CN114594092A - Method for measuring polymer content in oil field produced water - Google Patents
Method for measuring polymer content in oil field produced water Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 139
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 63
- 239000000243 solution Substances 0.000 claims abstract description 262
- 238000006243 chemical reaction Methods 0.000 claims abstract description 156
- 238000002835 absorbance Methods 0.000 claims abstract description 98
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims abstract description 61
- -1 zirconium ion compound Chemical class 0.000 claims abstract description 51
- DIZZDZCUMBBRSG-UHFFFAOYSA-J tetrasodium;2-[[5-[3-[3-[[bis(carboxylatomethyl)amino]methyl]-4-hydroxy-2-methyl-5-propan-2-ylphenyl]-1,1-dioxo-2,1$l^{6}-benzoxathiol-3-yl]-2-hydroxy-6-methyl-3-propan-2-ylphenyl]methyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC1=C(O)C(C(C)C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C(=C(CN(CC([O-])=O)CC([O-])=O)C(O)=C(C(C)C)C=2)C)=C1C DIZZDZCUMBBRSG-UHFFFAOYSA-J 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 239000012086 standard solution Substances 0.000 claims abstract description 19
- 238000004364 calculation method Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000000523 sample Substances 0.000 claims description 53
- 229910052726 zirconium Inorganic materials 0.000 claims description 37
- 239000012088 reference solution Substances 0.000 claims description 35
- 239000012488 sample solution Substances 0.000 claims description 30
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 19
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000005094 computer simulation Methods 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 10
- 239000008213 purified water Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 description 20
- 238000003756 stirring Methods 0.000 description 15
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 12
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 12
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000001913 cellulose Substances 0.000 description 6
- 229920002907 Guar gum Polymers 0.000 description 5
- 239000003637 basic solution Substances 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 5
- 238000011010 flushing procedure Methods 0.000 description 5
- 239000000665 guar gum Substances 0.000 description 5
- 229960002154 guar gum Drugs 0.000 description 5
- 235000010417 guar gum Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 229920013818 hydroxypropyl guar gum Polymers 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 3
- 229940000406 drug candidate Drugs 0.000 description 3
- 239000003777 experimental drug Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- G01—MEASURING; TESTING
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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Abstract
The embodiment of the application discloses a method for measuring the concentration of a polymer in produced water of an oil field, and belongs to the technical field of oil and gas exploitation. The method comprises the following steps: adding a zirconium ion compound and an acid compound into the standard solution to prepare a zirconium ion solution; adding methyl thymol blue into the standard solution to prepare a color developing agent solution; carrying out mixed reaction on the zirconium ion solution and the water produced by the oil field to obtain a first reaction solution; mixing the first reaction solution and the color developing agent solution for reaction to obtain a second reaction solution; reading the absorbance value of the second reaction solution under visible light; the concentration of the polymer in the oilfield produced water is determined based on the absorbance values. In the embodiment of the application, after the absorbance value corresponding to the oil field output water is determined through the oil field output water, the zirconium ion solution and the color developing agent solution, the absorbance value can be brought into a calculation model of a polymer, and the concentration of the polymer in the oil field output water is determined, so that the determination method of the concentration of the polymer in the oil field output water is simplified.
Description
Technical Field
The embodiment of the application relates to the technical field of oil and gas exploitation, in particular to a method for measuring the content of a polymer in produced water of an oil field.
Background
Because polymers such as polyacrylamide and derivatives thereof, cellulose and derivatives thereof, guar gum and derivatives thereof and the like have the advantages of good tackifying property, good suspension property and the like, the polyacrylamide suspension agent is widely applied to various processes in the oilfield exploitation process. For example, polyacrylamide and its derivatives are commonly used in oil displacement and profile control processes in oil fields; cellulose and its derivatives are commonly used in fracturing process processes in oil fields; guar gum and its derivatives are commonly used in well servicing processes in oil fields. To achieve effective tracking of each process, the polymer content of the water produced from each process is typically measured to determine the effectiveness of each process.
In the related art, polyacrylamide and its derivatives are exemplified, and the method is generally performed by gel chromatography, chemiluminescence nitrogen determination, and the like. Gel chromatography and chemiluminescence nitrogen determination methods are difficult to popularize because test instruments are expensive. There is therefore a need for a simpler method of determining polymer content.
Disclosure of Invention
The embodiment of the application provides a method for measuring the concentration of a polymer in produced water of an oil field, which can conveniently determine the concentration of the polymer in the produced water of the oil field. The technical scheme is as follows:
there is provided a method of determining the concentration of a polymer in oilfield produced water, the method comprising:
adding a zirconium ion compound and an acid compound into a standard solution to prepare a zirconium ion solution, wherein the pH value of the zirconium ion solution is more than or equal to 3.5 and less than or equal to 4.5;
adding methyl thymol blue into the standard solution to prepare a color developing agent solution;
mixing and reacting the zirconium ion solution and the oil field produced water according to a first preset proportion, and standing for a first preset time to obtain a first reaction solution, wherein the content of a polymer in the first reaction solution is 0;
mixing the first reaction solution and the color developing agent solution according to a second preset proportion for reaction, and standing for a second preset time to obtain a second reaction solution, wherein the content of zirconium ions in the second reaction solution is 0;
reading an absorbance value of the second reaction solution under visible light by a spectrophotometer;
determining a concentration of the polymer in the oilfield produced water based on the absorbance values and a computational model of the polymer.
Optionally, the adding a zirconium ion compound and an acidic compound to the standard solution to prepare a zirconium ion solution includes:
adding zirconium hydroxide into the standard solution to prepare a zirconium hydroxide solution;
adding hydrochloric acid into the zirconium hydroxide solution to adjust the pH value of the zirconium hydroxide solution;
and taking the zirconium hydroxide solution with the adjusted pH value as the zirconium ion solution.
Optionally, cetyl trimethyl ammonium bromide is also added to the developer solution.
Optionally, the mass ratio of the cetyltrimethylammonium bromide and the methyl thymol blue is 10: 1.
Optionally, the standard solution is distilled or purified water.
Optionally, the wavelength of the visible light is 630 nm.
Optionally, the concentration of zirconium ions in the zirconium ion solution is 100mg/l, the concentration of methyl thymol blue in the developer solution is 400 mg/l, the first preset ratio is 1:1, and the second preset ratio is 10: 1.
Optionally, said determining the concentration of polymer in said oilfield produced water based on said absorbance values and said computational model of polymer comprises:
determining a corresponding target calculation model based on the type of the polymer in the oilfield produced water;
determining the concentration of the polymer in the oilfield produced water based on the absorbance value and the target calculation model.
Optionally, before determining the concentration of the polymer in the oilfield produced water based on the absorbance value and the computational model of the polymer, the method further comprises:
preparing a reference solution and a plurality of sample solutions, wherein the volumes of the reference solution and the sample solutions are the same, the polymer content of the reference solution is 0, and the polymer concentrations of the sample solutions are different;
respectively carrying out mixing reaction on the reference solution and the plurality of sample solutions and the zirconium ion solution according to the first preset proportion, and standing for the first preset time to obtain a first reference reaction solution and a plurality of first sample reaction solutions, wherein the content of polymers in the plurality of first sample reaction solutions is 0;
mixing the first reference reaction solution and the plurality of first sample reaction solutions with the color developing agent solution according to a second preset proportion, and standing for a second preset time to obtain a second reference reaction solution and a plurality of second sample reaction solutions, wherein the contents of zirconium ions in the second reference reaction solution and the plurality of second sample reaction solutions are both 0;
reading, by the spectrophotometer, a reference absorbance value of the second reference reaction solution under the visible light, and sample absorbance values of the plurality of second sample reaction solutions respectively under the visible light;
determining a computational model of the polymer based on the reference absorbance value, the plurality of polymer concentrations, and the plurality of sample absorbance values.
Optionally, the polymer concentrations of the plurality of sample solutions are in an arithmetic series or an equal proportional series.
Optionally, the computational model of the polymer is a first formula as follows:
Y＝K(A-X)+B (1)
wherein in the first formula, Y refers to the concentration of the polymer, K refers to the slope corresponding to the polymer, A refers to the reference absorbance value corresponding to the polymer, and X refers to the absorbance value corresponding to the polymer solution; the B refers to the corresponding intercept of the polymer.
The beneficial effects brought by the technical scheme provided by the embodiment of the application at least comprise:
in the embodiment of the application, based on the reaction of the prepared zirconium ion solution and the oilfield produced water, the content of the polymer in the first reaction solution is 0; based on the reaction of the prepared developer solution and the first reaction solution, the content of zirconium ions in the second reaction solution is 0; and then reading an absorbance value corresponding to the second reaction solution by a spectrophotometer, wherein the absorbance value corresponds to the residual zirconium ions in the first reaction solution, and then bringing the absorbance value into a calculation model of the polymer in the oil field produced water to determine the concentration of the polymer in the oil field produced water, thereby simplifying the determination method of the concentration of the polymer in the oil field produced water.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for determining a polymer concentration in oilfield produced water according to an embodiment of the present disclosure.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the following describes the embodiments of the present application in further detail with reference to the accompanying drawings.
Before explaining the embodiments of the present application in detail, the application scenarios related to the embodiments of the present application are explained first.
Various process steps are typically taken during the production of an oil field to enhance the recovery of hydrocarbons. Such as fracturing, well flushing, flooding and profile control, etc. Different types of polymers are commonly used in the above processes, for example, hydroxymethyl cellulose and its derivatives are commonly used as polymers in fracturing processes, hydroxypropyl guar and its derivatives are commonly used as polymers in well-flushing processes, and polyacrylamide and its derivatives are commonly used as polymers in flooding and profile control processes. In order to determine the effectiveness of each process, the concentration of a polymer in produced water (a well flushing fluid, a fracturing fluid and a flooding profile control fluid) of an oil field in each process is usually detected, and in the related art, when the concentration of the polymer is detected, a testing instrument is high in cost and difficult to popularize. Based on the scene, the embodiment of the application provides a method for measuring the concentration of polymers in produced water of an oil field.
Fig. 1 is a schematic flow chart of a method for determining a polymer concentration in oilfield produced water according to an embodiment of the present disclosure. As shown in fig. 1, the method includes the following steps.
In this application embodiment, for the convenience of the survey of polymer concentration in the oil field output water, can add in the oil field output water and can produce chemical reaction with the polymer, and can be by the compound of quantitative calibration in solution, and then through the indirect measurement to this chemical, realize the survey to polymer concentration. Illustratively, the chemical is a compound containing zirconium ions. The detection of the polymer concentration in the oilfield produced water in combination with the zirconium ion containing compound is explained in detail below.
Step 101: and adding a zirconium ion compound and an acid compound into the standard solution to prepare a zirconium ion solution.
The standard solution is distilled water or purified water, but may be other liquids as long as the liquid does not contain a polymer, and this is not limited in the examples of the present application. The zirconium ion-containing compound is at least one of zirconium hydroxide, zirconyl oxychloride, zirconium oxychloride octahydrate, and the like. The acidic compound is hydrochloric acid, sulfuric acid, or the like, as long as the pH of the zirconium ion reagent solution can be adjusted.
Optionally, adding zirconium hydroxide into the standard solution to prepare a zirconium hydroxide solution; adding hydrochloric acid into the zirconium hydroxide solution to adjust the pH value of the zirconium hydroxide solution; and taking the zirconium hydroxide solution with the adjusted pH value as a zirconium ion solution. Of course, the zirconium ion solution may also be prepared by other methods, which is not limited in the embodiment of the present application.
Wherein the pH value of the prepared zirconium ion solution is more than or equal to 3.5 and less than or equal to 4.5. Of course, the pH of the zirconium ion solution may be other values as long as the zirconium ions in the zirconium ion solution can react with the polymer, and the residual zirconium ions in the solution after the reaction can be calibrated, which is not limited in the embodiment of the present application.
In order to ensure that zirconium ions in the zirconium ion solution fully react with the polymer in the oilfield produced water and remain zirconium ions in the reacted solution so as to be calibrated, the concentration of zirconium ions in the zirconium ion solution is 100 mg/l. Of course, in other embodiments, the concentration of zirconium ions in the zirconium ion solution may be other values as long as the above conditions are satisfied, and this is not limited in this application.
Step 102: and adding methyl thymol blue into the standard solution to prepare a color developing agent solution.
In order to ensure that the methyl thymol blue can effectively label the zirconium ions in the reacted solution when the developer solution is prepared, the concentration of the methyl thymol blue in the developer solution is 400 mg/l. Of course, the concentration of the methyl thymol blue may be other values as long as the above conditions are satisfied, and the present application does not limit the concentration.
Alternatively, cetyltrimethylammonium bromide may also be added when formulating the developer solution.
Wherein, cetyl trimethyl ammonium bromide is used as a surfactant to improve the activity of the methyl thymol blue. And when cetyltrimethylammonium bromide was added, illustratively, the mass ratio of cetyltrimethylammonium bromide and methyl thymol blue was 10: 1.
Of course, the mass ratio of the cetyltrimethylammonium bromide and the methyl thymol blue can be other ratios, which is not limited in the examples of the present application. In addition, after cetyl trimethyl ammonium bromide and methyl thymol blue are added into the standard solution, the standard solution can be fully stirred so as to ensure the uniformity of the color developing agent solution.
Step 103: and mixing and reacting the zirconium ion solution and the produced water of the oil field according to a first preset proportion, and standing for a first preset time to obtain a first reaction solution.
When the zirconium ion solution is mixed with the oil field produced water, the zirconium ions in the zirconium ion solution and the polymer in the oil field produced water are subjected to a cross-linking reaction, so that the polymer in the oil field produced water is fully reacted to generate a zirconium cross-linked polymer gel, the content of the polymer in the first reaction solution obtained after the reaction is 0, and a certain amount of zirconium ions are remained. In the process of reacting the zirconium ion solution with the produced water of the oil field, the zirconium ion solution can be fully stirred so as to ensure the sufficiency of the reaction.
Optionally, the zirconium ion solution and the oilfield produced water can be mixed and reacted according to the ratio of 1:1 by combining the concentration of zirconium ions in the zirconium ion solution. That is, the first predetermined ratio is 1: 1. Of course, the zirconium ion solution and the oilfield produced water may be mixed and reacted in a ratio of 1.1:1, 1.2:1, 1.5:1, etc., as long as the content of the polymer in the first reaction solution after the reaction is ensured to be 0, which is not limited in the examples of the present application.
Step 104: and mixing the first reaction solution and the color developing agent solution according to a second preset proportion for reaction, and standing for a second preset time to obtain a second reaction solution.
When the first reaction solution is mixed with the color developing agent solution, the residual zirconium ions in the first reaction solution and the color developing agent in the color developing agent solution generate a fading reaction, and the content of the zirconium ions in the second reaction solution obtained after the reaction is 0. In the process of reacting the first reaction solution with the color developing agent solution, the first reaction solution and the color developing agent solution can be fully stirred so as to ensure the sufficiency of the reaction.
Alternatively, the first reaction solution and the color developer solution may be mixed and reacted at a ratio of 10:1 in combination with the concentration of zirconium ions in the zirconium ion solution, the concentration of the color developer in the color developer solution, and the mixing ratio of the zirconium ion solution and the oil field produced water described above. That is, the second predetermined ratio is 10: 1. Of course, the first reaction solution and the developer solution may be mixed and reacted at a ratio of 7:1, 8:1, or 9:1, etc., as long as the content of zirconium ions in the second reaction solution after the reaction is ensured to be 0, which is not limited in the examples of the present application.
Step 105: the absorbance value of the second reaction solution in visible light was read by a spectrophotometer.
After the second reaction solution obtained in the above step 104, optionally, distilled water or purified water is used as a reference solution, and then cuvettes respectively containing the reference solution and the second reaction solution are placed in a sample chamber of a spectrophotometer, and an absorbance value of the second reaction solution in a visible light range is read on the spectrophotometer with reference to the reference solution. The absorbance value corresponds to the concentration of zirconium ions remaining in the first reaction solution.
Optionally, the wavelength of visible light is 630 nanometers. Of course, in other embodiments, the wavelength of the visible light is other values, and for example, the wavelength of the visible light is any value from 400 nm to 800 nm.
In the embodiment of the present application, after determining the absorbance value corresponding to the oilfield produced water through step 105, a calculation model of the polymer may be determined. Specifically, this can be achieved by steps 106 to 110 as follows.
The process of determining the polymer calculation model may be performed after step 105, or may be performed after the polymer calculation model is determined in advance and step 105 is performed, which is not limited in this embodiment.
Step 106: a reference solution and a plurality of sample solutions are prepared.
The volumes of the reference solution and the sample solutions are the same, the polymer content of the reference solution is 0, and the polymer concentrations of the sample solutions are different.
Alternatively, the polymer concentrations of the plurality of sample solutions are in an arithmetic series or an equal proportional series.
In the embodiment of the application, when the reference solution and the plurality of sample solutions are configured, in order to ensure that the reference solution and the plurality of sample solutions have referential property, the reference solution and the plurality of sample solutions are configured by using the same basic solution, and in order to ensure that the determined calculation model is more practical, the basic solution can select blank water which is produced in an oil field and does not contain polymers as the basic solution. Of course, since the blank water is difficult to obtain, the standard solution described above may be used as the base solution, which is not limited in the examples of the present application.
Illustratively, when the polymer is polyacrylamide and its derivatives, blank water without polyacrylamide produced by oil fields in oil displacement and profile control processes can be used as a base solution; when the polymer is guar gum and derivatives thereof, blank water which is produced in an oil field in a well flushing process and does not contain hydroxypropyl guar gum can be used as a base solution; when the polymer is cellulose and its derivatives, the blank water produced in the oil field in the fracturing process without hydroxymethyl cellulose can be used as the base solution.
In the embodiment of the application, one part of the basic solution can be directly used as a reference solution, and the same type of polymers with different amounts can be added into other parts of the basic solution to obtain a plurality of sample solutions
Of course, when a plurality of sample solutions are prepared, a plurality of sample solutions may be prepared by preparing a polymer reference solution in advance and then diluting the polymer reference solution, which is not limited in the examples of the present application.
Step 107: and respectively mixing and reacting the reference solution and the plurality of sample solutions with the zirconium ion solution according to a first preset proportion, and standing for a first preset time to obtain a first reference reaction solution and a plurality of first sample reaction solutions.
Wherein the polymer content in each of the plurality of first sample reaction solutions is 0. For a specific implementation process of step 107, reference may be made to step 103, which is not described in detail in this embodiment of the application.
Step 108: and mixing the first reference reaction solution and the plurality of first sample reaction solutions with the color developing agent solution according to a second preset proportion, and standing for a second preset time to obtain a second reference reaction solution and a plurality of second sample reaction solutions.
Wherein the contents of zirconium ions in the second reference reaction solution and the plurality of second sample reaction solutions are both 0. For a specific implementation process of step 107, reference may be made to step 103, which is not described in detail in this embodiment of the application.
Step 109: reading, by a spectrophotometer, a reference absorbance value of the second reference reaction solution under visible light, and sample absorbance values of the plurality of second sample reaction solutions respectively under visible light.
For the specific implementation process of reading the reference absorbance value of the second reference solution and reading the absorbance value of the second sample reaction solution in step 109, reference may be made to the process of reading the absorbance value of the second reaction solution in step 105, which is not described in detail in this embodiment of the present application.
In conjunction with the above description, the reference absorbance value corresponds to the concentration of zirconium ions in the first reference reaction solution, and the sample absorbance value corresponds to the concentration of zirconium ions in the first sample reaction solution.
Step 110: a computational model of the polymer is determined based on the reference absorbance value, the plurality of polymer concentrations, and the plurality of sample absorbance values.
As can be seen from the above description, the absorbance difference between the reference absorbance and the sample absorbance corresponds to the concentration of zirconium ions reacting with the polymer in the sample solution, i.e., the absorbance difference corresponds to the concentration of the polymer in the sample solution. Therefore, the absorbance difference between the reference absorbance value and the absorbance values of the multiple samples can be determined firstly, and the multiple absorbance differences are obtained and correspond to the multiple polymer concentrations one by one. And then, determining each absorbance difference value and a corresponding coordinate point corresponding to the polymer concentration by taking the absorbance difference value as an abscissa and the polymer concentration as an ordinate, and further fitting the plurality of coordinate points to obtain a linear equation taking the absorbance difference value as an independent variable and the polymer concentration as a dependent variable.
Wherein, the absorbance difference value can be replaced by a reference absorbance value and an absorbance value corresponding to the polymer solution. At this time, since the reference absorbance value is constant, the independent variable of the linear equation is the absorbance value corresponding to the polymer solution, and the dependent variable is the polymer concentration of the polymer solution.
Alternatively, the calculation model of the polymer is a first formula as follows:
Y＝K(A-X)+B (1)
in the first formula, Y refers to the concentration of the polymer, K refers to the slope corresponding to the polymer, A refers to the reference absorbance value corresponding to the polymer, and X refers to the absorbance value corresponding to the polymer solution; b refers to the corresponding intercept of the polymer.
Step 111: the concentration of the polymer in the oilfield produced water is determined based on the absorbance values and a computational model of the polymer.
In combination with the above description, the polymer may be any one of polyacrylamide and its derivatives, guar gum and its derivatives, and cellulose and its derivatives, and in this case, in order to determine the concentration of the polymer, a corresponding target calculation model may be determined based on the type of the polymer in the produced water of the oil field; and then determining the concentration of the polymer in the produced water of the oil field based on the absorbance value and the target calculation model.
In the embodiment of the application, calculation models of different types of polymers can be determined through a reference solution, a plurality of sample solutions, a zirconium ion solution and a color developing agent solution which are configured in advance, so that the content of the polymer in a first reaction solution is 0 based on the reaction of the prepared zirconium ion solution and the produced water of the oil field; based on the reaction of the prepared developer solution and the first reaction solution, the content of zirconium ions in the second reaction solution is 0; and then reading an absorbance value corresponding to the second reaction solution by a spectrophotometer, wherein the absorbance value corresponds to the residual zirconium ions in the first reaction solution, and then bringing the absorbance value into a calculation model corresponding to the polymer in the oilfield produced water to determine the concentration of the polymer in the oilfield produced water, thereby simplifying the determination method of the concentration of the polymer in the oilfield produced water.
Next, the embodiments of the present application will be explained by showing three examples.
Example 1: detecting the concentration of polyacrylamide and its derivatives in oil field produced water in oil displacement profile control process
Experimental drugs: zirconium oxychloride octahydrate, analytically pure; cetyl trimethylammonium bromide, analytically pure; methyl thymol blue, indicator; polyacrylamide, analytically pure.
The method for detecting the concentration of polyacrylamide and derivatives thereof in the oilfield produced water comprises the following operation steps:
(1) preparing a zirconium ion reagent solution with a reduced zirconium ion concentration of 100mg/l by using distilled water and zirconium oxychloride octahydrate, and adjusting the pH of the zirconium ion reagent solution to 4 by using hydrochloric acid with a concentration of 10% to obtain the zirconium ion solution.
(2) And preparing a developer solution with the cetyl trimethyl ammonium bromide and the methyl thymol blue by using distilled water, wherein the concentration of the methyl thymol blue is 400 mg/L, and the mass ratio of the cetyl trimethyl ammonium bromide to the methyl thymol blue is 10: 1.
(3) And (2) taking 20.0 ml of oilfield produced water, adding 20.0 ml of the zirconium ion solution prepared in the step (1), stirring and standing for 15 minutes to obtain a first reaction solution, wherein the content of the polymer in the first reaction solution is 0.
(4) And (3) adding 4.0 ml of the color developing agent solution prepared in the step (2) into the first reaction solution, uniformly stirring and standing for 10 minutes to obtain a second reaction solution, wherein the content of zirconium ions in the second reaction solution is 0.
(5) The absorbance value 0.40102 of the second reaction solution at a wavelength of 630 nm was read under a spectrophotometer.
(6) Preparing a polyacrylamide reference solution with the concentration of 2000 mg/L by using blank water which is produced by an oil field and does not contain polymers, then sequentially adding 0.25 ml, 0.5 ml, 1.0 ml and 2.0 ml of the polyacrylamide reference solution into 4 beakers, and sequentially adding 19.75 ml, 19.5 ml, 19.0 ml and 18.0 ml of blank water; then fully stirring to obtain 4 sample solutions with the polyacrylamide concentrations of 25mg/L, 50mg/L, 100mg/L and 200 mg/L; then 20 ml of blank water was added as a reference solution in a fifth beaker.
(7) And (3) respectively adding 20 ml of the zirconium ion solution prepared in the step (1) into the 4 cups of sample solution and one cup of reference solution obtained in the step (3), fully stirring and standing for 15 minutes to obtain 4 cups of first sample reaction solution and one cup of first reference reaction solution, wherein the content of the polymer in the 4 cups of first sample reaction solution and the content of the polymer in the one cup of first reference reaction solution are both 0.
(8) And (3) adding 4.0 ml of developer solution into each of the 4 cups of first sample reaction solution and the one cup of first reference reaction solution in the step (4), fully stirring, and standing for 10 minutes to obtain 4 cups of second sample reaction solution and one cup of second reference reaction solution, wherein the content of zirconium ions in the 4 cups of second sample reaction solution and the one cup of second reference reaction solution is 0.
(9) Respectively reading the sample absorbance values of 4 cups of the second sample reaction solution at the wavelength of 630 nm and the reference absorbance value of one cup of the second reference reaction solution at the wavelength of 630 nm on a spectrophotometer to obtain the following absorbance values:
TABLE 1
| Polymer concentration (mg/l) | 0 | 25 | 50 | 100 | 200 |
| Absorbance value (A) | 0.001 | 0.09182 | 0.17232 | 0.32492 | 0.63182 |
(10) And drawing a standard curve of the polyacrylamide concentration by taking the absorbance difference between the reference absorbance value and the sample absorbance value as an abscissa and the polyacrylamide concentration as an ordinate. The standard equation obtained by linear fitting is as follows:
Y1＝-319.8(A1-X1)+237.09
wherein, Y1Refers to the concentration of polyacrylamide, A1Refers to the corresponding reference absorbance value, X, of the polyacrylamide solution1Refers to the absorbance value corresponding to the polyacrylamide solution.
(11) And (4) substituting the absorbance value read in the step (5) into the standard equation to obtain the concentration of the polyacrylamide and the derivative thereof in the oilfield produced water to be 125.0 mg/L.
Example 2: detecting the concentration of hydroxypropyl guar gum in the produced water of oilfield in the fracturing process
Experimental drugs: zirconium hydroxide, analytically pure; cetyl trimethylammonium bromide, analytically pure; methyl Thymol Blue (MTB), indicator; hydroxypropyl guar, analytically pure.
The method for detecting the concentration of the hydroxypropyl guar gum in the produced water of the oil field comprises the following operation steps:
(1) preparing a zirconium ion reagent solution with a reduced zirconium ion concentration of 100mg/l by using distilled water and zirconium hydroxide, and adjusting the pH of the zirconium ion reagent solution to 4 by using hydrochloric acid with a concentration of 10% to obtain the zirconium ion solution.
(2) And preparing a developer solution with the cetyl trimethyl ammonium bromide and the methyl thymol blue by using distilled water, wherein the concentration of the methyl thymol blue is 400 mg/L, and the mass ratio of the cetyl trimethyl ammonium bromide to the methyl thymol blue is 10: 1.
(3) And (3) taking 20.0 ml of oilfield produced water, adding 20.0 ml of the zirconium ion solution prepared in the step (1), stirring and standing for 15 minutes to obtain a first reaction solution, wherein the content of the polymer in the first reaction solution is 0.
(4) And (3) adding 4.0 ml of the color developing agent solution prepared in the step (2) into the first reaction solution, uniformly stirring and standing for 30 minutes to obtain a second reaction solution, wherein the content of zirconium ions in the second reaction solution is 0.
(5) The absorbance value 0.4777 of the second reaction solution at a wavelength of 630 nm was read under a spectrophotometer.
(6) Preparing a hydroxypropyl guar reference solution with the concentration of 2000 mg/L by using blank water which is produced in an oil field and does not contain polymers, sequentially adding 0.25 ml, 0.5 ml, 1.0 ml and 2.0 ml of hydroxypropyl guar reference solution into 4 beakers, and sequentially adding 19.75 ml, 19.5 ml, 19.0 ml and 18.0 ml of blank water; then fully stirring to obtain 4 sample solutions with the hydroxypropyl guar gum concentration of 25mg/L, 50mg/L, 100mg/L and 200 mg/L; then 20 ml of blank water was added as a reference solution in a fifth beaker.
(7) And (3) respectively adding 20 ml of the zirconium ion solution prepared in the step (1) into the 4 cups of sample solution and one cup of reference solution obtained in the step (3), fully stirring and standing for 15 minutes to obtain 4 cups of first sample reaction solution and one cup of first reference reaction solution, wherein the content of the polymer in the 4 cups of first sample reaction solution and the content of the polymer in the one cup of first reference reaction solution are both 0.
(8) And (3) adding 4.0 ml of developer solution into each of the 4 cups of first sample reaction solution and the one cup of first reference reaction solution in the step (4), fully stirring, and standing for 30 minutes to obtain 4 cups of second sample reaction solution and one cup of second reference reaction solution, wherein the content of zirconium ions in the 4 cups of second sample reaction solution and the one cup of second reference reaction solution is 0.
(9) Respectively reading the sample absorbance values of 4 cups of the second sample reaction solution at the wavelength of 630 nm and the reference absorbance value of one cup of the second reference reaction solution at the wavelength of 630 nm on a spectrophotometer, and obtaining the absorbance values as the following table 2:
TABLE 2
| Polymer concentration (mg/l) | 0 | 25 | 50 | 100 | 200 |
| Absorbance value (A) | 0 | 0.09169 | 0.1578 | 0.3201 | 0.6191 |
(10) And drawing a standard curve of the hydroxypropyl guar concentration by taking the absorbance difference between the reference absorbance value and the sample absorbance value as an abscissa and taking the hydroxypropyl guar concentration as an ordinate. The standard equation obtained by linear fitting is as follows:
Y2＝-325.05(A2-X2)+231.73
wherein, Y2Is the concentration of hydroxypropyl guar A2Is a reference absorbance value, X, corresponding to hydroxypropyl guar2Refers to the corresponding absorbance value of the hydroxypropyl guar solution.
(11) And (5) substituting the absorbance value read in the step (5) into the standard equation to obtain that the concentration of the guar gum and the derivative thereof in the produced water of the oil field is 152.0 mg/L.
Example 3: detecting the concentration of hydroxymethyl cellulose in oil field produced water in a well-flushing process
Experimental drugs: zirconium oxychloride octahydrate, analytically pure; cetyl trimethylammonium bromide, analytically pure; methyl thymol blue, indicator; hydroxymethyl cellulose, analytically pure.
The detection method of the concentration of the hydroxymethyl cellulose in the produced water of the oil field comprises the following operation steps:
(1) preparing a zirconium ion reagent solution with a reduced zirconium ion concentration of 100mg/l by using distilled water and zirconium oxychloride octahydrate, and adjusting the pH of the zirconium ion reagent solution to 4 by using hydrochloric acid with a concentration of 10% to obtain the zirconium ion solution.
(2) And a developer solution containing cetyltrimethylammonium bromide and methyl thymol blue at a concentration of 400 mg/l was prepared with distilled water.
Wherein the mass ratio of the hexadecyl trimethyl ammonium bromide to the methyl thymol blue is 10: 1.
(3) And (3) taking 20.0 ml of oilfield produced water, adding 20.0 ml of the zirconium ion solution prepared in the step (1), stirring and standing for 15 minutes to obtain a first reaction solution, wherein the content of the polymer in the first reaction solution is 0.
(4) And (3) adding 4.0 ml of the color developing agent solution prepared in the step (2) into the first reaction solution, uniformly stirring and standing for 15 minutes to obtain a second reaction solution, wherein the content of zirconium ions in the second reaction solution is 0.
(5) The absorbance value 0.35522 of the second reaction solution at a wavelength of 630 nm was read under a spectrophotometer.
(6) Preparing a hydroxymethylcellulose reference solution with the concentration of 2000 mg/L by using blank water which is produced by an oil field and does not contain polymers, sequentially adding 0.25 ml, 0.5 ml, 1.0 ml and 2.0 ml of the hydroxymethylcellulose reference solution into 4 beakers, and sequentially adding 19.75 ml, 19.5 ml, 19.0 ml and 18.0 ml of blank water; then fully stirring to obtain 4 sample solutions with the hydroxymethyl cellulose concentration of 25mg/L, 50mg/L, 100mg/L and 200 mg/L; then 20 ml of blank water was added as a reference solution in a fifth beaker.
(7) And (3) respectively adding 20 ml of the zirconium ion solution prepared in the step (1) into the 4 cups of sample solution and one cup of reference solution obtained in the step (3), fully stirring and standing for 15 minutes to obtain 4 cups of first sample reaction solution and one cup of first reference reaction solution, wherein the content of the polymer in the 4 cups of first sample reaction solution and the content of the polymer in the one cup of first reference reaction solution are both 0.
(8) And (3) adding 4.0 ml of developer solution into each of the 4 cups of first sample reaction solution and the one cup of first reference reaction solution in the step (4), fully stirring, and standing for 15 minutes to obtain 4 cups of second sample reaction solution and one cup of second reference reaction solution, wherein the content of zirconium ions in the 4 cups of second sample reaction solution and the one cup of second reference reaction solution is 0.
(9) Respectively reading the sample absorbance values of 4 cups of the second sample reaction solution at the wavelength of 630 nm and the reference absorbance value of one cup of the second reference reaction solution at the wavelength of 630 nm on a spectrophotometer, and obtaining the following absorbance values:
TABLE 3
| Polymer concentration (mg/l) | 0 | 25 | 50 | 100 | 200 |
| Absorbance value (A) | 0.00812 | 0.10782 | 0.20032 | 0.35304 | 0.66734 |
(10) And drawing a standard curve of the concentration of the hydroxymethyl cellulose by taking the absorbance difference between the reference absorbance value and the sample absorbance value as an abscissa and the concentration of the hydroxymethyl cellulose as an ordinate. The standard equation obtained by linear fitting is as follows:
Y3＝-307.15(A3-X3)+201.21
wherein Y is3Refers to the concentration of hydroxymethylcellulose, A3Is a reference absorbance value, X, corresponding to hydroxymethyl cellulose3Refers to the corresponding absorbance value of the hydroxymethyl cellulose solution.
(11) And (4) substituting the absorbance value read in the step (5) into the standard equation to obtain that the concentration of the cellulose and the derivatives thereof in the oilfield produced water is 102.0 mg/L.
The above description is only an alternative embodiment of the present application and should not be construed as limiting the present application, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (11)
1. A method for determining the concentration of a polymer in oilfield produced water, the method comprising:
adding a zirconium ion compound and an acid compound into a standard solution to prepare a zirconium ion solution, wherein the pH value of the zirconium ion solution is more than or equal to 3.5 and less than or equal to 4.5;
adding methyl thymol blue into the standard solution to prepare a color developing agent solution;
mixing and reacting the zirconium ion solution and the oil field produced water according to a first preset proportion, and standing for a first preset time to obtain a first reaction solution, wherein the content of a polymer in the first reaction solution is 0;
mixing the first reaction solution and the color developing agent solution according to a second preset proportion for reaction, and standing for a second preset time to obtain a second reaction solution, wherein the content of zirconium ions in the second reaction solution is 0;
reading an absorbance value of the second reaction solution under visible light by a spectrophotometer;
determining a concentration of the polymer in the oilfield produced water based on the absorbance values and a computational model of the polymer.
2. The method of claim 1, wherein the adding of the zirconium ion compound and the acidic compound to the standard solution to prepare the zirconium ion solution comprises:
adding zirconium hydroxide into the standard solution to prepare a zirconium hydroxide solution;
adding hydrochloric acid into the zirconium hydroxide solution to adjust the pH value of the zirconium hydroxide solution;
and taking the zirconium hydroxide solution with the adjusted pH value as the zirconium ion solution.
3. The method of claim 1 wherein cetyl trimethylammonium bromide is also added to the developer solution.
4. A method according to claim 3, wherein the mass ratio of cetyltrimethylammonium bromide to methyl thymol blue is 10: 1.
5. The method of any one of claims 1 to 4, wherein the standard solution is distilled or purified water.
6. The method of claim 1, wherein the visible light has a wavelength of 630 nanometers.
7. The method of claim 1, wherein the concentration of zirconium ions in the zirconium ion solution is 100mg/l, the concentration of methyl thymol blue in the developer solution is 400 mg/l, the first predetermined ratio is 1:1, and the second predetermined ratio is 10: 1.
8. The method of claim 1, wherein said determining a concentration of a polymer in the oilfield produced water based on the absorbance value and the computational model of the polymer comprises:
determining a corresponding target calculation model based on the type of the polymer in the oilfield produced water;
determining the concentration of the polymer in the oilfield produced water based on the absorbance value and the target calculation model.
9. The method of claim 1, wherein prior to determining the concentration of the polymer in the oilfield produced water based on the absorbance value and the computational model of the polymer, further comprising:
preparing a reference solution and a plurality of sample solutions, wherein the volumes of the reference solution and the sample solutions are the same, the polymer content of the reference solution is 0, and the polymer concentrations of the sample solutions are different;
respectively carrying out mixing reaction on the reference solution and the plurality of sample solutions and the zirconium ion solution according to the first preset proportion, and standing for the first preset time to obtain a first reference reaction solution and a plurality of first sample reaction solutions, wherein the content of polymers in the plurality of first sample reaction solutions is 0;
mixing the first reference reaction solution and the plurality of first sample reaction solutions with the color developing agent solution according to a second preset proportion, and standing for a second preset time to obtain a second reference reaction solution and a plurality of second sample reaction solutions, wherein the contents of zirconium ions in the second reference reaction solution and the plurality of second sample reaction solutions are both 0;
reading, by the spectrophotometer, a reference absorbance value of the second reference reaction solution under the visible light, and sample absorbance values of the plurality of second sample reaction solutions respectively under the visible light;
determining a computational model of the polymer based on the reference absorbance value, the plurality of polymer concentrations, and the plurality of sample absorbance values.
10. The method of claim 9, wherein the polymer concentrations of the plurality of sample solutions are in an arithmetic or proportional series.
11. The method of claim 9, wherein the computational model of the polymer is a first formula as follows:
Y＝K(A-X)+B (1)
in the first formula, Y refers to the concentration of the polymer, K refers to the slope corresponding to the polymer, A refers to the reference absorbance value corresponding to the polymer, and X refers to the absorbance value corresponding to the polymer solution; the B refers to the intercept corresponding to the polymer.
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