CN107304078B - Environment-friendly slow-release polymer scale inhibitor and preparation method thereof - Google Patents
Environment-friendly slow-release polymer scale inhibitor and preparation method thereof Download PDFInfo
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- CN107304078B CN107304078B CN201610247058.5A CN201610247058A CN107304078B CN 107304078 B CN107304078 B CN 107304078B CN 201610247058 A CN201610247058 A CN 201610247058A CN 107304078 B CN107304078 B CN 107304078B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/105—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances combined with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/04—Surfactants, used as part of a formulation or alone
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Abstract
The invention discloses an environment-friendly slow-release polymer scale inhibitor which has good scale inhibition and slow release effects, can estimate the amount of the scale inhibitor required to be added in an overhaul period in advance according to the actual production condition of an oil well, is placed in a sieve tube at the lower end of an oil well pump in the periodic repair and maintenance process of an oil well pipeline and a gathering and transportation pipeline, when produced liquid flows through the sieve tube, scale inhibition components are slowly dissolved and released, the effect of long-term scale inhibition by one-time addition is achieved, the effective concentration for a long time can be maintained, the scale inhibition rate in the effective use period (about 90-120 days) is more than 85 percent, the effective release time is more than 90 days, the protection period of the pipeline is long, and the production and maintenance cost of an oil field can be effectively reduced; the environment-friendly slow-release polymer scale inhibitor is non-toxic, harmless and degradable, does not cause any harm to the stratum and the surrounding environment, is environment-friendly, and is suitable for popularization and application.
Description
Technical Field
The invention belongs to the field of oil field water treatment agents, and mainly relates to an environment-friendly slow-release polymer scale inhibitor and a preparation method thereof.
Background
With the development of the petroleum industry, most oil fields in China enter the middle and later stages of petroleum exploitation, the water content of oil well produced liquid is high (more than 85 percent, even 90 percent), and calcium, magnesium and other ions in formation water have high concentration, so that scaling is easily formed in oil well pipelines and gathering and transportation pipelines, the problems of oil well pump blockage, internal diameter reduction of gathering and transportation pipelines, flow reduction and the like are caused, and the production efficiency of oil wells is seriously influenced. The increasing scaling problem brings huge economic loss to oil exploitation, and frequent overhauling greatly influences the yield of oil fields, and the overhauling and maintenance cost is high. In order to solve the scaling problem of oil wells and gathering pipelines, a method of adding scale inhibitor is generally adopted, and the traditional method of adding liquid scale inhibitor has a series of problems such as great dosing difficulty caused by great oil pumping pump pressure, bringing out of scale inhibitor by produced liquid when the scale inhibitor does not reach a specified position, short protection period, complex dosing process, frequent dosing, high cost and the like. The development of high-efficiency solid slow-release scale inhibitors is an urgent need for oil field water treatment, researchers have developed some solid scale inhibitor products at present, but the problems that the release speed is unstable and difficult to adjust, and the solid slow-release scale inhibitors can be agglomerated and fall off in the using process to cause blockage exist.
Disclosure of Invention
The invention aims to provide an environment-friendly slow-release polymer scale inhibitor and a preparation method thereof, the environment-friendly slow-release polymer scale inhibitor has the characteristics of good slow-release effect, rich raw material sources, good scale inhibition effect, long effective period, environmental friendliness, low cost and the like, and the related preparation method is easy to operate, is suitable for relieving the scaling problem in the fields of oil well pipelines, gathering and transportation pipelines and the like, and has important practical application value.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of an environment-friendly slow-release polymer scale inhibitor comprises the following steps:
1) uniformly mixing the environment-friendly scale inhibition component, the carrier material and the additive, transferring the mixture into a mold, pressing the mixture for 10 to 20min under the pressure of 10 to 25MPa, and demolding to obtain a block preparation;
2) respectively preparing a polymer wall material solution and a curing agent solution, placing the obtained block preparation in the polymer wall material solution to react for 3-8 min so that the wall material is uniformly coated on the surface of the block preparation, taking out the block preparation and placing the block preparation in the curing agent solution to react for 15-20 min;
3) and (3) repeating the step 2) for 2-5 times, washing the obtained block preparation with absolute ethyl alcohol, and drying in an environment of 30-40 ℃ to obtain the environment-friendly slow-release polymer scale inhibitor.
In the scheme, the environment-friendly scale inhibition component, the carrier material and the additive in the step 1) are as follows by mass percent: 30-50% of scale inhibition component, 49-69% of carrier material and 0.2-1% of additive.
In the scheme, the scale inhibition component is one or more of carboxymethyl inulin, polyepoxysuccinic acid powder and polyaspartic acid powder.
In the scheme, the carboxymethyl inulin in the environment-friendly scale inhibition component is prepared by the following method: stirring and dissolving inulin in water, heating to 75-95 ℃, then adding NaOH solution to react for 10-30 min, then adding chloroacetic acid solution, continuing to react for 4-6 h under the condition of water bath at 75-95 ℃, carrying out rotary evaporation on the yellow solution obtained by the reaction at 60-80 ℃ for 15-20 min, washing with anhydrous methanol, stirring uniformly, standing for 4-6 h, filtering, collecting supernatant liquor, carrying out suction filtration, washing light yellow powder obtained by suction filtration with anhydrous methanol, and drying to obtain the carboxymethyl inulin; wherein the mass ratio of inulin, NaOH and chloroacetic acid is 1 (1.4-1.8) to 0.8-1.6.
In the scheme, polyepoxysuccinic acid powder and polyaspartic acid powder are respectively subjected to rotary evaporation at 60-80 ℃ by polyepoxysuccinic acid or polyaspartic acid liquid reagent to be viscous, washed by anhydrous acetone and dried in a constant-temperature environment at 50-80 ℃ to obtain a white powdery medicament.
In the above scheme, the carrier material is polyvinyl alcohol 1788, which is white powder.
In the scheme, the additive is boric acid and is white powdery crystal.
In the scheme, the polymer wall material solution is a uniform emulsion formed by mixing a sodium alginate solution and a gelatin solution according to the volume ratio of (2) - (0-1), then mixing the mixture with a polyvinyl alcohol solution according to the volume ratio of (3-1): 1, and then stirring the mixture at a constant temperature in an environment of 40-70 ℃; wherein the concentration of the sodium alginate solution is 2-5 wt%, the concentration of the polyvinyl alcohol solution is 5-7 wt%, and the concentration of the gelatin solution is 4-8 wt%.
In the scheme, the polyvinyl alcohol is introduced into the wall material solution to promote the tight combination between the wall material and the solid preparation.
In the scheme, the curing agent solution is a hydrochloric acid solution or a calcium chloride solution, and the concentration of the curing agent solution is 10-30 wt%.
The average release rate of the scale inhibition component in the simulated oil field water at 50 ℃ of the environment-friendly slow-release polymer scale inhibitor prepared according to the scheme is 10-20 mg/L/day (the average release mass of the scale inhibition component in each liter of simulated oil field water per day), and the release rate of the scale inhibition component is increased when the temperature is increased.
The environment-friendly slow-release polymer scale inhibitor is suitable for relieving the scaling problem of oil well pipelines and gathering pipelines, the slow release effect is good, the using method is simple, compared with the existing liquid scale inhibitor, the scale inhibitor has the advantages of long effective protection period, high utilization rate of effective components, low scale prevention cost and the like, the prepared solid slow release scale inhibitor is added into a sieve tube at the lower end of an oil well pump in the maintenance period of an oil well, slowly dissolves in the produced liquid along with the outflow of the produced liquid in the oil exploitation process, can play an effective anti-scaling effect in one oil well maintenance period, does not need to be supplemented, reduces the cost problem caused by frequent filling of the liquid scale inhibitor, meanwhile, production stop caused by scaling blockage of the oil well pipeline and the gathering pipeline in a non-overhaul period can be effectively avoided, the production efficiency of the oil field is improved, the service life of oil field pipeline equipment is prolonged, and huge manpower and material resources are saved.
The invention selects the biodegradable environment-friendly scale inhibition component with wide raw material sources, uniformly mixes the component with the carrier material and the additive, and then molds and molds, and then selects the specific polymer wall material to coat the prepared solid scale inhibitor to prepare the environment-friendly slow-release scale inhibitor, so as to meet the actual requirement of adding the scale inhibitor once and maintaining the scale inhibition effect for a long time.
The invention has the beneficial effects that:
1) the scale inhibition component is prepared by taking animal and plant extracts as raw materials, has the characteristic of biodegradability, does not generate polluted residues in the using process, and does not generate any harm to the stratum and the surrounding environment; the selected other raw materials such as polyvinyl alcohol, sodium alginate, gelatin and the like also have the characteristics of rich sources, environmental protection, no pollution, low price and the like in nature, and the prepared environment-friendly slow-release polymer scale inhibitor has low cost and important economic and environmental benefits.
2) The environment-friendly slow-release polymer scale inhibitor has good scale inhibition effect, has high scale inhibition rate at lower dosage, has excellent inhibition effect on carbonate scale and sulfate scale, and can effectively relieve the scale formation problem of a shaft and a gathering pipeline; the scale inhibition rate of the used scale inhibitor is higher than 90 percent when the adding amount of the scale inhibitor is 10 ppm.
3) The environment-friendly slow-release polymer scale inhibitor prepared by the invention has good slow-release effect, effective scale inhibition components in the environment-friendly slow-release polymer scale inhibitor are slowly and uniformly released along with the slow swelling and dissolution of a wall material in the use process, the dosage of the scale inhibitor required to be added in an overhaul period can be estimated in advance according to the actual production condition of an oil well, the environment-friendly slow-release polymer scale inhibitor is placed in a sieve tube at the lower end of an oil well pump in the regular repair and maintenance process of an oil well pipeline and a gathering and transportation pipeline, when produced liquid flows through the sieve tube, the scale inhibition components are slowly dissolved and released to achieve the effect of one-time adding and long-term scale inhibition, so that the environment-friendly slow-release polymer scale inhibitor has long-term effective concentration, the scale inhibition rate in the effective use period (about 90-120 days) is more than 85%.
4) The environment-friendly slow-release polymer scale inhibitor disclosed by the invention is simple in use method, convenient to store and manage, good in slow-release effect, high in scale inhibition efficiency, long in period, non-toxic, harmless, degradable, free of any harm to the stratum and the surrounding environment and environment-friendly.
Detailed Description
For a better understanding of the present invention, the present invention is further described below with reference to the following examples, but the following examples should not be construed as limiting the present invention.
In the following examples, reagents used were commercially available chemical reagents unless otherwise specified.
In the following examples, the preparation method of carboxymethyl inulin comprises the following steps: stirring and dissolving inulin in water, heating to 85 ℃, then adding NaOH solution for reaction for 20min, then adding chloroacetic acid solution, continuing to react for 4h under the condition of water bath at 85 ℃, carrying out rotary evaporation on the yellow solution obtained by the reaction at 75 ℃ for 20min, washing with anhydrous methanol, uniformly stirring, standing for 6h, filtering and collecting supernatant liquid, carrying out suction filtration, washing light yellow powder obtained by suction filtration with anhydrous methanol, and drying to obtain the carboxymethyl inulin (light yellow powder); wherein the mass ratio of the inulin to the NaOH to the chloroacetic acid is 1:1.7: 0.9.
And the polyepoxysuccinic acid powder and the polyaspartic acid powder are respectively subjected to rotary evaporation in a 75 ℃ constant-temperature water bath by polyepoxysuccinic acid or polyaspartic acid liquid reagent to be viscous, washed by anhydrous acetone and dried in a 55 ℃ constant-temperature environment to obtain a white powdery medicament.
The carrier material is powdery 1788 polyvinyl alcohol and white powder; the additive is boric acid and white powdery crystals.
In the following examples, the simulated oil field water used was provided by Daqing oil field oil recovery II plant.
Example 1
An environment-friendly slow-release polymer scale inhibitor, the preparation method comprises the following steps:
1) uniformly mixing a scale inhibition component (carboxymethyl inulin), a carrier material (polyvinyl alcohol) and an additive, wherein the mass percentage of each component is as follows: 38% of carboxymethyl inulin, 61% of carrier material and 1% of additive; stirring at room temperature, adding the mixture into a mold, pressurizing to 10MPa, maintaining the pressure for 20min, opening the mold, ejecting the block preparation, and oven drying;
2) respectively preparing sodium alginate with the mass concentration of 3% and polyvinyl alcohol solution with the mass concentration of 6%, mixing the sodium alginate solution and the polyvinyl alcohol solution according to the volume ratio of 2:1, mechanically stirring for 30min at 40 ℃ to uniformly mix the sodium alginate solution and the polyvinyl alcohol solution to form stable uniform emulsion to be used as polymer wall material solution, preparing hydrogen chloride solution (hydrochloric acid solution) with the mass concentration of 10% to be used as curing agent solution, immersing the solid scale inhibitor which is subjected to compression molding in the wall material solution for reaction for 3min until the solid scale inhibitor is fully coated on the surface of a solid preparation, taking the solid scale inhibitor out and placing the solid scale inhibitor in the curing agent solution for 15min to enable the polymer solution in the wall material to be crosslinked and cured to form a film to be tightly coated on the solid preparation, and repeating the steps to coat the solid scale; and washing the obtained colloidal solid preparation with absolute ethyl alcohol to remove the residual curing agent solution on the surface, repeatedly washing for a plurality of times, evaporating the ethanol on the surface to dryness, and carrying out vacuum drying in a constant temperature environment of 35 ℃ to obtain the environment-friendly slow-release polymer scale inhibitor (solid preparation).
The average release rate of the scale inhibition component of the environment-friendly slow-release polymer scale inhibitor obtained in the embodiment in simulated oilfield water at 50 ℃ is 10 mg/L/day, and the release rate of the scale inhibition component becomes fast when the temperature rises; the scale inhibition rate is 85.1%.
Example 2
An environment-friendly slow-release polymer scale inhibitor, the preparation method comprises the following steps:
1) uniformly mixing scale inhibiting components (carboxymethyl inulin and polyepoxysuccinic acid powder), a carrier material (polyvinyl alcohol) and an additive, wherein the mass percentage of each component is as follows: 25% of carboxymethyl inulin, 25% of polyepoxysuccinic acid powder, 49.5% of carrier material and 0.5% of additive; stirring at room temperature, adding the mixture into a mold, pressurizing to 20MPa, maintaining the pressure for 15min, opening the mold, ejecting the block preparation, and drying;
2) respectively preparing sodium alginate with the mass concentration of 3%, polyvinyl alcohol solution with the mass concentration of 6% and gelatin solution with the mass concentration of 5%, mixing the sodium alginate solution, the gelatin solution and the polyvinyl alcohol solution according to the volume ratio of 2:1:1, mechanically stirring for 30min at 50 ℃ to uniformly mix them to form stable uniform emulsion to be used as polymer wall material solution, preparing calcium chloride solution with the mass concentration of 20% as curing agent solution, immersing the solid scale inhibitor which is subjected to compression molding in the wall material solution for reaction for 3min until the solid scale inhibitor is fully wrapped on the surface of the solid preparation, taking out the solid scale inhibitor and placing the solid scale inhibitor in the curing agent solution for 15min to enable the polymer solution in the wall material to be crosslinked and cured to form a film to be tightly wrapped on the solid preparation, and repeating the steps to wrap the solid scale inhibitor for 2 times; and washing the obtained colloidal solid preparation with absolute ethyl alcohol to remove the residual curing agent solution on the surface, repeating the washing step for a plurality of times, evaporating the surface ethyl alcohol to dryness, and carrying out vacuum drying on the colloidal solid preparation at the constant temperature of 35 ℃ to obtain the environment-friendly slow-release polymer scale inhibitor (solid preparation).
The average release rate of the scale inhibition component of the environment-friendly slow-release polymer scale inhibitor obtained in the embodiment in simulated oilfield water at 50 ℃ is 20 mg/L/day, and the release rate of the scale inhibition component is increased when the temperature is increased; the scale inhibition rate is 91.4%.
Example 3
An environment-friendly slow-release polymer scale inhibitor, the preparation method comprises the following steps:
1) uniformly mixing scale inhibiting components (carboxymethyl inulin and polyaspartic acid powder), a carrier material (polyvinyl alcohol) and an additive, wherein the mass ratio of the carboxymethyl inulin is 20%, the polyaspartic acid powder is 25%, the carrier material amount is 54.5% and the additive amount is 0.5%, fully stirring at room temperature to uniformly mix, pouring the mixture into a mold and pressurizing to 10MPa, and opening the mold to eject a block preparation and dry after maintaining the pressure for 20 min;
2) respectively preparing sodium alginate with mass concentration of 4% and polyvinyl alcohol solution with mass concentration of 7%, mixing the sodium alginate solution and the polyvinyl alcohol solution according to a volume ratio of 1:1, mechanically stirring for 30min at 40 ℃ to uniformly mix the sodium alginate solution and the polyvinyl alcohol solution to form stable emulsion to be used as polymer wall material solution, preparing hydrogen chloride solution with mass concentration of 10% to be used as curing agent solution, immersing the solid scale inhibitor which is subjected to compression molding in the wall material solution for reaction for 5min until the solid scale inhibitor is fully wrapped on the surface of the solid preparation, taking out the solid scale inhibitor and placing the solid scale inhibitor in the curing agent solution for 20min to enable the polymer solution in the wall material to be crosslinked and cured to form a film to be tightly wrapped on the solid preparation, and repeating the steps to wrap the solid scale inhibitor for 3; and washing the obtained colloidal solid preparation with absolute ethyl alcohol to remove the residual curing agent solution on the surface, repeating the steps for a plurality of times, evaporating the surface ethyl alcohol to dryness, and carrying out vacuum drying in a constant temperature environment of 35 ℃ to obtain the environment-friendly slow-release polymer scale inhibitor (solid preparation).
The release rate of the scale inhibition component in simulated oil field water at 50 ℃ of the environment-friendly slow-release polymer scale inhibitor obtained by the implementation is about 16 mg/L/day, and the release rate is increased when the temperature is increased; the scale inhibition rate is 88.6%.
The above description is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various modifications and changes without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method of an environment-friendly slow-release polymer scale inhibitor is characterized by comprising the following steps:
1) uniformly mixing the environment-friendly scale inhibition component, the carrier material and the additive, transferring the mixture into a mold, pressing the mixture for 10 to 20min under the pressure of 10 to 25MPa, and demolding to obtain a block preparation;
2) respectively preparing a polymer wall material solution and a curing agent solution, immersing the obtained block preparation in the polymer wall material solution for reaction for 3-8 min to ensure that the wall material is uniformly coated on the surface of the block preparation, and then taking out the block preparation to be immersed in the curing agent solution for reaction for 15-20 min;
3) repeating the step 2) for 2-5 times, washing the obtained block preparation with absolute ethyl alcohol, and drying at the temperature of 30-40 ℃ to obtain the environment-friendly slow-release polymer scale inhibitor;
the polymer wall material solution is a uniform emulsion formed by mixing a sodium alginate solution and a gelatin solution according to the volume ratio of (2) - (0-1), then mixing the mixture with a polyvinyl alcohol solution according to the volume ratio of (3-1): 1, and then stirring the mixture at a constant temperature in an environment of 40-70 ℃; wherein the concentration of the sodium alginate solution is 2-5 wt%, the concentration of the polyvinyl alcohol solution is 5-7 wt%, and the concentration of the gelatin solution is 4-8 wt%.
2. The preparation method according to claim 1, wherein the environment-friendly scale inhibiting component, the carrier material and the additive in the step 1) are as follows by mass percent: 30-50% of scale inhibition component, 49-69% of carrier material and 0.2-1% of additive.
3. The preparation method according to claim 1, wherein the scale inhibiting component is one or more of carboxymethyl inulin, polyepoxysuccinic acid powder and polyaspartic acid powder.
4. The production method according to claim 3, wherein the carboxymethyl inulin is produced by: stirring and dissolving inulin in water, heating to 75-95 ℃, then adding NaOH solution to react for 10-30 min, then adding chloroacetic acid solution, continuing to react for 4-6 h under the condition of water bath at 75-95 ℃, carrying out rotary evaporation on the yellow solution obtained by the reaction at 60-80 ℃ for 15-20 min, washing with anhydrous methanol, stirring uniformly, standing for 4-6 h, filtering, collecting supernatant liquor, carrying out suction filtration, washing light yellow powder obtained by suction filtration with anhydrous methanol, and drying to obtain the carboxymethyl inulin; wherein the mass ratio of inulin, NaOH and chloroacetic acid is 1 (1.4-1.8) to 0.8-1.6.
5. The preparation method according to claim 3, wherein the polyepoxysuccinic acid powder and the polyaspartic acid powder are prepared by respectively performing rotary evaporation on polyepoxysuccinic acid or polyaspartic acid at 60-80 ℃ to form a viscous state, washing with anhydrous acetone, and drying at a constant temperature of 50-80 ℃ to obtain a white powdery medicament.
6. The method of claim 1, wherein the carrier material is polyvinyl alcohol 1788 in the form of a white powder.
7. The method according to claim 1, wherein the additive is boric acid crystallized in a white powder.
8. The method according to claim 1, wherein the curing agent solution is a hydrochloric acid solution or a calcium chloride solution, and has a concentration of 10 to 30 wt%.
9. The environment-friendly slow-release polymer scale inhibitor prepared by the preparation method of any one of claims 1 to 8 is characterized in that the average release rate of scale inhibition components in a simulated oil field water medium at 50 ℃ of the environment-friendly slow-release polymer scale inhibitor is 10 to 20 mg/L/day.
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| CN108002552B (en) * | 2018-01-11 | 2020-12-11 | 东莞市倍益清环保科技有限公司 | Water purification and scale inhibition material and preparation method thereof |
| CN111320519B (en) * | 2018-12-14 | 2024-01-23 | 中国石油化工股份有限公司 | Separation method and equipment of polymer grade piperylene |
| CN111320520B (en) * | 2018-12-14 | 2024-01-23 | 中国石油化工股份有限公司 | Extractive distillation tower for butadiene separation and separation method |
| CN111318045B (en) * | 2018-12-14 | 2022-12-16 | 中国石油化工股份有限公司 | Extractive distillation column for isoprene separation and separation method |
| CN110157401A (en) * | 2019-05-06 | 2019-08-23 | 中国石油天然气股份有限公司 | A kind of preparation method of controllable long-acting slow-release scale inhibition agent capsules |
| CN111909675B (en) * | 2020-07-17 | 2023-02-28 | 中国石油天然气股份有限公司 | Solid particle scale inhibitor and preparation method thereof |
| CN113249106B (en) * | 2021-05-14 | 2023-01-13 | 中国石油大学(华东) | Solid antiscaling block and preparation method thereof |
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| JP2003010885A (en) * | 2001-06-29 | 2003-01-14 | Nippon Zeon Co Ltd | Scale preventing agent for toilet |
| CN103848509A (en) * | 2014-02-25 | 2014-06-11 | 上海大学 | Hydrogel sustained release system used for corrosion prevention and scale inhibition of industrial water conveying pipeline and preparation method thereof |
| CN103937477A (en) * | 2014-04-29 | 2014-07-23 | 大连理工大学 | Controlled-release solid corrosion inhibitor capable of solving underground corrosion of oil well and preparation method thereof |
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| JP2003010885A (en) * | 2001-06-29 | 2003-01-14 | Nippon Zeon Co Ltd | Scale preventing agent for toilet |
| CN103848509A (en) * | 2014-02-25 | 2014-06-11 | 上海大学 | Hydrogel sustained release system used for corrosion prevention and scale inhibition of industrial water conveying pipeline and preparation method thereof |
| CN103937477A (en) * | 2014-04-29 | 2014-07-23 | 大连理工大学 | Controlled-release solid corrosion inhibitor capable of solving underground corrosion of oil well and preparation method thereof |
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