CN111073617A - Self-emulsifying blockage removing liquid and preparation method thereof - Google Patents
Self-emulsifying blockage removing liquid and preparation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/32—Anticorrosion additives
Abstract
The invention discloses a self-emulsifying blockage removing liquid and a preparation method thereof. The invention provides a self-emulsifying blockage removing liquid which comprises the following components: 0.2-3 wt% of nonionic emulsifier, 0.5-5 wt% of cationic surfactant, 1-5 wt% of water-soluble oxidant, 1-15 wt% of organic acid corrosion inhibitor, 0.5-2 wt% of corrosion inhibitor and the balance of water. The invention also provides a preparation method of the self-emulsifying blockage removing liquid, which comprises the following steps: mixing and stirring a nonionic emulsifier and part of water to obtain a mixed solution A; mixing and stirring a cationic surfactant, a water-soluble oxidant, an organic acid corrosion inhibitor, a corrosion inhibitor and the rest water to obtain a mixed solution B; and mixing and stirring the mixed solution A and the mixed solution B to obtain the self-emulsifying unblocking liquid. The self-emulsifying blockage removing liquid provided by the invention has excellent oil washing capacity and blockage removing performance, and is remarkable in blockage removing effect, low in corrosivity to pipelines and high in safety.
Description
Technical Field
The invention relates to the technical field of oilfield chemistry. More particularly, relates to a self-emulsifying blockage removing liquid and a preparation method thereof.
Background
The polymer flooding technology is tested and applied successively in many oil fields in China, with the continuous injection of the polymer, although the oil well yield can be improved, the polymer and the crude oil are crosslinked and adsorbed in the stratum, so that a serious blocking phenomenon occurs, the injection pressure is increased, the liquid absorption index of the stratum is reduced, and the polymer flooding effect is influenced. Therefore, the problem of polymer injection well plugging needs to be solved. In the blockage, a large amount of polymer and thick oil are wound, so that the blockage removal difficulty is high.
The common blocking remover for oil fields often contains a large amount of aromatic hydrocarbons, petroleum ethers, alkanes and other organic extraction type oil detergents which have high toxicity, have the problems of easy volatilization, low flash point and the like, bring about great potential safety hazards in the injection process and have high use cost. Therefore, on the premise of ensuring the effect of removing the blockage of the polymer injection well, how to improve the safety of the blockage removing system is of great importance.
Therefore, the invention provides a self-emulsifying blockage removing liquid and a preparation method thereof, which aim to solve the problems.
Disclosure of Invention
One object of the present invention is to provide a self-emulsifying deblocking fluid.
The invention also aims to provide a preparation method of the self-emulsifying blockage removing liquid.
In order to achieve the purpose, the invention adopts the following technical scheme:
the self-emulsifying blockage removing liquid comprises the following components in percentage by mass:
the nonionic emulsifier in the self-emulsifying deblocking liquid can generate a synergistic effect with a cationic surfactant, can remarkably reduce the oil-water interfacial tension, change the surface wettability of a blockage, and form a stable emulsion under slight stirring, so that oil can be automatically separated from the blockage, and the self-emulsifying deblocking liquid has excellent oil washing capacity, avoids the use of an organic extractant, has no flash point, and has high stability and safety; in addition, a water-soluble oxidant and an organic acid corrosion inhibitor are introduced into the self-emulsifying blockage removing liquid, so that the exposed polymer and inorganic blockage can be effectively degraded, and the self-emulsifying blockage removing liquid has an excellent composite blockage removing effect and higher blockage removing efficiency; and the corrosion inhibitor is added, so that the corrosion of the plugging removing liquid to a shaft can be effectively reduced.
Preferably, the non-ionic emulsifier is one or more of polyvinyl alcohol, polyoxyethylene octyl phenol ether-10 and alkyl glycoside.
Preferably, the alkyl glycoside is decyl glucoside and/or octyl decyl glucoside.
Preferably, the cationic surfactant is one or more of dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium bromide and hexadecyl trimethyl ammonium chloride.
Preferably, the water-soluble oxidizing agent is a persulfate and/or a peroxide.
Preferably, the peroxide is urea peroxide and/or calcium peroxide.
Preferably, the persulfate is ammonium persulfate and/or potassium persulfate.
Preferably, the organic acid corrosion inhibitor is one or more of citric acid, oxalic acid, maleic acid, organic phosphate and peroxyacetic acid.
Preferably, the corrosion inhibitor is one or more of mannich base, imidazoline quaternary ammonium salt, polyoxyethylene alkylphenol ether and thiourea.
Preferably, the water is distilled water.
The invention also provides a preparation method of the self-emulsifying blockage removing liquid, which comprises the following steps:
mixing and stirring a nonionic emulsifier and part of water to obtain a mixed solution A;
mixing and stirring a cationic surfactant, a water-soluble oxidant, an organic acid corrosion inhibitor, a corrosion inhibitor and the rest water to obtain a mixed solution B;
and mixing and stirring the mixed solution A and the mixed solution B to obtain the self-emulsifying unblocking liquid. The invention has no special requirements on the dosage of partial water and residual water, and the reagent can be fully dissolved and the total amount of the water is in the dosage range.
Preferably, the temperature of the nonionic emulsifier and part of water during mixing and stirring is 45-55 ℃.
Preferably, the rotation speed of the nonionic emulsifier and part of water during mixing and stirring is 300-500 r/min.
Preferably, the temperature for mixing and stirring the cationic surfactant, the water-soluble oxidant, the organic acid corrosion inhibitor, the corrosion inhibitor and the residual water is 45-55 ℃.
Preferably, the rotating speed of mixing and stirring the cationic surfactant, the water-soluble oxidant, the organic acid corrosion inhibitor, the corrosion inhibitor and the residual water is 300-500 r/min.
Preferably, the temperature for mixing and stirring the mixed solution A and the mixed solution B is 45-55 ℃.
Preferably, the rotation speed of the mixed liquid A and the mixed liquid B during mixing and stirring is 500-1000 r/min.
Preferably, the preparation method specifically comprises the following steps: adding a nonionic emulsifier into a container, adding part of water, setting the stirring speed to be 300-500 r/min, uniformly stirring at 45-55 ℃ to obtain a mixed solution A, and filling the mixed solution A into a sealed container for later use; then, uniformly mixing the residual water, the cationic surfactant, the water-soluble oxidant, the organic acid corrosion inhibitor and the corrosion inhibitor under stirring at 300-500 r/min to obtain a mixed solution B; and finally, mixing the mixed solution A and the mixed solution B, uniformly stirring at 500-1000 r/min to obtain the self-emulsifying unblocking liquid, and sealing for later use.
In addition, unless otherwise specified, any range recited herein includes any value between the endpoints and any sub-range defined by any value between the endpoints or any value between the endpoints.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) the self-emulsifying blockage removing liquid provided by the invention has excellent oil washing capacity and blockage removing capacity, and meanwhile, the self-emulsifying blockage removing liquid has low corrosivity to pipelines and high safety.
(2) The self-emulsifying deblocking liquid provided by the invention constructs a self-emulsifying deblocking system by using the nonionic emulsifier and the cationic surfactant, avoids using an organic extractant, has a stable system without a flash point, and has high safety.
(3) The self-emulsifying blockage removing liquid provided by the invention can automatically emulsify and strip oil stains on the surface of a blockage under the oil reservoir condition, and has stable residual liquid and excellent oil washing capacity.
(4) The self-emulsifying blockage removing liquid provided by the invention is a composite blockage removing agent, a water-soluble oxidant can quickly remove blockage caused by polymers, a self-emulsifying system has strong capacity of removing oil stains, and organic acid is adopted to dissolve inorganic scales, so that the blockage with complex components of a polymer injection well can be effectively removed, and the corrosion rate to a shaft is low.
Drawings
FIG. 1 is a graph showing the injection pressure of the self-emulsifying plugging removal fluid obtained in example 5 of the invention on a sand-packed pipe plugging model as a function of time.
Fig. 2 is a graph showing the comparison of the emulsification effect of the self-emulsifying deblocking liquid obtained in example 3 of the present invention and the deblocking liquid obtained in comparative example 2.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the invention, the preparation method is a conventional method if no special description is provided; the starting materials used are commercially available from published sources unless otherwise specified.
In the following embodiments of the invention, the self-emulsifying deblocking liquid prepared by the method comprises the following steps:
filling the self-emulsifying blockage removing liquid into a plastic test tube; then put in the mass m1The obtained on-site plug is evenly shaken for 5 times and then put into a 60 ℃ oven; standing for 24h, taking out a dirty sample, filtering and washing for 3 times; putting the dirty sample into a 60 ℃ oven for drying, taking out the dirty sample, weighing the dirty sample by weight m2Calculating a resolution according to formula (I);
in the formula (I), the compound is shown in the specification,
m1represents the mass of the plug in situ in g;
m2represents the mass of the scale sample in g;
repeating the steps for three times, and taking an average value.
In the following examples of the invention, the prepared self-emulsifying deblocking liquid was subjected to the following corrosion test conditions: the corrosion experiments were carried out using a3 iron sheet, the experimental standards being referred to the industry standard (SY-5273).
In the following embodiments of the invention, the steps of the self-emulsifying deblocking liquid prepared for the physical model experiment of the sand-packed pipe are as follows:
drying the on-site plug to constant weight, and mixing the on-site plug with 100-mesh quartz sand according to the mass ratio of 1: 10; measuring the basic data of sand sample, saturating the simulated formation water of oil field, measuring the original water and measuring the permeability k1(ii) a Calculating pore bodyAccumulating; injecting self-emulsifying deblocking liquid at an injection speed of 0.5mL/min, performing subsequent water flooding after the injection volume is 5PV, and calculating the permeability k2(ii) a Calculating the blockage removal rate according to a formula (II);
in the formula (II), the compound is shown in the specification,
phi represents the blockage removal rate, and the unit is%;
k1representing the original water permeability in mD;
m2the measured permeability of the self-emulsifying plugging removal liquid is expressed in mD.
Example 1
This embodiment 1 provides a self-emulsifying deblocking fluid, and the raw material composition of this self-emulsifying deblocking fluid includes:
the preparation method of the self-emulsifying deblocking liquid provided in the embodiment 1 includes the following steps:
adding 1g of polyvinyl alcohol into a container, adding 10g of distilled water, setting the stirring speed to be 300r/min, uniformly stirring at 45 ℃ to obtain a mixed solution A, and filling the mixed solution A into a sealed container for later use; then, uniformly mixing 62g of distilled water, 5g of hexadecyl trimethyl ammonium bromide, 5g of ammonium persulfate, 15g of citric acid and 2g of imidazoline quaternary ammonium salt under the stirring of 300r/min to obtain a mixed solution B; and finally, mixing the mixed solution A and the mixed solution B, uniformly stirring at 1000r/min to obtain the self-emulsifying unblocking liquid, and sealing for later use.
The self-emulsifying plugging removal liquid prepared in the embodiment 1 is used for degradation capacity test: the on-site plug with the mass of 2g is used, the residual mass after degradation is 0.2096g, and the removal rate reaches 89.52 wt%.
Comparative example 1
The comparative example 1 provides a plugging removal liquid, and the raw material components and the preparation method of the plugging removal liquid are the same as those of the example 1, and the differences are only that: 0.5g of polyvinyl alcohol was used in place of 1g of polyvinyl alcohol in example 1, and 72.5g of distilled water was used in place of 72g of distilled water in example 1.
The plugging removal solution prepared in the comparative example 1 is used for degradation capacity test: the in-situ plug mass of 2g was used, the mass remaining after degradation was 0.4182g, and the release rate was reduced to 79.09 wt%.
In comparison with example 1, in comparative example 1, the release rate is reduced by 10.43 percentage points (wt%) without changing other conditions and only the mass concentration of polyvinyl alcohol is changed, and therefore, the mass concentration of polyvinyl alcohol is not preferably too low.
Example 2
This embodiment 2 provides a self-emulsifying deblocking fluid, and this self-emulsifying deblocking fluid's raw materials component includes:
the preparation method of the self-emulsifying deblocking liquid provided in the embodiment 2 includes the following steps:
adding 0.5g of polyoxyethylene octyl phenol ether-10 into a container, adding 5g of distilled water, stirring at the speed of 300r/min, uniformly stirring at 45 ℃ to obtain a mixed solution A, and filling the mixed solution A into a sealed container for later use; then, uniformly mixing 76g of distilled water, 3g of hexadecyl trimethyl ammonium bromide, 4g of urea peroxide, 10g of citric acid and 1.5g of Mannich base under the stirring of 300r/min to obtain a mixed solution B; and finally, mixing the mixed solution A and the mixed solution B, uniformly stirring at 500r/min to obtain the self-emulsifying unblocking liquid, and sealing for later use.
The self-emulsifying plugging removal liquid prepared in the embodiment 2 is used for degradation capacity test: the in-situ plug mass of 2g was used, the mass remaining after degradation was 0.3668g, the release rate was 81.66 wt%.
Example 3
This embodiment 3 provides a self-emulsifying deblocking fluid, and this self-emulsifying deblocking fluid's raw materials component includes:
the preparation method of the self-emulsifying deblocking liquid provided in the embodiment 3 includes the following steps:
adding 2g of polyoxyethylene octyl phenol ether-10 into a container, adding 10g of distilled water, stirring at the speed of 300r/min, uniformly stirring at 45 ℃ to obtain a mixed solution A, and filling the mixed solution A into a sealed container for later use; then, uniformly mixing 62.5g of distilled water, 5g of dodecyl trimethyl ammonium chloride, 4g of ammonium persulfate, 15g of citric acid and 1.5g of polyoxyethylene alkylphenol ether under the stirring of 300r/min to obtain a mixed solution B; and finally, mixing the mixed solution A and the mixed solution B, uniformly stirring at 1000r/min to obtain the self-emulsifying unblocking liquid, and sealing for later use.
The self-emulsifying plugging removal liquid prepared in the embodiment 3 is used for corrosion test: the average corrosion rate over 24h tested at 60 ℃ was: 1.2299 g/(m)2h) And the corrosiveness is low.
The self-emulsifying plugging removal liquid prepared in the embodiment 3 is used for carrying out degradation capability test: the in-situ plug mass of 2.0g was used, the mass remaining after degradation was 0.3398g, and the release rate was 83.01 wt%.
Comparative example 2
The comparative example 2 provides a plugging removal liquid, which has the same raw material components and preparation method as the example 3, and only differs from the following components: tween 60 was used in place of polyoxyethylene octylphenol ether-10 in example 3.
The plugging removal solution prepared in the comparative example 2 is used for degradation capacity test: the amount of the in-situ plug used was 2g, and the mass remaining after degradation was 0.7378g, with a release rate of 63.11 wt%.
Fig. 2 is a graph comparing the emulsification effects of the plugging removal solution of example 3 and the plugging removal solution of comparative example 2, and it can be seen that the self-emulsifying plugging removal solution formed by the red polyoxyethylene octyl phenol ether-10 of example 3 and the dodecyl trimethyl ammonium chloride has excellent oil washing effect.
Example 4
This embodiment 4 provides a self-emulsifying deblocking fluid, and this self-emulsifying deblocking fluid's raw materials component includes:
the preparation method of the self-emulsifying deblocking liquid provided in this embodiment 4 includes the following steps:
adding 1g of decyl glucoside into a container, adding 9g of distilled water, stirring at a speed of 300r/min, uniformly stirring at 45 ℃ to obtain a mixed solution A, and filling the mixed solution A into a sealed container for later use; then, uniformly mixing 72.5g of distilled water, 2.5g of dodecyl trimethyl ammonium bromide, 3g of ammonium persulfate, 10g of citric acid and 2g of polyoxyethylene alkylphenol ether under the stirring of 500r/min to obtain a mixed solution B; and finally, mixing the mixed solution A and the mixed solution B, uniformly stirring at 1000r/min to obtain the self-emulsifying unblocking liquid, and sealing for later use.
The self-emulsifying plugging removal fluid prepared in this example 4 was used for corrosion testing: the average corrosion rate over 24h tested at 60 ℃ was: 1.1725 g/(m)2H), the corrosiveness is low.
The self-emulsifying plugging removal liquid prepared in the embodiment 4 is used for degradation capacity test: the in-situ plug mass of 2g was used, the mass remaining after degradation was 0.3156g, and the release rate was 84.22 wt%.
Comparative example 3
The comparative example 3 provides a plugging removal liquid, which has the same raw material components and preparation method as the example 4, and only differs from the following components: sulfuric acid was used instead of citric acid in example 4.
The plugging removal liquid prepared in the comparative example 3 is used for corrosion test: the average corrosion rate over 24h tested at 60 ℃ was: 5.1267 g/(m)2H), the corrosion rate increases.
The plugging removal solution prepared in the comparative example 3 is adopted to carry out degradation capability test: the in-situ plug mass of 2g was used, the mass remaining after degradation was 0.3122g, the release rate was 84.39 wt%.
The results show that the corrosivity becomes strong without a significant increase in the plug removal rate.
Example 5
This embodiment 5 provides a self-emulsifying deblocking fluid, and the raw material composition of this self-emulsifying deblocking fluid includes:
the preparation method of the self-emulsifying deblocking liquid provided in this embodiment 5 includes the following steps:
adding 1g of polypropylene glycol into a container, adding 7g of distilled water, stirring at a speed of 500r/min, uniformly stirring at 45 ℃ to obtain a mixed solution A, and filling the mixed solution A into a sealed container for later use; then, uniformly mixing 70g of distilled water, 5g of hexadecyl trimethyl ammonium bromide, 5g of ammonium persulfate, 10g of citric acid and 2g of polyoxyethylene alkylphenol ether under the stirring of 500r/min to obtain a mixed solution B; and finally, mixing the mixed solution A and the mixed solution B, uniformly stirring at 1000r/min to obtain the self-emulsifying unblocking liquid, and sealing for later use.
The self-emulsifying plugging removal liquid prepared in the embodiment 5 is used for degradation capacity test: the in-situ plug mass of 2g was used, the mass remaining after degradation was 0.3844g, and the release rate was 80.78 wt%.
The self-emulsifying plugging removal fluid prepared in this example 5 was used for corrosion testing: the average corrosion rate over 24h tested at 60 ℃ was: 1.1205 g/(m)2H), the corrosiveness is low.
The self-emulsifying plugging removal liquid prepared in the embodiment 5 is adopted to carry out a physical model experiment of a sand-filled pipe: the final blockage removing rate of the self-emulsifying blockage removing liquid to the sand-packed pipe blockage model is 65.09%, and the injection pressure changes along with time as shown in figure 1.
The present invention is not limited to the above-described embodiments. The foregoing description of the specific embodiments is intended to describe and illustrate the technical solutions of the present invention, and the above specific embodiments are merely illustrative and not restrictive. Those skilled in the art can make many changes and modifications to the invention without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The self-emulsifying deblocking fluid is characterized by comprising the following components in percentage by mass:
2. the self-emulsifying deblocking fluid of claim 1, wherein the non-ionic emulsifier is one or more of polyvinyl alcohol, polyoxyethylene octylphenol ether-10, and alkyl glycoside.
3. The self-emulsifying deblocking fluid of claim 2, wherein said alkyl glycoside is decyl glucoside and/or octecyl glucoside.
4. The self-emulsifying deblocking fluid of claim 1, wherein the cationic surfactant is one or more of dodecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, and hexadecyltrimethylammonium chloride.
5. The self-emulsifying unplugging fluid of claim 1, wherein the water soluble oxidant is a persulfate and/or a peroxide.
6. The self-emulsifying deblocking fluid of claim 5, wherein the peroxide is urea peroxide and/or calcium peroxide.
7. The self-emulsifying unplugging fluid of claim 5, wherein the persulfate is ammonium persulfate and/or potassium persulfate.
8. The self-emulsifying deblocking fluid of claim 1, wherein the organic acid corrosion inhibitor is one or more of citric acid, oxalic acid, maleic acid, organophosphates, and peroxyacetic acid.
9. The self-emulsifying deblocking liquid of claim 1, wherein the corrosion inhibitor is one or more of mannich base, imidazoline quaternary ammonium salt, polyoxyethylene alkylphenol ether and thiourea.
10. A method for preparing the self-emulsifying unblocking fluid of any one of claims 1 to 9, comprising the steps of:
mixing and stirring a nonionic emulsifier and part of water to obtain a mixed solution A;
mixing and stirring a cationic surfactant, a water-soluble oxidant, an organic acid corrosion inhibitor, a corrosion inhibitor and the rest water to obtain a mixed solution B;
and mixing and stirring the mixed solution A and the mixed solution B to obtain the self-emulsifying unblocking liquid.
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| CN114672296A (en) * | 2022-03-15 | 2022-06-28 | 中国石油大学(华东) | Efficient blocking remover for polymer flooding oilfield composite blockage and preparation method and application thereof |
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| CN114316934A (en) * | 2021-12-23 | 2022-04-12 | 东营才聚科技有限责任公司 | Low-corrosivity polyacrylic acid blocking remover capable of being mixed with acid liquor, and preparation method and application thereof |
| CN114316934B (en) * | 2021-12-23 | 2023-08-15 | 东营才聚科技有限责任公司 | Low-corrosiveness polyacrylic acid blocking remover capable of being mixed with acid solution, and preparation method and application thereof |
| CN114672296A (en) * | 2022-03-15 | 2022-06-28 | 中国石油大学(华东) | Efficient blocking remover for polymer flooding oilfield composite blockage and preparation method and application thereof |
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Application publication date: 20200428 |