Stable isotope solid tracer and preparation method thereof

Abstract

The invention belongs to the technical field of preparation of tracers, and provides a stable isotope solid tracer and a preparation method thereof. The preparation method comprises the following steps: under the action of an acid catalyst, mixing CH313COOH and ammonia gas, and reacting to obtain glycine, mixing glycine with water to obtain a glycine solution; a glycine solution and the activated resin microspheres are mixed and then subjected to adsorption treatment, and the stable isotope solid tracer is obtained. The 13C-labeled glycine is used as a tracer ionic compound to be adsorbed on the resin microspheres, the tracer ionic compound is desorbed after sampling, and the content of 13C is tested. The preparation method is low in cost and simple in steps; and the prepared stable isotope solid tracer agent is high in pressure resistance and can be used for inter-well monitoring. In addition, the analysis and test means for inter-well monitoring are simple and easy to popularize.

Description

Technical Field

[0001] The invention relates to the technical field of tracer preparation, and in particular to a stable isotope solid tracer and a preparation method thereof. Background Art

[0002] The principle of oilfield tracer technology is to inject the tracer from the injection well, then take samples in the monitoring well according to certain sampling regulations, monitor the tracer production, analyze the samples taken, obtain the tracer production curve of the monitoring well and perform fitting analysis on it, so as to understand important information such as the flow speed, direction and affected area of ​​the injected water, and also realize quantitative analysis of reservoir properties, such as thickness, permeability and pore throat radius, etc., to provide important data for oilfield exploitation and production.

[0003] Isotope tracers are an important means developed in recent years to describe the heterogeneity and fluidity of inter-well oil layers. Compared with traditional chemical tracers, isotope tracer technology has obvious technological advancement, with many types, high detection sensitivity, good stability and versatility, good compatibility with formation fluids, etc., which can meet the needs of multiple well groups, multiple layers, and multiple tracers in oil fields. Isotope tracers include radioactive isotope tracers and stable isotope tracers. Among them, stable isotopes have the advantages of small dosage, no radioactive hazards, easy operation, high detection accuracy, and no high-temperature conversion. At the same time, they also avoid the safety issues of personnel and the environment during the use of radioactive isotopes. Therefore, how to provide a stable isotope tracer that can be used for inter-well monitoring has become a problem that technicians in this field urgently need to solve. Summary of the invention

[0004] In view of this, the present invention provides a stable isotope solid tracer and a preparation method thereof, the purpose of which is to solve the technical problem of radioactive hazards existing in existing radioactive oil field tracers, and also solve the technical problem of complex detection procedures of existing stable isotope tracers.

[0005] In order to achieve the above object, the present invention adopts the following technical solution:

[0006] The present invention provides a method for preparing a stable isotope solid tracer, comprising the following steps:

[0007] Under the action of acid catalyst, CH3 13 COOH and ammonia are mixed and reacted to obtain glycine; glycine is mixed with water to obtain a glycine solution; the glycine solution is mixed with activated resin microspheres and then adsorbed to obtain a stable isotope solid tracer.

[0008] Furthermore, the acid catalyst includes any one of sulfuric acid, sulfonic acid, phosphoric acid and hydrochloric acid.

[0009] Furthermore, the mass concentration of the acid catalyst is 30-80%.

[0010] Furthermore, the reaction temperature is 100-150° C., the reaction time is 1-10 h, and the reaction pressure is 1-20 MPa.

[0011] Furthermore, the concentration of the glycine solution is 1-5 g / L.

[0012] Furthermore, the temperature of the adsorption treatment is 20-40° C., the time of the adsorption treatment is 30-60 min, and the pH of the adsorption treatment is 6-8.

[0013] Furthermore, the adsorption treatment is accompanied by stirring and shaking, and the rotation speed of the stirring and shaking is 200 to 300 rpm.

[0014] Further, the resin microspheres include D001 resin, D201 resin or D202 resin;

[0015] The specific steps of the activation include: soaking the resin microspheres in ethanol, rinsing with ethanol after soaking, and washing with water after rinsing to complete the activation of the resin microspheres.

[0016] Furthermore, the mass volume ratio of the resin microspheres to the glycine solution is 0.1-1 kg: 1-10 L.

[0017] The present invention also provides a stable isotope solid tracer prepared by the above preparation method.

[0018] It can be seen from the above technical solution that compared with the prior art, the beneficial effects of the present invention are as follows:

[0019] The present invention uses resin microspheres as tracer carriers, which not only have good physical and chemical stability, but also have excellent temperature resistance and wear resistance. The particles are not easy to break and are completely suitable for well monitoring. In addition, the tracer carrier has good adsorption properties, resulting in 13 The low C desorption rate ensures the detection accuracy.

[0020] The present invention will 13 C-labeled glycine was adsorbed on the resin microspheres as a tracer ion compound. After sampling, the tracer ion compound was desorbed and detected by ICP-MS. 13 The C content simplifies the analysis and testing methods for inter-well monitoring and is easy to promote. DETAILED DESCRIPTION

[0021] The present invention provides a method for preparing a stable isotope solid tracer, comprising the following steps:

[0022] Under the action of acid catalyst, CH313 COOH and ammonia are mixed and reacted to obtain glycine; glycine is mixed with water to obtain a glycine solution; the glycine solution is mixed with activated resin microspheres and then adsorbed to obtain a stable isotope solid tracer.

[0023] In the present invention, CH3 13 COOH 13 The C abundance is 20 to 60%, preferably 30 to 50%, and more preferably 40%.

[0024] In the present invention, the acid catalyst includes any one of sulfuric acid, sulfonic acid, phosphoric acid and hydrochloric acid, preferably any one of sulfuric acid, phosphoric acid and hydrochloric acid, and more preferably sulfuric acid or phosphoric acid.

[0025] In the present invention, the mass concentration of the acid catalyst is 30 to 80%, preferably 40 to 70%, and more preferably 50 to 60%.

[0026] In the present invention, CH3 13 The molar ratio of COOH to ammonia is 1:1.

[0027] In the present invention, the reaction temperature is 100-150°C, preferably 110-140°C, and more preferably 120-130°C; the reaction time is 1-10h, preferably 2-8h, and more preferably 4-6h; the reaction pressure is 1-20MPa, preferably 5-18MPa, and more preferably 10-15MPa.

[0028] In the present invention, the concentration of the glycine solution is 1 to 5 g / L, preferably 2 to 4 g / L, and more preferably 3 g / L.

[0029] In the present invention, the temperature of the adsorption treatment is 20-40°C, preferably 25-35°C, and more preferably 30°C; the time of the adsorption treatment is 30-60min, preferably 35-55min, and more preferably 40-50min; the pH of the adsorption treatment is 6-8, preferably 6.5-7.5, and more preferably 7.

[0030] In the present invention, the adsorption treatment is accompanied by stirring and shaking, and the rotation speed of the stirring and shaking is 200 to 300 rpm, preferably 220 to 280 rpm, and more preferably 240 to 260 rpm.

[0031] In the present invention, the resin microspheres include D001 resin, D201 resin or D202 resin, preferably D001 resin or D201 resin, and more preferably D001 resin;

[0032] The specific steps of the activation include: soaking the resin microspheres in ethanol, rinsing with ethanol after the soaking, and washing with water after the rinsing to complete the activation of the resin microspheres; the soaking time is 3 to 8 hours, preferably 4 to 7 hours, and more preferably 5 to 6 hours; the rinsing times are 5 to 10 times, preferably 6 to 9 times, and more preferably 7 to 8 times; the water washing times are 1 to 5 times, preferably 2 to 4 times, and more preferably 3 times; the purpose of activation is to activate the resin microspheres and improve and stabilize the performance of the resin microspheres.

[0033] In the present invention, the mass volume ratio of the resin microspheres to the glycine solution is 0.1-1 kg: 1-10 L, preferably 0.2-0.8 kg: 2-8 L, and more preferably 0.4-0.6 kg: 4-6 L.

[0034] The present invention also provides a stable isotope solid tracer prepared by the above preparation method.

[0035] In the present invention, 13 C-labeled glycine is adsorbed on the resin microspheres as a tracer ion compound, and the tracer ion compound is desorbed after sampling. The desorption steps are as follows: the resin microspheres in the sample are placed in an alcohol solution with a mass concentration of 75%, desorbed for 20 to 40 minutes, preferably 25 to 35 minutes, and more preferably 30 minutes, and then the alcohol solution is detected by ICP-MS. 13 The alcohol solution can destroy the interaction between glycine and the resin, thereby achieving the desorption of the resin with less damage to the resin.

[0036] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0037] Example 1

[0038] The same amount of CH3 13 COOH and ammonia were placed in a reactor, the pressure of the reactor was adjusted to 18 MPa, the temperature was raised to 120°C, and then the reaction was carried out using 50% sulfuric acid as a catalyst. After the reaction for 8 hours, the reaction solution was diluted with water, and glycine was separated by distillation. The glycine was prepared into a glycine solution with a concentration of 5 g / L for later use.

[0039] The D001 resin was soaked in ethanol for 6 hours, then rinsed with ethanol for 8 times, and then washed with water for 5 times to complete the activation; the D001 resin and glycine solution were mixed in a ratio of 1kg:10L, the pH of the mixture was adjusted to 7, and then the mixture was placed in a constant temperature oscillating box (40°C, 220rpm) for adsorption treatment. After 50 minutes of treatment, the stable isotope solid tracer was obtained.

[0040] Example 2

[0041] The same amount of CH3 13 COOH and ammonia were placed in a reactor, the pressure of the reactor was adjusted to 16 MPa, the temperature was raised to 130°C, and then the reaction was carried out using 45% sulfuric acid as a catalyst. After the reaction for 7 hours, the reaction solution was diluted with water, and glycine was separated by distillation. The glycine was prepared into a glycine solution with a concentration of 4 g / L for later use.

[0042] The D201 resin was soaked in ethanol for 7 hours, then rinsed with ethanol for 6 times, and then washed with water for 4 times to complete the activation; the D201 resin and glycine solution were mixed in a ratio of 1kg:8L, the pH of the mixture was adjusted to 7.5, and then the mixture was placed in a constant temperature oscillating box (30°C, 240rpm) for adsorption treatment. After 55 minutes of treatment, the stable isotope solid tracer was obtained.

[0043] Example 3

[0044] The same amount of CH3 13 COOH and ammonia were placed in a reactor, the pressure of the reactor was adjusted to 14 MPa, the temperature was raised to 140°C, and then the reaction was carried out using 55% phosphoric acid as a catalyst. After the reaction for 5 hours, the reaction solution was diluted with water, and glycine was separated by distillation. The glycine was prepared into a glycine solution with a concentration of 3 g / L for later use.

[0045] The D202 resin was soaked in ethanol for 5 hours, then rinsed with ethanol for 9 times, and then washed with water for 3 times to complete the activation; the D202 resin and glycine solution were mixed in a ratio of 1kg:7L, the pH of the mixture was adjusted to 8, and then the mixture was placed in a constant temperature oscillating box (25°C, 250rpm) for adsorption treatment. After 60 minutes of treatment, the stable isotope solid tracer was obtained.

[0046] Example 4

[0047] The same amount of CH3 13 COOH and ammonia were placed in a reactor, the pressure of the reactor was adjusted to 10 MPa, the temperature was raised to 110°C, and then the reaction was carried out using 40% phosphoric acid as a catalyst. After the reaction for 7 hours, the reaction solution was diluted with water, and glycine was separated by distillation. The glycine was prepared into a glycine solution with a concentration of 2 g / L for later use.

[0048] The D001 resin was soaked in ethanol for 4 hours, then rinsed with ethanol for 5 times, and then washed with water for 2 times to complete the activation; the D001 resin and glycine solution were mixed in a ratio of 1 kg:10 L, the pH of the mixture was adjusted to 6.5, and then the mixture was placed in a constant temperature oscillating box (30°C, 260rpm) for adsorption treatment. After 40 minutes of treatment, the stable isotope solid tracer was obtained.

[0049] Example 5

[0050] The same amount of CH3 13 COOH and ammonia were placed in a reactor, the pressure of the reactor was adjusted to 5 MPa, the temperature was raised to 100°C, and then the reaction was carried out using 50% sulfuric acid as a catalyst. After the reaction for 4 hours, the reaction solution was diluted with water, and glycine was separated by distillation. The glycine was prepared into a glycine solution with a concentration of 1 g / L for later use.

[0051] The D001 resin was soaked in ethanol for 4 hours, then rinsed with ethanol for 6 times, and then washed with water for 3 times to complete the activation; the D001 resin and glycine solution were mixed in a ratio of 1kg:10L, the pH of the mixture was adjusted to 6, and then the mixture was placed in a constant temperature oscillating box (40°C, 220rpm) for adsorption treatment. After 50 minutes of treatment, the stable isotope solid tracer was obtained.

[0052] Comparative Example 1

[0053] The same amount of CH3 13 COOH and ammonia were placed in a reactor, the pressure of the reactor was adjusted to 18 MPa, the temperature was raised to 120°C, and then the reaction was carried out using 50% sulfuric acid as a catalyst. After the reaction for 8 hours, the reaction solution was diluted with water, and glycine was separated by distillation. The glycine was prepared into a glycine solution with a concentration of 2.5 g / L for later use.

[0054] D001 resin and glycine solution were mixed at a ratio of 1 kg:10 L, the pH of the mixture was adjusted to 7.5, and then the mixture was placed in a constant temperature oscillating box (40°C, 220 rpm) for adsorption treatment. After 50 minutes of treatment, a stable isotope solid tracer was obtained.

[0055] The adsorption amounts of glycine by the resin microspheres in Examples 1 to 5 and Comparative Example 1 are shown in Table 1.

[0056] Table 1 Adsorption of glycine by resin microspheres

[0057]

[0058] As can be seen from Table 1, the tracer carrier used in the present invention has good adsorption properties, which ensures the subsequent detection accuracy.

[0059] The compressive strength test results of the stable isotope solid tracers of Examples 1 to 5 and Comparative Example 1 are shown in Table 2.

[0060] Table 2 Compressive strength test results of stable isotope solid tracers

[0061]

[0062] It can be seen from Table 2 that the compressive strength of the stable isotope solid tracers prepared by the present invention is above 60 MPa, which can be fully applicable to oil and gas production in medium-deep wells and complex geological production environments.

[0063] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a stable isotope solid tracer, characterized in that: The following steps are involved: Under the action of acid catalyst, CH3 13 COOH and ammonia are mixed and reacted to obtain glycine; glycine is mixed with water to obtain a glycine solution; the glycine solution is mixed with activated resin microspheres and then adsorbed to obtain a stable isotope solid tracer.

2. The preparation method according to claim 1, characterized in that: The acid catalyst includes any one of sulfuric acid, sulfonic acid, phosphoric acid and hydrochloric acid.

3. The preparation method according to claim 2, characterized in that: The mass concentration of the acid catalyst is 30-80%.

4. The preparation method according to any one of claims 1 to 3, characterized in that: The reaction temperature is 100-150° C., the reaction time is 1-10 hours, and the reaction pressure is 1-20 MPa.

5. The preparation method according to claim 4, characterized in that: The concentration of the glycine solution is 1-5 g / L.

6. The preparation method according to claim 2, 3 or 5, characterized in that: The temperature of the adsorption treatment is 20-40° C., the time of the adsorption treatment is 30-60 min, and the pH of the adsorption treatment is 6-8.

7. The preparation method according to claim 6, characterized in that: The adsorption treatment is accompanied by stirring and shaking, and the rotation speed of the stirring and shaking is 200 to 300 rpm.

8. The preparation method according to claim 1, 2, 3, 5 or 7, characterized in that: The resin microspheres include D001 resin, D201 resin or D202 resin; The specific steps of the activation include: soaking the resin microspheres in ethanol, rinsing with ethanol after soaking, and washing with water after rinsing to complete the activation of the resin microspheres.

9. The preparation method according to claim 8, characterized in that: The mass volume ratio of the resin microspheres to the glycine solution is 0.1-1 kg: 1-10 L.

10. The stable isotope solid tracer prepared by the preparation method according to any one of claims 1 to 9.

Images