CN109293831B - High-salt-resistance fluorescent oil field tracer agent and preparation method thereof - Google Patents
High-salt-resistance fluorescent oil field tracer agent and preparation method thereof Download PDFInfo
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- CN109293831B CN109293831B CN201811078214.5A CN201811078214A CN109293831B CN 109293831 B CN109293831 B CN 109293831B CN 201811078214 A CN201811078214 A CN 201811078214A CN 109293831 B CN109293831 B CN 109293831B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
- C08F228/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
Abstract
The invention discloses a preparation method of a salt-tolerant fluorescent oilfield tracer, which comprises the following steps: adding a monomer 1, 4-acid, sodium allylsulfonate, acrylic acid, a solvent and a catalyst into a high-pressure reaction container, uniformly mixing, introducing an inert gas, keeping the pressure of 5-10 MPa, controlling the temperature of 80-120 ℃, and reacting for 1-2 hours to obtain the product; the solvent is an alcohol or a mixture of alcohols; 1, 4-acid: sodium allyl sulfonate: acrylic acid: solvent: the mass ratio of the catalyst is 0.2-0.5: 10: 5-20: 20-50: 0.001 to 0.005; the viscosity-average molecular weight of the salt-tolerant fluorescent oilfield tracer polymer is 500-1000, the maximum fluorescence excitation wavelength is 240nm in a lambda ex mode, and the maximum emission wavelength is 420nm in a lambda em mode. The salt-tolerant fluorescent oilfield tracer prepared by the method has the characteristics of convenience in filling, good fluorescence stability, strong anti-interference capability, excellent salt tolerance and the like, and can be used for automatic detection of oilfield tracers developed by water injection.
Description
Technical Field
The invention relates to the field of oil field chemical additives, in particular to a salt-tolerant fluorescent tracer for oil extraction in an oil field and a preparation method thereof.
Background
At present, most oil fields in China adopt a water injection development mode, an oil field water injection tracing technology is one of important technologies for field production testing, and the principle of the technology is that a tracer agent with a certain concentration is injected from a water injection well, then an oil well around the water well is sampled according to a certain requirement, an oil water sample collected by the oil well is filtered, then the concentration of the tracer agent is measured by taking a water sample, the sample is analyzed according to a tracer agent concentration curve detected by the oil well to obtain a tracer agent output curve, then data fitting is carried out, the communication condition of the oil well and the water well in the water injection development process is reflected through data, the propelling direction, the displacement speed, the swept area, the reservoir heterogeneity, the residual oil saturation distribution and the like of injected water are mastered, and therefore the design of oil well exploitation and. The tracer monitoring result can provide a powerful basis for the adjustment of an oil field development scheme and the formulation of a stimulation measure.
The tracers currently mainly include four types: chemical tracers, mainly inorganic salts, halogenated hydrocarbons and alcohols; a radioisotope tracer; a non-radioactive isotope tracer; a trace element tracer. However, the existing tracers have a plurality of problems, the conventional tracers are greatly influenced by chemical agents such as polymers, the selectable types are few, the injection amount is large, the cost is high, radioactive tracers are harmful to human bodies and difficult to detect, and the like. Therefore, research on novel salt-tolerant oil field tracers is urgent.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a salt-tolerant fluorescent tracer for oil extraction in an oil field and a preparation method thereof. The tracer has good adaptability and selectivity, high testing resolution, no harm to the environment and the health of operators, difficult adsorption in the stratum, and is particularly suitable for the application of high-salt water injection wells.
In order to achieve the aim, the invention adopts the technical scheme that:
the invention provides a salt-tolerant fluorescent tracer for oil extraction in an oil field, which is prepared by the following steps: adding a monomer 1, 4-acid, sodium allylsulfonate, acrylic acid, a solvent and a catalyst into a high-pressure reaction container, uniformly mixing, introducing an inert gas, keeping the pressure of 5-10 MPa, controlling the temperature of 80-120 ℃, and reacting for 1-2 hours to obtain the product; the catalyst is an azo compound, and the solvent is alcohol or a mixture of alcohol; 1, 4-acid: sodium allyl sulfonate: acrylic acid: solvent: the mass ratio of the catalyst is 0.2-0.5: 10: 5-20: 20-50: 0.001 to 0.005;
the viscosity-average molecular weight of the high-salt-resistant fluorescent oil field tracer polymer is 500-1000, the maximum fluorescence excitation wavelength is 240nm in a lambda ex mode, and the maximum emission wavelength is 420nm in a lambda em mode.
The ratio of the 1, 4-acid: sodium allyl sulfonate: acrylic acid: solvent: the mass ratio of the catalyst is 0.1-0.5: 10: 5-20: 20-50: 0.001-0.01, and the optimal proportion is 0.4: 10: 10: 30: 0.003.
the catalyst is preferably azobisisobutyronitrile.
The solvent is selected from alcohol or a mixture of alcohol, the alcohol is ethylene glycol or propylene glycol or a mixture of the ethylene glycol and the propylene glycol, and the ethylene glycol is preferred.
The invention also provides a preparation method of the salt-tolerant fluorescent oil field tracer, which comprises the following steps: under the stirring condition of a closed high-pressure kettle, adding a monomer 1, 4-acid, sodium allylsulfonate, acrylic acid, a solvent and a catalyst into a high-pressure reaction container, uniformly mixing, introducing an inert gas, keeping the pressure of 5-10 MPa, controlling the temperature to be 80-120 ℃, and reacting for 1-2 hours to obtain the catalyst.
The invention has the beneficial effects that: the tracer disclosed by the invention has little influence on the environment, can be injected into a stratum from a water injection well along with injected water, and saves the cost; the actual operation is simple, and only direct addition is needed; the addition of the monomer allyl sulfonate greatly improves the salt resistance of the tracer.
Drawings
FIG. 1 is a graph showing the effect of total hardness on fluorescence intensity at a concentration of 8ppm for a fluorescent oilfield tracer of the present invention.
Detailed Description
The invention is further illustrated by the following application examples.
Example 1: adding 0.4g of 1, 4-acid, 10g of sodium allylsulfonate, 10g of acrylic acid and 30g of ethylene glycol into an autoclave, adding 0.003g of azobisisobutyronitrile, uniformly mixing, introducing nitrogen for replacement for 3 times, introducing nitrogen for maintaining the autoclave pressure at 6MPa, controlling the temperature at 100 ℃, reacting for 1-2 hours, and adding 50g of deionized water to prepare the salt-tolerant fluorescent tracer for oil extraction in the oil field. The weight average molecular weight of the gel was 650 as determined by GPC. The fluorescent tracer prepared in example 1 was subjected to 3-D scanning with a hitachi F-7000 spectrofluorometer, and the fluorescence maximum excitation wavelength λ ex was 240nm and the maximum emission wavelength λ em was 420 nm.
Example 2: adding 0.4g of 1, 4-acid, 8g of sodium allylsulfonate, 12g of acrylic acid and 25g of ethylene glycol into an autoclave, adding 0.003g of azobisisobutyronitrile, uniformly mixing, introducing nitrogen for replacement for 3 times, introducing nitrogen for maintaining the autoclave pressure at 6MPa, controlling the temperature at 100 ℃, reacting for 1-2 hours, and adding 45g of deionized water to prepare the salt-tolerant fluorescent tracer for oil extraction in the oil field. The weight average molecular weight of the gel was 800 as determined by GPC. The fluorescent tracer prepared in example 2 was subjected to 3-D scanning with a hitachi F-7000 spectrofluorometer, and the fluorescence maximum excitation wavelength λ ex was 240nm and the maximum emission wavelength λ em was 420 nm.
Example 3: adding 0.4g of 1, 4-acid, 10g of sodium allylsulfonate, 10g of acrylic acid and 30g of propylene glycol into an autoclave, adding 0.002g of azobisisobutyronitrile, uniformly mixing, introducing nitrogen for replacement for 3 times, introducing nitrogen to keep the autoclave pressure at 8MPa, controlling the temperature at 110 ℃, reacting for 1-2 hours, and adding 50g of deionized water to prepare the salt-tolerant fluorescent tracer for oil extraction in the oil field. The weight average molecular weight of the polycarbonate resin was 850 as determined by GPC. The fluorescent tracer prepared in example 3 was subjected to 3-D scanning with a hitachi F-7000 spectrofluorometer, and the fluorescence maximum excitation wavelength λ ex was 240nm and the maximum emission wavelength λ em was 420 nm.
The maximum excitation wavelength λ ex is 239nm, and the maximum emission wavelength λ em is 355 nm. The relationship between the concentration and the fluorescence intensity of the salt tolerant fluorescent oilfield tracer product obtained in example 1 is tested, and the test data is shown in table 1:
TABLE 1 relationship between fluorescent oilfield tracers and fluorescence intensity
As can be seen from Table 1, the fluorescence intensity of the salt-tolerant fluorescent oilfield tracer is in a linear relationship with the concentration within the range of 1.0-20 ppm, and the detected fluorescence intensity of the salt-tolerant fluorescent oilfield tracer reaches 7.1 when the concentration is 1ppm, so that the salt-tolerant fluorescent oilfield tracer has a strong application prospect.
The maximum excitation wavelength λ ex is 239nm, and the maximum emission wavelength λ em is 355 nm. And (3) inspecting the relation between the fluorescence intensity and the total hardness of the salt-tolerant fluorescent oilfield tracer with the concentration of 8ppm, wherein the test result is shown in figure 1.
As can be seen from fig. 1: the concentration of the salt-tolerant fluorescent oilfield tracer is 8ppm, the total hardness is within the range of 0-400 ppm, the fluorescence intensity is basically unchanged, the variation range is within 5%, and the fluorescence intensity is slightly reduced along with the extension of the retention time; when the concentration is more than 400ppm, the decrease rate increases, and the fluorescence intensity increases slightly with the increase of the retention time.
Through the tests, the salt-tolerant fluorescent oilfield tracer prepared by the method has the advantages of good fluorescence stability, strong salt resistance and strong application value.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical solutions of the present invention in any way. Any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention still fall within the scope of the technical solution of the present invention.
Claims (5)
1. The salt-tolerant fluorescent oilfield tracer is characterized by being prepared by the following steps: uniformly mixing a monomer 1, 4-acid, sodium allylsulfonate, acrylic acid, a solvent and a catalyst in a high-pressure reaction container, introducing an inert gas, keeping the pressure of 5-10 MPa, controlling the temperature of 80-120 ℃, and reacting for 1-2 hours to obtain the product; wherein the catalyst is an azo compound, and the solvent is alcohol or a mixture of alcohol; 1, 4-acid: sodium allyl sulfonate: acrylic acid: solvent: the mass ratio of the catalyst is 0.2-0.5: 10: 5-20: 20-50: 0.001 to 0.005;
the viscosity-average molecular weight of the high-salt-resistant fluorescent oil field tracer polymer is 500-1000, the maximum fluorescence excitation wavelength is 240nm in a lambda ex mode, and the maximum emission wavelength is 420nm in a lambda em mode.
2. The preparation method of the salt-tolerant fluorescent oilfield tracer according to claim 1, which is characterized by comprising the following steps: uniformly mixing a monomer 1, 4-acid, sodium allylsulfonate, acrylic acid, a solvent and a catalyst in a high-pressure reaction container, introducing an inert gas, keeping the pressure of 5-10 MPa, controlling the temperature of 80-120 ℃, and reacting for 1-2 hours to obtain the product; wherein the catalyst is an azo compound, and the solvent is alcohol or a mixture of alcohol; 1, 4-acid: sodium allyl sulfonate: acrylic acid: solvent: the mass ratio of the catalyst is 0.2-0.5: 10: 5-20: 20-50: 0.001 to 0.005.
3. The method according to claim 2, wherein the ratio of the 1, 4-acid: sodium allyl sulfonate: acrylic acid: solvent: the mass ratio of the catalyst is 0.4: 10: 10: 30: 0.003.
4. the process according to claim 2, wherein the catalyst is azobisisobutyronitrile.
5. The method of claim 1, wherein the solvent is ethylene glycol or propylene glycol or a mixture thereof.
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