CN111595963A - Method for measuring hydrolysis degree of partially hydrolyzed polyacrylamide in oil-gas field chemical flooding output fluid - Google Patents
Method for measuring hydrolysis degree of partially hydrolyzed polyacrylamide in oil-gas field chemical flooding output fluid Download PDFInfo
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- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8624—Detection of slopes or peaks; baseline correction
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N2030/042—Standards
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Abstract
The invention discloses a method for measuring the hydrolysis degree of partially hydrolyzed polyacrylamide in chemical flooding output fluid of an oil-gas field. The determination method comprises the following steps: s1, preparing hydrolysis degree standard samples of partially hydrolyzed polyacrylamide with different hydrolysis degrees, and calibrating the hydrolysis degree; s2, preparing a series of partially hydrolyzed polyacrylamide standard solutions; s3, drawing a relation curve between the chromatographic peak area or peak height of the partially hydrolyzed polyacrylamide standard solution and the concentration of the partially hydrolyzed polyacrylamide according to the measurement data; s5, determining a sample to be detected by adopting the same method as the determination of the partially hydrolyzed polyacrylamide standard solution, and calculating the slope kx of a straight line; and S6, finding out the corresponding hydrolysis degree on the curve according to the kx value of the sample to be detected or calculating by using a relational expression. The technical scheme of the invention is an effective method for rapidly determining the hydrolysis degree of partially hydrolyzed polyacrylamide in a chemical flooding system under the conditions of coexisting interferents and a small amount of samples.
Description
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a method for measuring the hydrolysis degree of partially hydrolyzed polyacrylamide in chemical flooding output fluid of an oil-gas field.
Background
Polyacrylamide (PAM) is a synthetic water-soluble high polymer with the largest global use amount and the widest application, polyacrylamide and derivatives thereof have wide application in industrial and agricultural production, and are mainly applied to the fields of pulping and papermaking, water treatment, oil-gas field exploitation, mineral separation and the like in China, China is a large country for producing polyacrylamide, and the yield of polyacrylamide is 26 × 10 in 2006-20154t increases to 85 × 104t, and demand has increased year by year. The molecular structure of polyacrylamide is easy to change, amide groups on the molecular chain are easy to hydrolyze to become carboxylic acid (sodium) and become partially hydrolyzed polyacrylamide(HPAM), the degree of hydrolysis is the percentage of the number of acrylic acid (sodium) chain links in the total number of chain links, is the main parameter for representing the HPAM molecular structure, and is also an important index for controlling the quality of HPAM products, and the degree of hydrolysis directly influences the solution performance and the stability thereof. Changes in the degree of hydrolysis of HPAM in subterranean hydrocarbon reservoirs are related to the physicochemical environment, temperature, time, etc. to which they are subjected. At present, the hydrolysis degree measuring method is mainly used for product quality control of factories and product quality inspection of users. The early nitrogen determination method based on elemental composition analysis measures the total nitrogen content in a polyacrylamide sample to determine the degree of hydrolysis of polyacrylamide. Such as the classical Kjeldahl method (GB/T5009.5), but the operation is relatively complicated. The nitrogen content can be rapidly determined by an organic element analyzer (GB/T19143), because urea or thiourea added in the industrial HPAM production process has influence on the analysis result of the nitrogen content, and therefore, the urea or the thiourea must be removed before sample preparation and analysis. The hydrochloric acid titration method using methyl orange-indigo disulfonate as indicator is simple and easy to implement, so that it is widely used, and is defined as national standard determination method (GB 12005.6), and is applicable to detection of powdered or colloidal hydrolyzed polyacrylamide products obtained by different polymerization methods, and its colour change determination at end point is difficult, then on the basis of said method the conductance titration method (CN1415956A) and potentiometric titration method (CN109557247A) are developed, and the titration end point can be defined according to the change of conductivity or potentiometric change of solution in the titration process, and because of using instrument detection, the artificial error in the titration process can be eliminated. The method for determining the hydrolysis degree by the thermogravimetry is not influenced by the sub-amination reaction and the ionization balance factor in the solution, overcomes the defects of a nitrogen determination method and a titration end point method by an indicator determination method respectively, and is suitable for product detection. The document with publication number CN 105424533a discloses a method for measuring high degree of hydrolysis by converting HPAM into sodium carbonate by burning, as a result of which it is susceptible to interference from carbon-containing organic impurities; the starch cadmium iodide method (Korea and other oil field chemical, 1997) utilizes the Hofmann rearrangement reaction principle between amide groups on molecular chains and bromine to determine HPAM hydrolysis degree, and since the visible light photometry is carried out at 590nm, the chromogenic impurities, reducing substances and temperature influence in water are determinedAnd (6) obtaining the result. In addition, apparent viscosity mutation method (Luofaint scent, high polymer material science and engineering, 2006) by using anion-cation reaction is also provided. Most of the existing methods require the concentration of known polyacrylamide or are interfered by colored substances, and HPAM needs to be purified or pretreated. High performance liquid chromatography size exclusion (GPC) has long been used to determine HPAM concentration (Beazley P. anal Chem.1985,57(11): 2098-2101. Gharfeh S.G, Ahmad M A. JChromatogr.1986,336: 343-350) Zhang Sheng et al, oilfield chemistry, 1995), but no literature has been reported for determining HPAM hydrolysis. In the chemical flooding production process of oil and gas fields, HPAM is widely applied, and oil and gas field chemical flooding produced liquid contains substances such as petroleum sulfonate, soluble substances in crude oil and the like which often exist, so that the determination of the hydrolysis degree of the HPAM is interfered, especially under the condition of trace amount of the HPAM.
Disclosure of Invention
The invention aims to provide a method for measuring the hydrolysis degree of partially hydrolyzed polyacrylamide in a chemical flooding output fluid of an oil and gas field, and provides a method for measuring the hydrolysis degree of partially hydrolyzed polyacrylamide in the presence of an interfering substance.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for determining the hydrolysis degree of a partially hydrolyzed polyacrylamide in oilfield chemical flooding produced water. The determination method comprises the following steps: s1, preparing hydrolysis degree standard samples of partially hydrolyzed polyacrylamide with different hydrolysis degrees, and calibrating the hydrolysis degree; s2, preparing a series of partially hydrolyzed polyacrylamide standard solutions; s3, determining the prepared partially hydrolyzed polyacrylamide standard solution by a liquid chromatography exclusion method, drawing a chromatographic peak area or a relation curve of the peak height and the concentration of the partially hydrolyzed polyacrylamide standard solution according to determination data, and calculating the slope ki of each straight line, wherein i is 1, 2, 3, 4, 5 ∙ ∙ ∙, and i is more than or equal to 5; s5, determining a sample to be detected by adopting the same method as the determination of the partially hydrolyzed polyacrylamide standard solution, drawing a relation curve between the chromatographic peak area or peak height of the partially hydrolyzed polyacrylamide in the sample to be detected and the dilution multiple, and calculating the slope kx of a straight line; and S6, drawing a relation curve of ki of the partially hydrolyzed polyacrylamide standard solution and the calibrated hydrolysis value or fitting to obtain a corresponding relation, and finding out the corresponding hydrolysis degree on the curve according to the kx value of the sample to be detected or calculating by using the relation.
Further, S1 includes: acrylamide is homopolymerized or acrylamide and acrylic acid are copolymerized into a series of partial hydrolysis polyacrylamide with different hydrolysis degrees.
Further, adopting a mode of homopolymerizing acrylamide and then adding NaOH for hydrolysis, and controlling the feed ratio to ensure that the hydrolysis degree range of the partially hydrolyzed polyacrylamide is between 15 and 60 percent; or adding water into the powdery partially hydrolyzed polyacrylamide industrial product to prepare jelly, adding NaOH, fully kneading, hydrolyzing, cutting into rubber blocks, drying and crushing, wherein the hydrolysis degree is controlled within the range of 23-60%.
Further, the calibration in S1 includes: preparing the hydrolysis degree standard sample of the partially hydrolyzed polyacrylamide prepared in the S1 into 500 mg/L-1000 mg/L solution by using distilled water, shearing for 10S-30S, and calibrating after the foam of the solution disappears.
Furthermore, the calibration method is to titrate by hydrochloric acid with known concentration in the range of 0.09 mol/L-0.1 mol/L and determine the end point of titration by conductivity.
Further, S2 includes: diluting a calibrated standard sample of the hydrolysis degree of the partially hydrolyzed polyacrylamide into mother liquor with the concentration range of 200 mg/L-500 mg/L by using distilled water, and diluting the mother liquor into a standard sample by using a liquid chromatography mobile phase, wherein the concentration range of the standard sample is 1 mg/L-150 mg/L; preferably, the concentration of the standard sample ranges from 1mg/L to 50 mg/L.
Further, the mobile phase of the liquid chromatography is methanol and 0.025mol/L NaH with the volume ratio of 40:602PO4A mixture of aqueous solutions.
Further, in S3, a GPC chromatographic column is selected, the particle size of the filler is 5 μm, the pore diameter is 0.09 nm-0.1 nm, and a silica matrix dihydroxy bonding phase is selected; the mobile phase is methanol and NaH of which the volume ratio is 40:60 and 0.025mol/L2PO4An aqueous solution; using UV spectrophotometric detectors or diode array detectors, the wavelength of the detectorsThe wavelength is set in the range of 190nm to 210nm, and an ultraviolet spectrophotometer is used, and the wavelength is set between 190nm to 210nm, preferably 200 nm.
Further, in S5, if the sample to be measured is a sample obtained from an oil production well in an oil field, standing, taking a lower layer of aqueous solution, diluting the lower layer of aqueous solution into at least five concentration points by using a liquid chromatography mobile phase, and then measuring by using a high performance liquid chromatograph; the peak height or peak area of the chromatographic peak of the partially hydrolyzed polyacrylamide in the sample to be detected should fall within the corresponding range of 1 mg/L-150 mg/L of the partially hydrolyzed polyacrylamide standard solution, and preferably ranges from 1mg/L to 50 mg/L.
Furthermore, a flowing phase volume multiple five-point method is adopted for a sample to be detected, a relation curve of a chromatographic peak area or peak height of partial hydrolyzed polyacrylamide in the sample to be detected and a dilution multiple is drawn, and the slope kx of a straight line is calculated.
By applying the technical scheme of the invention, the method combining molecular size exclusion and high performance liquid chromatography is adopted, so that the interferents are effectively separated, and the method has the advantages of high automation degree and high analysis speed; the anti-interference capability is strong, and the measurement result is not influenced when the coloring matter exists together with the petroleum sulfonate as the oil displacement agent; further, the method can be used for measuring trace HPAM and small sample amount, and the hydrolysis degree of the HPAM can be measured under the conditions that the concentration of the HPAM is as low as about 5mg/L and the sample amount is 5 ml. The method can also be used for measuring the resolution ratio under the condition that the concentration of the HPAM sample to be measured is unknown, and is an effective method for rapidly measuring the hydrolysis ratio of partially hydrolyzed polyacrylamide in a chemical flooding system under the condition that interferents coexist and a small amount of samples exist.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows the HPAM peak area versus dilution factor (in terms of concentration) of the polymer from a sample from an oil well taken in example 2.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
In view of the problems described in the background art, the present invention is directed to the measurement of the degree of hydrolysis of a partially hydrolyzed polyacrylamide in a trace amount in the presence of an interfering substance.
According to an exemplary embodiment of the present invention, a method for determining the hydrolysis degree of a partially hydrolyzed polyacrylamide in oilfield chemical flooding output water is provided. The determination method comprises the following steps: s1, preparing hydrolysis degree standard samples of partially hydrolyzed polyacrylamide with different hydrolysis degrees, and calibrating the hydrolysis degree; s2, preparing a series of partially hydrolyzed polyacrylamide standard solutions; s3, determining the prepared partially hydrolyzed polyacrylamide standard solution by a liquid chromatography exclusion method, drawing a chromatographic peak area or a relation curve of the peak height and the concentration of the partially hydrolyzed polyacrylamide standard solution according to determination data, and calculating the slope ki of each straight line, wherein i is 1, 2, 3, 4, 5 ∙ ∙ ∙, and i is more than or equal to 5; s5, determining a sample to be detected by adopting the same method as the determination of the partially hydrolyzed polyacrylamide standard solution, drawing a relation curve between the chromatographic peak area or peak height of the partially hydrolyzed polyacrylamide in the sample to be detected and the dilution multiple, and calculating the slope kx of a straight line; and S6, drawing a relation curve of ki of the partially hydrolyzed polyacrylamide standard solution and the calibrated hydrolysis value or fitting to obtain a corresponding relation, and finding out the corresponding hydrolysis degree on the curve according to the kx value of the sample to be detected or calculating by using the relation.
By applying the technical scheme of the invention, the method combining molecular size exclusion and high performance liquid chromatography is adopted, so that the interferents are effectively separated, and the method has the advantages of high automation degree and high analysis speed; the anti-interference capability is strong, and the measurement result is not influenced when the coloring matter exists together with the petroleum sulfonate as the oil displacement agent.
In an embodiment of the present invention, S1 includes: acrylamide is homopolymerized or acrylamide and acrylic acid are copolymerized into a series of partial hydrolysis polyacrylamide with different hydrolysis degrees. Adopting an acrylamide homopolymerization method, then adding NaOH for hydrolysis, and controlling the feed ratio to ensure that the hydrolysis degree range of the partially hydrolyzed polyacrylamide is between 15 and 60 percent; or adding water into the powdery partially hydrolyzed polyacrylamide industrial product to prepare jelly, adding NaOH, fully kneading, hydrolyzing, cutting into rubber blocks, drying and crushing, wherein the hydrolysis degree is controlled within the range of 23-60%. The method for preparing the standard substance has simple steps and good control of the feeding ratio. In an embodiment of the present invention, the calibrating in S1 includes: preparing a hydrolysis degree standard sample of the partially hydrolyzed polyacrylamide prepared in S1 into a solution of 500 mg/L-1000 mg/L (preferably 1000mg/L) by using distilled water, shearing for 10S-30S, and calibrating after the foam of the solution disappears. Preferably, the calibration is carried out by titrating hydrochloric acid with known concentration in the range of 0.09 mol/L-0.1 mol/L, and the conductivity is recommended to determine the titration end point. According to an exemplary embodiment of the present invention, S2 includes: diluting a calibrated standard sample of the hydrolysis degree of the partially hydrolyzed polyacrylamide into mother liquor with the concentration range of 200 mg/L-500 mg/L by using distilled water, and diluting the mother liquor into a standard sample by using a liquid chromatography mobile phase, wherein the concentration range of the standard sample is 1 mg/L-150 mg/L; preferably, the concentration of the standard sample ranges from 1mg/L to 50 mg/L. The concentration of the standard sample is controlled within the range, and more accurate results can be obtained, because if the concentration is too high, the chromatographic column is overloaded, the tailing of a peak is deformed, and the measurement result is influenced.
Preferably, the liquid chromatography mobile phase is methanol and 0.025mol/L NaH at a volume ratio of 40:602PO4A mixture of aqueous solutions.
Preferably, in S3, a GPC chromatographic column is selected, the filler particle size is 5 μm, the pore diameter is 0.09 nm-0.1 nm, and a silica matrix dihydroxy bonding phase is selected; the mobile phase is methanol and NaH of which the volume ratio is 40:60 and 0.025mol/L2PO4An aqueous solution; an ultraviolet spectrophotometric detector or a diode array detector is adopted, the wavelength of the detector is set to be in the range of 190nm to 210nm, and the wavelength of the ultraviolet spectrophotometric detector is set to be between 190nm and 210nm, preferably 200 nm. The lower limit of the wavelength is 190nm and the upper limit is 370nm under the influence of ultraviolet lamp parameters. Wave of accompanying waveThe long increase, the signal-to-noise ratio decreases rapidly, exceeding 210nm, the detection sensitivity does not meet the requirements, and 200nm is recommended for obtaining more accurate results. In an embodiment of the present invention, in S5, if the sample to be measured is a sample obtained from an oil field production well, the sample to be measured is left to stand, the lower layer aqueous solution is taken out, diluted into at least five concentration points by a liquid chromatography mobile phase, and then measured by a high performance liquid chromatograph; the peak height or peak area of the chromatographic peak of the partially hydrolyzed polyacrylamide in the sample to be detected should fall within the corresponding range of 1 mg/L-150 mg/L of the partially hydrolyzed polyacrylamide standard solution, and preferably ranges from 1mg/L to 50 mg/L.
In one embodiment of the invention, a flowing phase volume multiple five-point method is adopted for a sample to be detected, a relation curve of a chromatographic peak area or peak height of partial hydrolyzed polyacrylamide in the sample to be detected and a dilution multiple is drawn, and the slope kx of a straight line is calculated.
In an exemplary embodiment of the invention, the method for determining the hydrolysis degree of partially hydrolyzed polyacrylamide in oilfield chemical flooding produced water comprises the following steps:
(1) preparation of HPAM standards: acrylamide free radical initiated homopolymerization or acrylamide and acrylic acid copolymerization are synthesized into a series of HPAMs with different hydrolysis degrees, and a mode of hydrolysis after acrylamide homopolymerization and NaOH is recommended. Controlling the feed ratio to ensure that the hydrolysis degree range of the HPAM is between 15 and 60 percent; or adding water into the powdery HPAM industrial product to prepare jelly, adding NaOH, fully kneading, performing 'post hydrolysis', cutting into rubber blocks, drying and crushing, wherein the hydrolysis degree is controlled within the range of 23-60%;
(2) calibrating hydrolysis degree of HPAM standard sample: calibrating the hydrolysis degree of the synthesized HPAM sample, preparing the prepared standard sample into a solution of about 1000mg/L by using distilled water, shearing for 10-30 s, and calibrating after the foam of the solution disappears, wherein the calibration method comprises the steps of titrating (GB/T12005.2) by using hydrochloric acid with the known concentration in the range of 0.09-0.1 mol/L, and determining the titration end point by adopting the conductivity;
(3) preparation of HPAM standard solution: diluting the calibrated HPAM with distilled water to obtain a mother liquor with a concentration range of 200 mg/L-500 mg/L, and then using a liquid chromatography mobile phase (methanol to 0.025 volume ratio of 40: 60)mol/L NaH2PO4Aqueous solution) to be diluted into a standard sample, wherein the concentration range of the standard sample is between 1mg/L and 150mg/L, and preferably between 1mg/L and 50 mg/L;
(4) measurement of HPAM standard solution: the prepared series of standard samples are measured by a liquid chromatography exclusion method. Selecting a GPC chromatographic column, wherein the grain diameter of a filler is 5 mu m, the pore diameter is 0.09 nm-0.1 nm, and a silica matrix dihydroxy bonding phase; the mobile phase is methanol and NaH of which the volume ratio is 40:60 and 0.025mol/L2PO4An aqueous solution; adopting ultraviolet spectrophotometry detector or diode array detector, the wavelength of the detector is set in the range of 190 nm-210 nm, and preferably using ultraviolet spectrophotometry detector, the wavelength is set between 190 nm-210 nm, preferably 200 nm; measuring the prepared series of standard solutions according to the conditions, drawing a relation curve of chromatographic peak areas or peak heights of the series of standard samples and HPAM concentration according to measurement data, and calculating the slope ki of each straight line, wherein i is 1, 2, 3, 4, 5 ∙ ∙ ∙, and i is more than or equal to 5;
(5) and (3) determination of a sample: measuring a sample containing HPAM or other samples collected in the field by the same method as the HPAM standard sample solution; if the sample is obtained from an oil field oil production well, taking the lower layer aqueous solution after standing, diluting the lower layer aqueous solution into at least five concentration points by using a liquid chromatography mobile phase, and then measuring by using a high performance liquid chromatograph; the peak height or peak area of the chromatographic peak of the HPAM sample is generally in the corresponding range of 1 mg/L-150 mg/L HPAM standard sample, preferably in the range of 1 mg/L-50 mg/L; and drawing a relation curve of the HPAM chromatographic peak area or peak height and the dilution factor, and calculating the slope kx of the straight line.
(6) Calculation of degree of hydrolysis of HPAM samples: drawing a ki of the HPAM standard sample and a calibrated hydrolysis degree value (HD) relation curve or fitting to obtain a corresponding relation, and finding out the corresponding hydrolysis degree on the curve according to the kx value of the sample or calculating by using the relation.
The method can be used for measuring the amount of trace HPAM and small samples, and the hydrolysis degree of the HPAM can be measured under the conditions that the concentration of the HPAM is as low as about 5mg/L and the amount of 5ml of sample. The method can also be used for measuring the resolution ratio under the condition that the concentration of the HPAM sample to be measured is unknown, and is an effective method for rapidly measuring the hydrolysis ratio of partially hydrolyzed polyacrylamide in a chemical flooding system under the condition that interferents coexist and a small amount of samples exist.
The method for measuring the hydrolysis degree of the partially hydrolyzed polyacrylamide in the oil field chemical flooding produced water can be used for measuring the hydrolysis degree of polyacrylamide and dynamically tracking the oil displacement effect of an oil reservoir in the tertiary oil recovery process of an oil field, particularly, the dynamic change process of the hydrolysis reaction of the partially polyacrylamide in a chemical oil displacement system injected into the oil reservoir is known through the hydrolysis degree, the condition of the hydrolysis reaction of the polyacrylamide under the oil reservoir condition is reflected, and the propelling speed and the physical and chemical environment of the chemical oil displacement system containing the polyacrylamide in different layers or different displacement directions are further evaluated. The method can also be used for monitoring the degradation process of the partially hydrolyzed polyacrylamide material and researching the hydrolysis reaction kinetics.
The following examples are provided to further illustrate the advantageous effects of the present invention.
Example 1
Putting 1500g of 25% acrylamide solution into a 2500ml wide-mouth bottle, sealing the bottle, introducing nitrogen to remove dissolved oxygen in the solution, adding a proper amount of EDTA disodium salt, adding an initiator, initiating free radical to homopolymerize the acrylamide, cutting the product colloid into blocks, dividing the cut colloid into five equal parts, adding 10g, 12g, 14g, 16g and 18g of granular solid NaOH respectively, kneading uniformly, heating and hydrolyzing, drying, and granulating to obtain the HPAM dry powder. The dry powder obtained was tested for polymer solids content according to GB/T12005.2. Preparing the obtained dry powder into a solution with the concentration of 1000mg/L by using distilled water, shearing the solution by using a Wuyi mixing and adjusting device for 10s, titrating the obtained solution by using a GB/T12005.6 method, judging an end point method by using a conductivity method, titrating the solution in parallel for three times, and taking the average value as the hydrolysis degree of HPAM. Using 1000mg/L polymer solution prepared above as mother liquor, using 40:60 methanol and 0.025mol/L NaH2PO4Diluting the mobile phase of the aqueous solution to obtain HPAM concentrations of 10mg/L, 30mg/L, 50mg/L, 80mg/L and 100mg/L respectively, and determining by selecting a GPC chromatographic column, wherein the filler particle size is 5 μm, the pore size distribution is 0.09 nm-0.1 nm, the column is a silica matrix dihydroxy bonding phase column, the specification is 140mm × 46mm, and the mobile phase is in a volume ratio of 40:60 parts of methanol and 0.025mol/L of NaH2PO4An aqueous solution. An ultraviolet spectrophotometric detector is adopted, the wavelength of the detector is set to be 200nm, and the flow rate is 1 ml/min. And drawing a relation curve of the chromatographic peak area or peak height of the series of standard samples and the HPAM concentration according to the measurement data, and calculating the slope of each straight line.
Example 2
First, 10mg/L, 30mg/L, 50mg/L, 80mg/L and 100mg/L of standard samples were measured according to the procedure of example 1 to obtain k1、k2、k3、k4And k5Taking four oil well samples of XXx67, xxx56 and xxx37 of XX block gram lower group of oil reservoir chemical combination flooding injection station (injection well) and three extraction wells (production well) of Xinjiang Cramayi oil field, and mixing methanol and 0.025mol/L NaH according to the volume ratio of 40:602PO4The mobile phase of the aqueous solution was diluted to five concentration points, and the test results are shown in FIG. 1 (the concentration of HPAM was converted, and the concentration converted to the degree of hydrolysis of polyacrylamide was generally calculated by finding the area of the peak of polyacrylamide in the sample, and the concentration of polyacrylamide corresponding to the degree of hydrolysis, as shown in FIG. 1). The degree of HPAM hydrolysis in the four samples obtained was 27%, 38%, 45% and 47%, respectively.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The method for determining the hydrolysis degree of the partially hydrolyzed polyacrylamide in the oilfield chemical flooding output water is characterized by comprising the following steps of:
s1, preparing hydrolysis degree standard samples of partially hydrolyzed polyacrylamide with different hydrolysis degrees, and calibrating the hydrolysis degree;
s2, preparing a series of partially hydrolyzed polyacrylamide standard solutions;
s3, determining the prepared partially hydrolyzed polyacrylamide standard solution by a liquid chromatography exclusion method, drawing a chromatographic peak area or a relation curve of the peak height and the concentration of the partially hydrolyzed polyacrylamide standard solution according to determination data, and calculating the slope ki of each straight line, i is 1, 2, 3, 4, 5 ∙ ∙ ∙, i is more than or equal to 5;
s5, determining a sample to be detected by the same method as the determination of the partially hydrolyzed polyacrylamide standard solution, drawing a relation curve between the chromatographic peak area or peak height of the partially hydrolyzed polyacrylamide in the sample to be detected and the dilution multiple, and calculating the slope kx of a straight line; and
and S6, drawing a relation curve of ki of the partially hydrolyzed polyacrylamide standard solution and the calibrated hydrolysis value or fitting to obtain a corresponding relation, and finding out the corresponding hydrolysis degree on the curve according to the kx value of the sample to be detected or calculating by using the relation.
2. The method according to claim 1, wherein the step S1 includes: acrylamide is homopolymerized or acrylamide and acrylic acid are copolymerized into a series of partial hydrolysis polyacrylamide with different hydrolysis degrees.
3. The determination method according to claim 2, wherein the dosage ratio is controlled by adopting a mode of homopolymerization of acrylamide and then hydrolysis by adding NaOH, so that the hydrolysis degree of the partially hydrolyzed polyacrylamide is between 15% and 60%; or
Adding water into the powdery partially hydrolyzed polyacrylamide industrial product to prepare jelly, adding NaOH, fully kneading, hydrolyzing, cutting into rubber blocks, drying and crushing, wherein the hydrolysis degree is controlled within the range of 23-60%.
4. The assay of claim 1, wherein the calibrating in S1 comprises: preparing the partially hydrolyzed polyacrylamide hydrolysis degree standard sample prepared in the S1 into 500 mg/L-1000 mg/L solution by using distilled water, shearing for 10S-30S, and calibrating after the foam of the solution disappears.
5. The method of claim 2, wherein the calibration is performed by titration with hydrochloric acid of known concentration in the range of 0.09mol/L to 0.1mol/L, and the end point of the titration is determined by conductivity.
6. The method according to claim 1, wherein the step S2 includes: diluting the calibrated standard sample of the hydrolysis degree of the partially hydrolyzed polyacrylamide with distilled water into mother liquor with the concentration range of 200 mg/L-500 mg/L, and diluting the mother liquor into a standard sample with a liquid chromatography mobile phase, wherein the concentration range of the standard sample is 1 mg/L-150 mg/L; preferably, the concentration of the standard sample ranges from 1mg/L to 50 mg/L.
7. The method according to claim 6, wherein the liquid chromatography mobile phase is methanol and NaH at a volume ratio of 40:60 to 0.025mol/L2PO4A mixture of aqueous solutions.
8. The method according to claim 1, wherein in S3, a GPC column is used, and a silica-based dihydroxy bonding phase having a filler particle size of 5 μm and a pore size of 0.09nm to 0.1nm is used; the mobile phase is methanol and NaH of which the volume ratio is 40:60 and 0.025mol/L2PO4An aqueous solution; an ultraviolet spectrophotometric detector or a diode array detector is adopted, the wavelength of the detector is set to be in the range of 190nm to 210nm, and the wavelength of the ultraviolet spectrophotometric detector is set to be between 190nm and 210nm, preferably 200 nm.
9. The method according to claim 1, wherein in S5, if the sample to be tested is a sample obtained from an oil field production well, the lower aqueous solution is taken after standing, diluted to at least five concentration points by a liquid chromatography mobile phase, and then measured by a high performance liquid chromatograph; the peak height or peak area of the chromatographic peak of the partially hydrolyzed polyacrylamide in the sample to be detected should fall within the corresponding range of 1 mg/L-150 mg/L of the partially hydrolyzed polyacrylamide standard solution, and preferably ranges from 1mg/L to 50 mg/L.
10. The determination method according to claim 1, wherein a mobile phase volume multiple five-point method is adopted for the sample to be determined, a relation curve of a chromatographic peak area or peak height of partially hydrolyzed polyacrylamide in the sample to be determined and a dilution multiple is drawn, and a slope kx of a straight line is calculated.
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