CN103554126B - The fluorescein derivative preparation method of oil field tracer agent and application - Google Patents

Abstract

The preparation method and application of fluorescein derivatives used as tracers in oil fields. The preparation method first adds fluorescein to a reaction kettle, adds a solvent to dissolve, adds alkali under stirring, and then adds formaldehyde compounds and sulfites with fluorescein, and heats up Reflux, then cool the reactor to room temperature, evaporate the solvent, add salt, mix and grind to obtain the fluorescein derivative of the oil field tracer, and prepare the fluorescein derivative into a solution when used, and inject it into the well to be logged , collect water samples for quantitative analysis, until the above-mentioned fluorescein derivatives cannot be detected in the water samples, because fluorescein has increased the sulfomethyl group after the above-mentioned treatment, enhanced its water solubility, and reduced its solubility in crude oil; At the same time, the sulfomethyl group is a completely ionized group with a strong negative charge, which generates a strong electrostatic repulsion with the negative charge of the hydrated rock in the formation, which greatly reduces the adsorption consumption of fluorescein in the formation, thereby reducing the amount of fluorescein used as a tracer. dosage of the agent.

Description

Preparation method and application of fluorescein derivative of oil field tracer

technical field

The invention relates to the technical field of fluorescein derivatives of tracers used in oil fields, in particular to a preparation method and application of fluorescein derivatives of tracers used in oil fields.

Background technique

Oilfield water injection tracer technology is one of the on-site production test technologies. Its technology is to inject tracer from the injection well, and then take samples from the surrounding production wells according to certain sampling regulations, and monitor the change of the tracer over time, which can guide The design of oil well production and the adjustment in the late stage of oilfield development. Due to the limitation of the reservoir environment, the tracer must meet the three requirements of chemical stability, physical stability and biological stability. For a long time, the most commonly used tracers in oilfield development mainly include chemical tracers and isotope tracers. Although these tracer techniques are widely used in various oilfields, they also have disadvantages to varying degrees.

Fluorescent tracer technology has been widely used in the fields of medicine, biology and water treatment, and the application of fluorescent substances as oilfield tracers, especially in the field of testing the direction of groundwater movement and oil layer heterogeneity between oilfield wells, will be very important. New uses for fluorescent substance applications. There are many substances that can produce fluorescence, most of which are some organic compounds, which can be detected quickly, easily and with high sensitivity by a fluorescence spectrophotometer, which can achieve the purpose of tracing. Fluorescein is the most commonly used fluorescent reagent with high fluorescence efficiency. Under optimized conditions, the linear range of fluorescein detection is 1×10 ^-8 ~1×10 ^-10 mol/L, the detection limit is 7.5×10 ^-11 mol/L, and the emission wavelength is in the range of 500-500 nanometers It has a strong internal content, and is quite different from the fluorescent components in crude oil, so it is not easy to cause interference. However, because fluorescein itself has functional groups such as hydroxyl and carboxyl to form hydrogen bonds and an aromatic ring that is easily soluble in crude oil, it has the disadvantages of high formation adsorption consumption and weak water solubility.

Contents of the invention

In order to overcome the above-mentioned shortcomings of the prior art, the object of the present invention is to provide a preparation method and application of fluorescein derivatives used as oilfield tracers. The obtained products have good water solubility, strong stability, and are not easily adsorbed in formations, and are suitable for practical applications.

In order to achieve the above object, the technical scheme adopted in the present invention is:

A method for preparing a fluorescein derivative of a tracer for oil fields, comprising the following steps:

In the first step, add fluorescein into the reaction kettle, add a solvent with 10-100 times the mass of fluorescein to dissolve, and the solvent is water, methanol, ethanol and their mixtures of industrial grade and above purity;

In the second step, under stirring, add an alkali with a molar ratio of 1:1-2.5 to the fluorescein substance into the reaction kettle, and the alkali is sodium hydroxide, potassium hydroxide, lithium hydroxide, carbonic acid Sodium, potassium carbonate, trimethylamine, triethylamine, pyridine and mixtures thereof;

The third step is to add formaldehyde-containing compounds with a molar ratio of 1-4:1 to the fluorescein substance and sulfites of 1-3:1 to the reaction kettle under stirring, and heat up and reflux for 2-6 hours. Formaldehyde compounds are formaldehyde solution, paraformaldehyde, paraformaldehyde, hexamethylenetetramine and their mixtures of industrial grade and above purity, and sulfites are sodium sulfite, potassium sulfite, ammonium sulfite of industrial grade and above purity and mixtures thereof;

In the fourth step, the reactor is cooled to room temperature, the solvent is evaporated, the salt with 2-20 times the mass of the obtained substance is added, mixed and ground to more than 40 mesh, and the fluorescein derivative of the oil field tracer is obtained, and the salt is Sodium chloride, potassium chloride and their mixtures of industrial grade and above purity.

When in use, the fluorescein derivative is formulated into a solution with a mass concentration of 0.1-10 mg/L, and the solvent used is tap water or self-used oilfield water, which is injected into the well to be measured, and then water samples are collected in possible effective wells every day. Quantitative analysis was carried out by fluorescence analysis until the above-mentioned fluorescein derivatives could not be detected in the water samples taken.

After the above-mentioned treatment, the sulfomethyl group of fluorescein increases its water solubility and reduces its solubility in crude oil; at the same time, the sulfomethyl group is a completely ionized group with strong negative charge, which is compatible with the water in the formation. The negative charge of fossilized rocks produces strong electrostatic repulsion, which greatly reduces the adsorption consumption of fluorescein in the formation, thereby reducing the amount used as a tracer.

detailed description

The present invention will be further described below in conjunction with specific embodiments.

Example 1

A method for preparing a fluorescein derivative of a tracer for oil fields, comprising the following steps:

In the first step, fluorescein is added to the reaction kettle, and a solvent with 10 times the mass of fluorescein is added to dissolve, and the solvent is tap water;

In the second step, add an alkali with a molar ratio of 1:1 to the reaction kettle under stirring, and the alkali is industrial-grade sodium hydroxide;

The third step is to add formaldehyde-containing compounds and 1:1 sulfites with a molar ratio of 1:1 and 1:1 sulfite to the reaction kettle under stirring, and heat up and reflux for 4 hours. The concentration of the formaldehyde-containing compounds is 35% industrial grade formaldehyde solution, the sulfite is industrial grade sodium sulfite;

The fourth step is to cool the reaction kettle to room temperature, evaporate the solvent, add salt twice the mass of the obtained substance, mix and grind to a size above 40 mesh, and obtain a fluorescein derivative of a tracer for oil fields. The salt is an industrial grade of sodium chloride.

When in use, the fluorescein derivative is prepared into a solution with a mass concentration of 0.1 mg/L, and the solvent used is tap water, which is injected into the well to be measured, and then water samples are collected in possible effective wells every day, and quantified by fluorescence analysis Analyze until the above-mentioned fluorescein derivatives cannot be detected in the water samples taken.

Example 2

A method for preparing a fluorescein derivative of a tracer for oil fields, comprising the following steps:

In the first step, add fluorescein into the reaction kettle, add a solvent 15 times the mass of fluorescein to dissolve, and the solvent is industrial grade anhydrous methanol;

In the second step, add an alkali with a molar ratio of 1:1.5 to the fluorescein substance into the reaction kettle under stirring, and the alkali is industrial grade potassium hydroxide;

The third step is to add formaldehyde-containing compounds and 1:1 sulfite in the ratio of 1:1.2 and 1:1 sulfite to the reaction kettle under stirring, and heat up and reflux for 5 hours. The formaldehyde-containing compounds are industrial grade Paraformaldehyde, sulfite is technical grade potassium sulfite;

The fourth step is to cool the reaction kettle to room temperature, evaporate the solvent, add salt with 5 times the mass of the obtained substance, mix and grind to more than 40 mesh, and then obtain the fluorescein derivative of the oil field tracer. The salt is an industrial grade of potassium chloride.

When in use, the fluorescein derivative is prepared into a solution with a mass concentration of 0.2 mg/L, and the solvent used is tap water, which is injected into the well to be tested, and then water samples are collected in possible effective wells every day, and quantified by fluorescence analysis Analyze until the above-mentioned fluorescein derivatives cannot be detected in the water samples taken.

Example 3

A method for preparing a fluorescein derivative of a tracer for oil fields, comprising the following steps:

In the first step, add fluorescein into the reaction kettle, add a solvent 20 times the mass of fluorescein to dissolve, and the solvent is industrial grade absolute ethanol;

In the second step, under stirring, add an alkali with a molar ratio of 1:2 to the fluorescein substance into the reaction kettle, and the alkali is industrial grade lithium hydroxide;

The third step is to add formaldehyde-containing compounds with a molar ratio of 1:1.5 and 1:1.5 sulfite to the reaction kettle under stirring, and heat up and reflux for 3 hours. The formaldehyde-containing compounds are chemically pure Paraformaldehyde, sulfite is industrial grade ammonium sulfite;

The fourth step is to cool the reaction kettle to room temperature, evaporate the solvent, add salt with 8 times the mass of the obtained substance, mix and grind to more than 40 mesh, and obtain the fluorescein derivative of the oil field tracer. The salt is an industrial grade of sodium chloride.

When in use, the fluorescein derivative is prepared into a solution with a mass concentration of 0.5 mg/L, and the solvent used is tap water, which is injected into the well to be measured, and then water samples are collected in possible effective wells every day, and quantified by fluorescence analysis Analyze until the above-mentioned fluorescein derivatives cannot be detected in the water samples taken.

Example 4

A method for preparing a fluorescein derivative of a tracer for oil fields, comprising the following steps:

In the first step, add fluorescein into the reaction kettle, add a solvent 50 times the mass of fluorescein to dissolve, and the solvent is industrial grade 95# ethanol;

In the second step, under stirring, add an alkali with a molar ratio of 1:2.1 to the fluorescein substance into the reaction kettle, and the alkali is chemically pure triethylamine;

The third step is to add formaldehyde-containing compounds with a molar ratio of 1:2 and sulfite of 1:2.1 to the reaction kettle under stirring, and heat up and reflux for 2 hours. The formaldehyde-containing compounds are industrial grade Hexamethylenetetramine, the sulfite is industrial grade sodium sulfite;

The fourth step is to cool the reaction kettle to room temperature, evaporate the solvent, add salt 10 times the mass of the obtained substance, mix and grind to more than 40 mesh, and obtain the fluorescein derivative of the oil field tracer. The salt is an industrial grade of sodium chloride.

When in use, the fluorescein derivative is prepared into a solution with a mass concentration of 1 mg/L, and the solvent used is tap water, which is injected into the well to be tested, and then water samples are collected in possible effective wells every day, and quantitatively analyzed by fluorescence analysis until the above-mentioned fluorescein derivatives cannot be detected in the water samples.

Example 5

A method for preparing a fluorescein derivative of a tracer for oil fields, comprising the following steps:

In the first step, fluorescein is added to the reaction kettle, and a solvent with 80 times the mass of fluorescein is added to dissolve, and the solvent is industrial-grade deionized water;

In the second step, under stirring, add a base with a molar ratio of 1:2.5 to the fluorescein substance into the reaction kettle, and the base is analytically pure pyridine;

In the third step, add formaldehyde-containing compounds and sulfites with a molar ratio of 1:2.5 and 1:2.5 to the reaction kettle under stirring, and heat up and reflux for 4 hours. The formaldehyde-containing compounds are 30% industrial grade formaldehyde solution, the sulfite is industrial grade sodium sulfite;

The fourth step is to cool the reaction kettle to room temperature, evaporate the solvent, add salt 15 times the mass of the obtained substance, mix and grind to more than 40 mesh, and obtain the fluorescein derivative of the oil field tracer. The salt is the mass ratio It is a 1:1 mixture of industrial grade sodium chloride and potassium chloride.

When in use, the fluorescein derivative is prepared into a solution with a mass concentration of 2 mg/L, and the solvent used is tap water, which is injected into the well to be tested, and then water samples are collected in possible effective wells every day, and quantitatively analyzed by fluorescence analysis until the above-mentioned fluorescein derivatives cannot be detected in the water samples.

Example 6

A method for preparing a fluorescein derivative of a tracer for oil fields, comprising the following steps:

In the first step, add fluorescein into the reaction kettle, add a solvent 100 times the mass of fluorescein to dissolve, and the solvent is industrial-grade deionized water;

In the second step, under stirring, adding an alkali with a molar ratio of 1:1.8 to the fluorescein substance in the reaction kettle, the alkali is a mixture of industrial grade sodium hydroxide and potassium carbonate with a mass ratio of 1:1;

The third step is to add formaldehyde-containing compounds and 1:3 sulfite in the molar ratio of fluorescein to the reaction kettle under stirring, and heat up and reflux for 6 hours. The formaldehyde-containing compounds are chemically pure The paraformaldehyde, sulfite is industrial grade sodium sulfite;

The fourth step is to cool the reaction kettle to room temperature, evaporate the solvent, add salt 20 times the mass of the obtained substance, mix and grind to more than 40 mesh, and obtain the fluorescein derivative of the oil field tracer. The salt is an industrial grade of potassium chloride.

When in use, the fluorescein derivative is prepared into a solution with a mass concentration of 10 mg/L, and the solvent used is tap water, which is injected into the well to be tested, and then water samples are collected in possible effective wells every day, and quantitatively analyzed by fluorescence analysis until the above-mentioned fluorescein derivatives cannot be detected in the water samples.

Claims (8)

1. the fluorescein derivative preparation method of oil field tracer agent, is characterized in that, comprise the following steps:

The first step, adds fluorescein in reactor, adds the dissolution with solvents of fluorescein 10-100 times quality, and described solvent is the water of technical grade and above purity, methyl alcohol, ethanol and mixed solution thereof;

Second step, stir in downhill reaction still and add with fluorescein amount of substance than the alkali for 1:1-2.5, described alkali is the sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, salt of wormwood, Trimethylamine 99, triethylamine, pyridine and composition thereof of technical grade and above purity;

3rd step, stirs in downhill reaction still and adds with fluorescein amount of substance than the sulphite containing benzaldehyde compound and 1-3:1 for 1-4:1, temperature rising reflux 2-6 hour, describedcontaining formaldehyde solution, trioxymethylene, paraformaldehyde, hexamethylenetetramine and composition thereof that benzaldehyde compound is technical grade and above purity, sulphite is the S-WAT, potassium sulfite, ammonium sulphite and composition thereof of technical grade and above purity;

4th step, is cooled to room temperature by reactor, boils off solvent, add the salt of gained material 2-20 times of quality, more than mixed grinding to 40 order, namely obtain the fluorescein derivative of oil field tracer agent, described salt is the sodium-chlor, Repone K and composition thereof of technical grade and above purity.

2. the fluorescein derivative preparation method of oil field according to claim 1 tracer agent, it is characterized in that: solution during use, this fluorescein derivative being mixed with mass concentration 0.1-10mg/L, solvent for use is use by oneself water in tap water or oil field, it is being treated that well logging is injected, water sample is gathered by effect well every day subsequently possible, fluorometry is adopted to carry out quantitative analysis, until extraction water sample detection does not go out above-mentioned fluorescein derivative.

3. the fluorescein derivative preparation method of oil field according to claim 1 tracer agent, is characterized in that, comprise the following steps:

The first step, adds fluorescein in reactor, adds the dissolution with solvents of fluorescein 10 times of quality, and described solvent is tap water;

Second step, stir in downhill reaction still and add with fluorescein amount of substance than the alkali for 1:1, described alkali is the sodium hydroxide of technical grade;

3rd step, stir in downhill reaction still and add with fluorescein amount of substance than the sulphite containing benzaldehyde compound and 1:1 for 1:1, temperature rising reflux 4 hours, described containing benzaldehyde compound to be concentration be 35% technical grade formalin, sulphite is technical grade S-WAT;

4th step, is cooled to room temperature by reactor, boils off solvent, adds the salt of gained material 2 times of quality, more than mixed grinding to 40 order, namely obtains the fluorescein derivative of oil field tracer agent, and described salt is the sodium-chlor of technical grade.

4. the fluorescein derivative preparation method of oil field according to claim 1 tracer agent, is characterized in that, comprise the following steps:

The first step, adds fluorescein in reactor, adds the dissolution with solvents of fluorescein 15 times of quality, and described solvent is technical grade anhydrous methanol;

Second step, stir in downhill reaction still and add with fluorescein amount of substance than the alkali for 1:1.5, described alkali is the potassium hydroxide of technical grade;

3rd step, stir in downhill reaction still and add with fluorescein amount of substance than the sulphite containing benzaldehyde compound and 1:1 for 1:1.2, temperature rising reflux 5 hours, described is technical grade paraformaldehyde containing benzaldehyde compound, and sulphite is technical grade potassium sulfite;

4th step, is cooled to room temperature by reactor, boils off solvent, adds the salt of gained material 5 times of quality, more than mixed grinding to 40 order, namely obtains the fluorescein derivative of oil field tracer agent, and described salt is the Repone K of technical grade.

5. the fluorescein derivative preparation method of oil field according to claim 1 tracer agent, is characterized in that, comprise the following steps:

The first step, adds fluorescein in reactor, adds the dissolution with solvents of fluorescein 20 times of quality, and described solvent is technical grade dehydrated alcohol;

Second step, stir in downhill reaction still and add with fluorescein amount of substance than the alkali for 1:2, described alkali is the lithium hydroxide of technical grade;

3rd step, stir in downhill reaction still and add with fluorescein amount of substance than the sulphite containing benzaldehyde compound and 1:1.5 for 1:1.5, temperature rising reflux 3 hours, described is chemical pure trioxymethylene containing benzaldehyde compound, and sulphite is technical grade ammonium sulphite;

4th step, is cooled to room temperature by reactor, boils off solvent, adds the salt of gained material 8 times of quality, more than mixed grinding to 40 order, namely obtains the fluorescein derivative of oil field tracer agent, and described salt is the sodium-chlor of technical grade.

6. the fluorescein derivative preparation method of oil field according to claim 1 tracer agent, is characterized in that, comprise the following steps:

The first step, adds fluorescein in reactor, adds the dissolution with solvents of fluorescein 50 times of quality, and described solvent is technical grade 95# ethanol;

Second step, stir in downhill reaction still and add with fluorescein amount of substance than the alkali for 1:2.1, described alkali is chemical pure triethylamine;

3rd step, stir in downhill reaction still and add with fluorescein amount of substance than the sulphite containing benzaldehyde compound and 1:2.1 for 1:2, temperature rising reflux 2 hours, described is technical grade vulkacit H containing benzaldehyde compound, and sulphite is technical grade S-WAT;

4th step, is cooled to room temperature by reactor, boils off solvent, adds the salt of gained material 10 times of quality, more than mixed grinding to 40 order, namely obtains the fluorescein derivative of oil field tracer agent, and described salt is the sodium-chlor of technical grade.

7. the fluorescein derivative preparation method of oil field according to claim 1 tracer agent, is characterized in that, comprise the following steps:

The first step, adds fluorescein in reactor, adds the dissolution with solvents of fluorescein 80 times of quality, and described solvent is technical grade deionized water;

Second step, stir in downhill reaction still and add with fluorescein amount of substance than the alkali for 1:2.5, described alkali is analytically pure pyridine;

3rd step, stir in downhill reaction still and add with fluorescein amount of substance than the sulphite containing benzaldehyde compound and 1:2.5 for 1:2.5, temperature rising reflux 4 hours, described is the technical grade formalin of mass concentration 30% containing benzaldehyde compound, and sulphite is technical grade S-WAT;

4th step, is cooled to room temperature by reactor, boils off solvent, add the salt of gained material 15 times of quality, more than mixed grinding to 40 order, namely obtain the fluorescein derivative of oil field tracer agent, described salt is mass ratio is the sodium-chlor of 1:1 technical grade and the mixture of Repone K.

8. the fluorescein derivative preparation method of oil field according to claim 1 tracer agent, is characterized in that, comprise the following steps:

The first step, adds fluorescein in reactor, adds the dissolution with solvents of fluorescein 100 times of quality, and described solvent is technical grade deionized water;

Second step, stir in downhill reaction still and add with fluorescein amount of substance than the alkali for 1:1.8, described alkali is mass ratio is the sodium hydroxide of the technical grade of 1:1 and the mixture of salt of wormwood;

3rd step, stir in downhill reaction still and add with fluorescein amount of substance than the sulphite containing benzaldehyde compound and 1:3 for 1:3.5, temperature rising reflux 6 hours, described is chemical pure trioxymethylene containing benzaldehyde compound, and sulphite is technical grade S-WAT;

4th step, is cooled to room temperature by reactor, boils off solvent, adds the salt of gained material 20 times of quality, more than mixed grinding to 40 order, namely obtains the fluorescein derivative of oil field tracer agent, and described salt is the Repone K of technical grade.