CN108751446B - Environment-friendly multifunctional scale inhibitor and preparation method and application thereof - Google Patents

Environment-friendly multifunctional scale inhibitor and preparation method and application thereof Download PDF

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CN108751446B
CN108751446B CN201810634711.2A CN201810634711A CN108751446B CN 108751446 B CN108751446 B CN 108751446B CN 201810634711 A CN201810634711 A CN 201810634711A CN 108751446 B CN108751446 B CN 108751446B
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scale inhibitor
scale
acid
environment
copolymer
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CN108751446A (en
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路建萍
李轶
沈燕宾
王佳
司伟
周渝
谢元
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Shaanxi Chemical Research Institute Co.,Ltd.
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Shaanxi Research Design Institute of Petroleum and Chemical Industry
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/12Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The invention provides an environment-friendly multifunctional scale inhibitor, which consists of the following raw materials in percentage by weight: 45-70% of a phosphorus-free chelating agent, 3-10% of a natural polymer, 5-15% of a scale inhibitor, 0.3-1% of dodecyl dimethyl betaine, 0.1-0.5% of polyhexamethylene guanidine hydrochloride and the balance of water, wherein the scale inhibitor is at least one of a sulfonic acid copolymer and a maleic anhydride copolymer. Meanwhile, the invention also provides a preparation method and application of the scale inhibitor. The scale inhibitor provided by the invention is added in trace amounts with dodecyl dimethyl betaine and polyhexamethylene guanidine hydrochloride, has a coordinated and synergistic effect on scale inhibition, has a remarkable scale inhibition effect on three scales of calcium carbonate, calcium phosphate and barium sulfate, and can effectively solve the problems of scale formation and blockage of oil field water; the formula is phosphorus-free, and has no pollution to the environment and environmental protection.

Description

Environment-friendly multifunctional scale inhibitor and preparation method and application thereof
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to an environment-friendly multifunctional scale inhibitor, and a preparation method and application thereof.
Background
In the oil field development and secondary oil extraction process, the energy of the oil layer is continuously consumed, so that the pressure of the oil layer is continuously reduced, underground crude oil is greatly degassed, the viscosity is increased, the yield of an oil well is greatly reduced, the oil field must be injected with water in order to maintain or improve the pressure of the oil layer and obtain higher recovery ratio, and the oil field water is generally reinjected in order to save water resources. In addition, in the process of oil field exploitation, oil-gas well fracturing is a production increasing measure, and the purposes of increasing production and increasing injection are achieved by improving the flow conductivity of an oil layer.
However, the oilfield reinjection water, the fracturing water and the formation water contain different scale forming ions such as calcium, magnesium, strontium, barium and the like, and due to thermodynamic instability and chemical incompatibility of water, the scale forming ions interact to generate unstable and easily precipitated substances such as barium sulfate (strontium), calcium carbonate, calcium sulfate and the like. The deposits are accumulated on the surfaces of an oil casing and various devices and can form scale, the problems that an oil well pump is blocked, an annular space between a well pipe and an oil pumping rod is blocked, the inner diameter of a gathering and transportation pipeline is reduced sharply, the devices and the stratum are seriously blocked and the like can be caused frequently, the normal operation of oil field production is greatly influenced, and the production stop of an oil-gas well can be caused even in serious cases.
The existing scale mainly comprises carbonate scale and sulfate scale, the carbonate scale is easy to remove by acidification, but the sulfate scale, especially barium sulfate scale, is difficult to remove by a common method. Currently, scale inhibitors applied to oil fields generally have narrow trial range, most of scale inhibitors only aim at single type scales, and the research on scale inhibitors capable of simultaneously and efficiently blocking three scales of calcium carbonate scale, calcium sulfate scale and barium sulfate scale is very few, and the scale inhibitors also have the problems of weak scale prevention capability, poor scale inhibition effect and environmental pollution. Therefore, the development of an environment-friendly, low-toxicity and high-efficiency multifunctional scale inhibitor is attracting more and more attention.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an environment-friendly multifunctional scale inhibitor, a preparation method and an application thereof.
An environment-friendly multifunctional scale inhibitor is prepared from the following raw materials in percentage by weight:
45-70% of a phosphorus-free chelating agent, 3-10% of a natural polymer, 5-15% of a scale inhibitor, 0.3-1% of dodecyl dimethyl betaine, 0.1-0.5% of polyhexamethylene guanidine hydrochloride and the balance of water, wherein the scale inhibitor is at least one of a sulfonic acid copolymer and a maleic anhydride copolymer.
Preferably, the phosphorus-free chelating agent comprises polyepoxysuccinic acid and at least one of polyacrylic acid, polyaspartic acid or hydrolyzed polymaleic anhydride; the ratio between the components is any ratio.
Preferably, the natural polymer is at least one of lignosulfonate, chitosan, carboxymethyl starch, carboxymethyl cellulose.
Preferably, the sulfonic acid copolymer is any one or two of acrylic acid/2-acrylamide-2-methylpropanesulfonic acid binary copolymer, acrylic acid/2-acrylamide-2-methylpropanesulfonic acid/hydroxypropyl acrylate terpolymer, acrylic acid/methacrylic acid/2-acrylamide-2-methylpropanesulfonic acid ternary copolymer and 2-acrylamide-2-methylpropanesulfonic acid/acrylic acid/methyl acrylate ternary copolymer.
Preferably, the maleic anhydride copolymer is any one or two of maleic anhydride/vinyl acetate/acrylic acid terpolymer, propyl acrylate/maleic anhydride/methyl acrylate terpolymer or maleic anhydride/acrylic acid/acrylamide/sodium methallylsulfonate tetrapolymer.
When the natural polymer, the sulfonic acid copolymer and the maleic anhydride copolymer are non-single components, the proportion of the components is any proportion.
The preparation method of the environment-friendly multifunctional scale inhibitor comprises the following steps: adding water, a phosphorus-free chelating agent, a natural polymer, a scale inhibitor, dodecyl dimethyl betaine and polyhexamethylene guanidine hydrochloride into a reaction device in sequence, and then stirring and reacting for 1-3h at 30-40 ℃.
The application of the environment-friendly multifunctional scale inhibitor is to apply the environment-friendly multifunctional scale inhibitor to the technical field of oil field water treatment, and the usage amount is 50-100 mg/L.
The invention has the advantages that:
the scale inhibitor provided by the invention is added in trace amounts with dodecyl dimethyl betaine and polyhexamethylene guanidine hydrochloride, has a coordinated and synergistic effect on scale inhibition, and has a remarkable scale inhibition effect on three scales of calcium carbonate, calcium phosphate and barium sulfate, wherein the scale inhibition rate of calcium carbonate scale is more than 96.5%, the scale inhibition rate of calcium sulfate scale is more than 97.5%, and the scale inhibition rate of barium sulfate scale is more than 95.0%, so that the scale formation and blockage problems of oil field water can be effectively solved; the formula is phosphorus-free, and has no pollution to the environment and environmental protection.
Detailed description of the preferred embodiments
Example 1
An environment-friendly multifunctional scale inhibitor is prepared from the following raw materials in percentage by weight: 65% of phosphorus-free chelating agent, 10% of natural polymer, 5% of scale inhibitor, 0.3% of dodecyl dimethyl betaine, 0.1% of polyhexamethylene guanidine hydrochloride and 19.6% of water; wherein the phosphorus-free chelating agent is a mixture of polyepoxysuccinic acid and polyacrylic acid in a mass ratio of 11: 2; the natural polymer is lignosulfonate; the scale inhibitor is a sulfonic acid copolymer, in particular an acrylic acid/2-acrylamide-2-methylpropanesulfonic acid binary copolymer;
the preparation method of the environment-friendly multifunctional scale inhibitor comprises the following steps: adding water, a phosphorus-free chelating agent, a natural polymer, a scale inhibitor, dodecyl dimethyl betaine and polyhexamethylene guanidine hydrochloride into a reaction kettle in sequence, and then stirring and reacting for 3 hours at the temperature of 30 ℃ to obtain the product.
Example 2
An environment-friendly multifunctional scale inhibitor is prepared from the following raw materials in percentage by weight: 45% of phosphorus-free chelating agent, 10% of natural polymer, 10% of scale inhibitor, 1% of dodecyl dimethyl betaine, 0.1% of polyhexamethylene guanidine hydrochloride and 33.9% of water; wherein the phosphorus-free chelating agent is a mixture of polyepoxysuccinic acid and polyaspartic acid in a mass ratio of 4: 5; the natural polymer is chitosan; the scale inhibitor is maleic anhydride copolymer, in particular maleic anhydride/vinyl acetate/acrylic acid terpolymer sulfonic acid copolymer.
The preparation method is the same as example 1.
Example 3
An environment-friendly multifunctional scale inhibitor is prepared from the following raw materials in percentage by weight: 70% of phosphorus-free chelating agent, 3% of natural polymer, 15% of scale inhibitor, 0.5% of dodecyl dimethyl betaine, 0.5% of polyhexamethylene guanidine hydrochloride and 11% of water; wherein the phosphorus-free chelating agent is a mixture of polyepoxysuccinic acid and hydrolyzed polymaleic anhydride in a mass ratio of 8: 2; the natural polymer is carboxymethyl starch; the scale inhibitor is a sulfonic acid copolymer, in particular to an acrylic acid/2-acrylamide-2-methylpropanesulfonic acid/hydroxypropyl acrylate terpolymer.
The preparation method is the same as example 1.
Comparative example 1
The procedure of example 1 was repeated except that dodecyl dimethyl betaine was not contained and the water content was 19.9%.
Comparative example 2
The procedure is as in example 1 except that polyhexamethyleneguanidine hydrochloride is not contained and the water content is 19.7%.
Comparative example 3
The procedure is as in example 1 except that dodecyl dimethyl betaine and polyhexamethylene guanidine hydrochloride are not contained and the water content is 20%.
Comparative example 4
The procedure is as in example 2 except that dodecyl dimethyl betaine is not contained and the water content is 34.9%.
Comparative example 5
The procedure is as in example 2 except that polyhexamethyleneguanidine hydrochloride is not contained and the water content is 34%.
Comparative example 6
The procedure is as in example 2 except that dodecyl dimethyl betaine and polyhexamethylene guanidine hydrochloride are not contained and the water content is 35%.
Comparative example 7
The procedure is as in example 3 except that dodecyl dimethyl betaine is not contained and the water content is 11.5%.
Comparative example 8
The procedure is as in example 3 except polyhexamethyleneguanidine hydrochloride is not contained and the water content is 11.5%.
Comparative example 9
The procedure is as in example 3 except that dodecyl dimethyl betaine and polyhexamethylene guanidine hydrochloride are not contained and the water content is 12%.
Detection of Scale inhibition Effect
A water sample to be treated: oil field reinjection water and formation water are both taken from a certain oil field in northern Shaanxi and are mixed according to the volume ratio of 1:1, and the specific water quality is shown in Table 1;
TABLE 1 Water quality analysis results (mg/L) of Water samples to be treated
Figure DEST_PATH_IMAGE001
The scale inhibitors provided in examples 1 to 3 and comparative examples 1 to 9 were added to a sample of water to be treated at an amount of 50 mg/L, stirred, left at 50. + -. 1 ℃ for 24 hours, and then the concentrations of calcium, barium and ion in the sample were measured to calculate the scale inhibition rates of calcium carbonate scale, calcium sulfate scale and barium sulfate scale, and the results are shown in Table 2.
TABLE 2 results of scale inhibition rates (%)
Figure 225521DEST_PATH_IMAGE002
As can be seen from table 2, the scale inhibitors prepared in examples 1 to 3 can simultaneously inhibit calcium carbonate scale, calcium sulfate scale and barium sulfate scale, and have significant scale inhibition effect; meanwhile, the addition of the dodecyl dimethyl betaine and the polyhexamethylene guanidine hydrochloride has a synergistic effect on scale inhibition.
Example 4
An environment-friendly multifunctional scale inhibitor is prepared from the following raw materials in percentage by weight: 60% of phosphorus-free chelating agent, 8% of natural polymer, 10% of scale inhibitor, 0.5% of dodecyl dimethyl betaine, 0.5% of polyhexamethylene guanidine hydrochloride and 21% of water; wherein the phosphorus-free chelating agent is a mixture of polyepoxysuccinic acid, polyaspartic acid and hydrolyzed polymaleic anhydride with equal mass; the natural polymer is a mixture of carboxymethyl cellulose and carboxymethyl starch with equal mass; the scale inhibitor is a mixture of a sulfonic acid copolymer and a maleic anhydride copolymer, and specifically is a mixture of 2-acrylamide-2-methylpropanesulfonic acid/acrylic acid/methyl acrylate terpolymer and a propyl acrylate/maleic anhydride/methyl acrylate terpolymer which are equal in mass;
the preparation method of the environment-friendly multifunctional scale inhibitor comprises the following steps: adding water, a phosphorus-free chelating agent, a natural polymer, a scale inhibitor, dodecyl dimethyl betaine and polyhexamethylene guanidine hydrochloride into a reaction kettle in sequence, and then stirring and reacting for 1h at 40 ℃.
Comparative example 10
The same procedure as in example 4 was repeated except that dodecyl dimethyl betaine was not contained and the water content was 21.5%.
Comparative example 11
The procedure is as in example 4 except that polyhexamethyleneguanidine hydrochloride is not contained and the water content is 21.5%.
Comparative example 12
The procedure is as in example 4 except that dodecyl dimethyl betaine and polyhexamethylene guanidine hydrochloride are not contained and the water content is 22%.
Detection of Scale inhibition Effect
A water sample to be treated: the water for the oil field fracturing fluid and the formation water are both taken from a certain oil field in northern Shaanxi and are mixed according to the volume ratio of 1:1, and the specific water quality is shown in Table 3;
TABLE 3 Water quality analysis results (mg/L) of Water samples to be treated
Figure DEST_PATH_IMAGE003
The scale inhibitor provided in example 4 and comparative examples 10 to 12 was added to a water sample to be treated at an amount of 100mg/L, stirred, and left at 50. + -. 1 ℃ for 24 hours, and then the concentrations of calcium, barium and ion in the water sample were measured to calculate the scale inhibition rates of calcium carbonate scale, calcium sulfate scale and barium sulfate scale, and the results are shown in Table 4.
TABLE 4 results of scale inhibition rates (%)
Figure 94993DEST_PATH_IMAGE004
As can be seen from table 4, the scale inhibitor prepared in example 4 can inhibit calcium carbonate scale, calcium sulfate scale and barium sulfate scale simultaneously, and has a significant scale inhibition effect; meanwhile, the addition of the dodecyl dimethyl betaine and the polyhexamethylene guanidine hydrochloride has a synergistic effect on scale inhibition.
Example 5
An environment-friendly multifunctional scale inhibitor is prepared from the following raw materials in percentage by weight: 55% of phosphorus-free chelating agent, 5% of natural polymer, 15% of scale inhibitor, 0.3% of dodecyl dimethyl betaine, 0.2% of polyhexamethylene guanidine hydrochloride and 24.5% of water; wherein the phosphorus-free chelating agent is a mixture of polyepoxysuccinic acid, polyacrylic acid, polyaspartic acid and hydrolyzed polymaleic anhydride in a mass ratio of 7:2:4: 3; the natural polymer is chitosan; the scale inhibitor is a mixture of a sulfonic acid copolymer and a maleic anhydride copolymer, and specifically is a mixture of acrylic acid/2-acrylamide-2-methylpropanesulfonic acid/hydroxypropyl acrylate, acrylic acid/methacrylic acid/2-acrylamide-2-methylpropanesulfonic acid, and maleic anhydride/acrylic acid/acrylamide/sodium methallylsulfonate in a mass ratio of 3:3: 4;
the preparation method of the environment-friendly multifunctional scale inhibitor comprises the following steps: adding water, a phosphorus-free chelating agent, a natural polymer, a scale inhibitor, dodecyl dimethyl betaine and polyhexamethylene guanidine hydrochloride into a reaction kettle in sequence, and then stirring and reacting for 2 hours at 35 ℃.
Comparative example 13
The same procedure as in example 5 was repeated except that dodecyl dimethyl betaine was not contained and the water content was 24.8%.
Comparative example 14
The procedure is as in example 5 except that polyhexamethyleneguanidine hydrochloride is not contained and the water content is 24.7%.
Comparative example 15
The procedure is as in example 5 except that dodecyl dimethyl betaine and polyhexamethylene guanidine hydrochloride are not contained and the water content is 25%.
Detection of Scale inhibition Effect
A water sample to be treated: the oil field water is taken from a certain oil field in northern Shaanxi, and the specific water quality is shown in Table 5;
TABLE 5 Water quality analysis results (mg/L) of Water samples to be treated
Figure DEST_PATH_IMAGE005
The scale inhibitor provided in example 5 and comparative examples 13 to 15 was added to a water sample to be treated at an amount of 75mg/L, stirred, and left at 50. + -. 1 ℃ for 24 hours, and then the concentrations of calcium, barium and ion in the water sample were measured to calculate the scale inhibition rates of calcium carbonate scale, calcium sulfate scale and barium sulfate scale, and the results are shown in Table 6.
TABLE 6 results of scale inhibition rates (%)
Figure 812414DEST_PATH_IMAGE006
As can be seen from table 6, the scale inhibitor prepared in example 5 can simultaneously inhibit calcium carbonate scale, calcium sulfate scale and barium sulfate scale, and has a significant scale inhibition effect; meanwhile, the addition of the dodecyl dimethyl betaine and the polyhexamethylene guanidine hydrochloride has a synergistic effect on scale inhibition.

Claims (3)

1. An environment-friendly multifunctional scale inhibitor is characterized in that: the composite material consists of the following raw materials in percentage by weight:
45-70% of a phosphorus-free chelating agent, 3-10% of a natural polymer, 5-15% of a scale inhibitor, 0.3-1% of dodecyl dimethyl betaine, 0.1-0.5% of polyhexamethylene guanidine hydrochloride and the balance of water, wherein the scale inhibitor is at least one of a sulfonic acid copolymer and a maleic anhydride copolymer;
wherein the sulfonic acid copolymer is any one or any two of acrylic acid/2-acrylamide-2-methylpropanesulfonic acid binary copolymer, acrylic acid/2-acrylamide-2-methylpropanesulfonic acid/hydroxypropyl acrylate terpolymer, acrylic acid/methacrylic acid/2-acrylamide-2-methylpropanesulfonic acid ternary copolymer and 2-acrylamide-2-methylpropanesulfonic acid/acrylic acid/methyl acrylate ternary copolymer;
wherein the maleic anhydride copolymer is any one or two of maleic anhydride/vinyl acetate/acrylic acid terpolymer, propyl acrylate/maleic anhydride/methyl acrylate terpolymer or maleic anhydride/acrylic acid/acrylamide/sodium methallylsulfonate tetrapolymer;
the phosphorus-free chelating agent comprises polyepoxysuccinic acid and at least one of polyacrylic acid, polyaspartic acid or hydrolyzed polymaleic anhydride;
the natural polymer is at least one of lignosulfonate, chitosan, carboxymethyl starch and carboxymethyl cellulose.
2. The preparation method of the environment-friendly multifunctional scale inhibitor of claim 1 is characterized in that: the preparation method comprises the following steps: adding water, a phosphorus-free chelating agent, a natural polymer, a scale inhibitor, dodecyl dimethyl betaine and polyhexamethylene guanidine hydrochloride into a reaction device in sequence, and then stirring and reacting for 1-3h at 30-40 ℃.
3. The application of the environment-friendly multifunctional scale inhibitor belongs to the technical field of oil field water treatment, the usage amount of the environment-friendly multifunctional scale inhibitor is 50-100mg/L, and the environment-friendly multifunctional scale inhibitor is the scale inhibitor in claim 1.
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CN109231509A (en) * 2018-11-15 2019-01-18 山东泰和水处理科技股份有限公司 A kind of scale inhibitor for salt manufacture and its application
CN111137991B (en) * 2020-03-23 2022-04-22 克拉玛依翎昊科技有限责任公司 Corrosion and scale inhibition bactericide and application thereof
CN113045096B (en) * 2021-03-30 2022-08-02 上海有江化工有限公司 Crystallization inhibitor and preparation method and application thereof
CN114106803A (en) * 2021-11-24 2022-03-01 克拉玛依新科澳石油天然气技术股份有限公司 Oil well slow-speed descaling antiscaling agent and preparation and use methods thereof
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