antique foam-drain agent, compared with the product prepared by using the mixture containing sulfonated AEO₃The mixture prepared by the method has the same effect in the aspect of secondary foaming capacity, has strong effect and shows that the mixture contains sulfonated AEO₃The superiority of the synthesis process of the mixture.

3. Liquid carrying capacity test in downhole choke demonstration device

Respectively weighing 4.50g of the foam discharging agent prepared in the embodiments 1-22 and the conventional foam discharging agent in a 5L liquid storage barrel, adding 250g/L of a mineralization degree water sample, and diluting to 1500mL to obtain a sample liquid to be detected with the concentration of the agent of 0.003g/mL (namely the total volume of the sample liquid). And starting a metering pump, and completely pumping the prepared sample liquid into a vertical well demonstration instrument with a restrictor. Starting an air compressor, introducing 16L/min of gas to foam the solution, collecting the liquid taken out by a liquid collector until no foam is taken out, and measuring the volume of the liquid taken out (the liquid carrying rate is the volume of the liquid taken out/the total volume of the sample liquid multiplied by 100 percent), namely the liquid carrying capacity of the experimental sample.

Because the demonstration device simulates the state of the on-site shaft, a pocket is arranged. Therefore, in calculation, the total volume of the sample liquid is 1000mL by the volume of the liquid above the gas source port through the actual test.

Tables 2 to 3: liquid carrying capacity test result of foam discharging agent in underground restrictor demonstration device

As can be seen from tables 2-3, the liquid carrying state of the conventional foam discharging agent in the underground throttling demonstration device is unstable and the slip is serious, and the liquid carrying rate is only 39.0 percent; the foam discharging agent prepared in the embodiment 18-22 has unstable liquid carrying state and serious slippage in the underground throttling demonstration device, and the liquid carrying rate is equivalent to that of the conventional foam discharging agent, while the ancient foam discharging agent in the invention has stable liquid carrying state in the underground throttling demonstration device, and the liquid carrying rate is as high as 81.3%; comparison of examples 7 to 11 and examples 13 to 17 shows that the purified sulfonated AEO is used₃The antique foam-drain agent prepared from the raw materials is prepared by the method comprising the sulfonated AEO₃The mixture of (A) and (B) is slightly superior to the ancient foam discharging agent prepared from the raw material in the aspect of liquid carrying capacity, but the difference between the two is not the sameLarge, and all have strong liquid-carrying capacity, and show that the sulfonated AEO is contained₃The superiority of the synthesis process of the mixture.

4. The ancient foam-drain agent was tested in the large flat X well (the test effect is shown in FIG. 2).

Statistics are carried out on production data from 5 months, 11 days to 17 days in 2021, the average oil pressure of the well production is 1.43MPa, the casing pressure is 5.69MPa, and the average daily gas production is 1823m³D, the well is unstable in production, cannot carry liquid by itself, needs to frequently take depressurization and carry liquid, particularly 5 months and 16-17 days, and has the gas production rate lower than 1000m³And d. The well bore has serious effusion and is in a water flooded state.

In 2021, 5 and 18 days, the ancient foam discharging agent prepared in example 7 is added into the well for the first time, the filling concentration is properly improved in consideration of severe liquid accumulation in the well bore which is in a water flooded state, 105L of mixed liquid of the ancient foam discharging agent and water is added from a well head oil pipe (wherein the volume ratio of the ancient foam discharging agent to the water is 1:6), a pressure reducing zone liquid is matched in a station to forcibly discharge the liquid accumulation in the well bore, normal production is recovered in the same day, and gas production is 4103m in a gas well³0.54m of liquid production³。

Injecting mixed liquid of the ancient foam discharging agent and water from the wellhead oil for 3 consecutive days for 5 months and 18 to 20 days to obtain 105L (wherein the volume ratio of the ancient foam discharging agent to the water is 1:6), obviously improving the production of a gas well after implementing the first stage foam discharging, and accumulating the produced gas for three days to obtain 12743m³Cumulative liquid production 2.05m³。

The total volume of 55L of mixed liquid of the ancient foam discharging agent and water is sleeved and injected at the wellhead every day by using the wellhead automatic injection device within 5 months and 21-6 months and 15 days (wherein the volume ratio of the ancient foam discharging agent to the water is 1:10), the gas well production is stable, and the daily average gas production is 3244m³Average daily liquid production of 0.90m³。

Table 2-4 comparative table of test effect

As can be seen from tables 2-4, the daily average gas production and daily average liquid production of the ancient foam discharging agent prepared by the invention are far greater than those of the conventional foam discharging agent. Since the antique foam-drain agent prepared in example 7 is not the optimal choice as compared with other antique foam-drain agents, the antique foam-drain agent can exert a good effect while the other antique foam-drain agents can exert a better effect.

The foregoing is merely a preferred embodiment of the invention, it is to be understood that the invention is not limited to the forms disclosed herein, but is not intended to be exhaustive or to limit the invention to other embodiments, and to various other combinations, modifications, and environments and may be modified within the scope of the inventive concept as expressed herein, by the teachings or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims

1. A foam drainage agent for exploitation of ancient sulfur-containing natural gas is characterized by comprising the following components in percentage by mass:

2. The foam drainage agent for developing ancient sulfur-containing natural gas according to claim 1, which is characterized by comprising the following components in percentage by mass:

3. The foam drainage agent for developing ancient sour natural gas of claim 1, wherein the sulfonated AEO is used as a drainage agent₃Instead of containing sulfonated AEO₃Said mixture comprising sulfonated AEO₃The mixture of (a) was synthesized by the following method:

AEO (ethylene oxide)₃、HSO₃NH₂And a catalyst in a mass ratio of7: 2.5-3.5: 0.42-0.7, and fully reacting under a vacuum condition to obtain the sulfonated AEO₃A mixture of (a);

4. The foam drainage agent for developing ancient sour natural gas according to claim 3, wherein the AEO is₃、HSO₃NH₂And the mass ratio of the catalyst is 7:3: 0.49.

5. The foam drainage agent for developing ancient sulfur-containing natural gas according to claim 3, wherein the sulfonation reaction temperature is 120 ℃, the stirring time is 2h, and the stirring speed is 100 r/min.

6. The foam drainage agent for ancient sour natural gas exploitation according to claim 3, wherein the catalyst is dimethylformamide or urea.

7. A preparation method of the foam drainage agent for ancient sour natural gas exploitation, which is used for preparing the foam drainage agent for ancient sour natural gas exploitation according to any one of claims 1 to 6, and the preparation method comprises the following steps:

8. The method for preparing the foam drainage agent for developing ancient sulfur-containing natural gas according to claim 7, wherein in the first mixing process: the stirring speed is 120-180 r/min, and the stirring time is 1.8-2.2 h; in the second mixing process: the stirring speed is 120-180 r/min, and the stirring time is 1.8-2.2 h; the temperature in the preparation process is 38-42 ℃.

9. The method for preparing the foam drainage agent for developing ancient sulfur-containing natural gas according to claim 8, wherein in the first mixing process: the stirring speed is 150r/min, and the stirring time is 2 h; in the second mixing process: the stirring speed is 150r/min, and the stirring time is 2 h; the temperature during the preparation was 40 ℃.