CN103217360A - Method for detecting molecular weight of hydrolyzed polyacrylamide - Google Patents
Method for detecting molecular weight of hydrolyzed polyacrylamide Download PDFInfo
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- CN103217360A CN103217360A CN2013101232980A CN201310123298A CN103217360A CN 103217360 A CN103217360 A CN 103217360A CN 2013101232980 A CN2013101232980 A CN 2013101232980A CN 201310123298 A CN201310123298 A CN 201310123298A CN 103217360 A CN103217360 A CN 103217360A
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- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000001514 detection method Methods 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 12
- 238000012821 model calculation Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 238000005259 measurement Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 33
- 238000002474 experimental method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000523 sample Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
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Abstract
The invention discloses a method for detecting the molecular weight of hydrolyzed polyacrylamide, which solves the problem of complex operation of the existing detection method; the method comprises the steps of measuring rheological curves of hydrolyzed polyacrylamide solutions with different molecular weights by using a rotational rheometer, calculating zero shear viscosity of the hydrolyzed polyacrylamide solutions with different molecular weights by using a Carreu model, drawing a graph of the molecular weights by taking the zero shear viscosity as a horizontal coordinate to obtain a relational expression of the zero shear viscosity and the molecular weights, measuring the zero shear viscosity of the hydrolyzed polyacrylamide to be measured, and obtaining the molecular weight of the hydrolyzed polyacrylamide to be measured by using the relational expression. The method can simplify the operation process, shorten the working time and improve the working efficiency on the premise of ensuring the measurement accuracy.
Description
Technical field
The present invention relates to the detection method that a kind of field polymers displacement of reservoir oil water is separated the polyacrylamide molecular weight.
Background technology
Polymer flooding mainly is to increase recovery ratio by improving the viscosity of injecting water and reducing water phase permeability.Polymer molecular weight is one of major parameter of the above-mentioned mechanism of influence, and high more its tackifying of polymer molecular weight is good more, and the ability that reduces water phase permeability is strong more.If but that molecular weight is selected is too high, can stops up oil reservoir and cause the oil reservoir injury.If it is low excessively that molecular weight is selected, because tackifying is poor, certainly will to increase the consumption of polymkeric substance, the techno-economic effect that impact polymer drives, therefore how selecting molecular weight is very crucial problem.Daqing oil field is poly-, and to drive used polymkeric substance mainly be partially hydrolyzed polyacrylamide, and the sign to the molecular weight of hydro-polyacrylamide in the company standard Q/SY 119-2005 of the PetroChina Company Ltd. relevant criterion mainly is to adopt the Ubbelohde viscometer dilution method to detect mean molecular weight.This method is to calculate viscosity average molecular weigh according to intrinsic viscosity [η], by the η c/c value that (0.04%, 0.06%, 0.08%, 0.1%) under the variable concentrations (c) is measured c is mapped, by curve to extrapolating of c=0 the value of ordinate intercept just for intrinsic viscosity, according to formula M=([η]/0.000373)
1.515Calculate its molecular weight.Concrete operation steps is at first will use sodium citrate, sodium dihydrogen phosphate and sodium chloride preparation buffer solution, and measure its flowing time between viscosity meter two scales.Each sample needs that all its mother liquor is diluted to concentration and is respectively 0.04%, 0.06%, 0.08%, 0.1% polymer solution, each solution all will filter through the glass sand core funnel, before each the mensuration, viscosity meter all will wash 2 times to 3 times with solution to be measured, measure the flowing time of variable concentrations polymer solution between viscosity meter two scales then, molecular weight is big more, and the spent time is long more.In addition, the cleaning of Ubbelohde viscometer is difficulty very, need soak with poisonous solution, also needs to use oven for drying after the cleaning.In a word, this method test process is loaded down with trivial details, and work efficiency is very low.
Summary of the invention
The purpose of this invention is to provide a kind of new method that detects the hydro-polyacrylamide molecular weight, this method can simplify the operation course under the prerequisite of measurement accuracy guaranteeing, shortens working hours, and increases work efficiency.
For achieving the above object, the technical solution used in the present invention is: a kind of method that detects the hydro-polyacrylamide molecular weight, and concrete steps are as follows:
One: at first find hydro-polyacrylamide solution zero-shear viscosity
η 0 Relational expression with molecular weight:
1, chooses some different molecular hydrolyzed polyacrylamides, prepare hydro-polyacrylamide solution according to the compound method of the polymer mother liquor in the molecular weight detection method of the hydro-polyacrylamide among the company standard Q/SY 119-2005 of PetroChina Company Ltd.;
2, adopt rotational rheometer, record range of shear rate at 0.001-1000s
-1Step 1 in different molecular hydrolyzed polyacrylamide flow of solution varied curve, and calculate the zero-shear viscosity of variant molecular weight hydro-polyacrylamide solution
η 0 Size;
3, the result according to step 2 draws zero-shear viscosity
η 0 Relation curve with molecular weight;
4, according to the relation curve of step 3, obtain zero-shear viscosity
η 0 Relational expression with molecular weight:
M w =?Ax
η 0 b
In the formula:
M w ---molecular weight;
A, b---regression coefficient;
Two: the molecular weight of measuring hydro-polyacrylamide to be measured
At first prepare hydro-polyacrylamide solution, and test its flow of solution varied curve, use its zero-shear viscosity of Carreu Model Calculation then according to step 2 method according to the method for above-mentioned steps 1
η 0 , with zero-shear viscosity
η 0 Zero-shear viscosity in the substitution step 4
η 0 With the relational expression of molecular weight, calculate the molecular weight of this hydro-polyacrylamide at last by this relational expression.
Beneficial effect: adopt this method, do not need to prepare buffer solution, each hydro-polyacrylamide sample only needs to adopt distilled water to prepare a kind of polymer solution of concentration, does not need solution is filtered, the vertebral plate measuring system that adopts is highly susceptible to cleaning, and does not need to adopt any poisonous solution.With respect to original detection method, this method has the advantage of environmental protection, energy-conservation, high efficiency.
Description of drawings
Fig. 1 is 3,268 ten thousand hydro-polyacrylamide flow of solution varied curve figure for molecular weight among the present invention.
Fig. 2 is 1,907 ten thousand hydro-polyacrylamide flow of solution varied curve figure for molecular weight among the present invention.
Fig. 3 is 1,566 ten thousand hydro-polyacrylamide flow of solution varied curve figure for molecular weight among the present invention.
Fig. 4 is 8,000,000 hydro-polyacrylamide flow of solution varied curve figure for molecular weight among the present invention.
Fig. 5 is 4,000,000 hydro-polyacrylamide flow of solution varied curve figure for molecular weight among the present invention.
Fig. 6 is molecular weight and zero-shear viscosity relation curve fitted figure among the present invention.
Fig. 7 is 2,003 ten thousand polymer solution rheological curve figure for the molecular weight by canonical measure among the present invention.
Fig. 8 is the repeated experiment of molecular weight 3,153 ten thousand polymer samples among the present invention figure as a result.
Embodiment
To sum up, the present invention proposes the employing rotational rheometer, record range of shear rate at 0.001-1000s
-1Different molecular hydrolyzed polyacrylamide flow of solution varied curve, use the zero-shear viscosity of Carreu Model Calculation different molecular weight polyacrylamide solution then, with the zero-shear viscosity is that horizontal ordinate is mapped to molecular weight, adopt power rate model that curve is carried out match at last, obtain the relational expression of zero-shear viscosity and molecular weight:
M w =?Ax
η 0 b
In the formula:
M w ---molecular weight;
The A---regression coefficient;
The b---regression coefficient;
η 0 ---zero-shear viscosity;
Measure the molecular weight of a certain hydro-polyacrylamide to be measured, at first test its flow of solution varied curve, use its zero-shear viscosity of Carreu Model Calculation then, zero-shear viscosity
η 0 The relational expression of substitution zero-shear viscosity and molecular weight just can calculate the molecular weight of this polymkeric substance.
Describe the mean molecular weight of how measuring a certain hydro-polyacrylamide solution in detail with the inventive method below in conjunction with specific embodiment:
1, the preparation of different molecular hydrolyzed polyacrylamide solution:
Raw material: choose five kinds of hydro-polyacrylamides, molecular weight is respectively 400,800,1566,1907,3,268 ten thousand, from Daqing Refinery company.These five kinds of hydro-polyacrylamides are mixed with solution, and compound method is seen the preparation with sample solution in the assay method of partially hydrolyzed polyacrylamide degree of hydrolysis of the displacement of reservoir oil in the company standard Q/SY 119-2005 of the PetroChina Company Ltd. relevant criterion.
2, different molecular hydrolyzed polyacrylamide flow of solution varied curve in the measuring process 1:
1) starts U.S. TA company by correct boot program and produce ARES-LS1 type rotational rheometer;
2) open computing machine, TA Orchestrator icon and instrument are online on the double-click desktop;
3) after the online success, enter the main operation interface, select that control (control)---edit(edit)/start test(begins to test) enter to test the interface is set, select the C50/0.04rad measuring system, select (Steady Experiment) stable state experiment model, select Steady Rate Sweep (steady state shearing rate scanning), range of shear rate is arranged on 0.001-1000s
-1, experimental temperature is set to 45 ℃;
4) make zero in the gap, load sample, reach temperature is set after, enter the main operation interface, edit(edit to select control (control)----)/start test(begins experiment), click begin test (beginning to test); Preserve experimental result;
5) repeat above-mentioned experiment, obtain different molecular hydrolyzed polyacrylamide flow of solution varied curve (seeing Fig. 1-5).
3, adopt the Carreu model that curve is carried out match, obtain different molecular hydrolyzed polyacrylamide solution zero-shear viscosity:
1) at TA Orchestrator main operation interface, open file--select Curve Fit (curve fitting)--Fit Data to Model(model fitting data)--Viscosity Models(viscosity model)--Carreu Model(Carreu model)--the Fit(match)--Save fit (preservation match)---close window;
2) select Curve Fit (curve fitting)---Stamp Fit (stickup match);
3) obtain zero-shear viscosity
η 0
4) repeat above-mentioned steps, obtain different molecular hydrolyzed polyacrylamide solution zero-shear viscosity, see the following form 1:
Table 1 different molecular hydrolyzed polyacrylamide solution zero-shear viscosity fitting result
| Molecular weight (ten thousand) | 400 | 800 | 1566 | 1907 | 3268 |
| Zero-shear viscosity (Pa.s) | 0.93408 | 2.45081 | 8.16371 | 9.1592 | 17.5226 |
4, determine the relational expression of molecular weight and zero-shear viscosity:
1) in EXCEL, is the relation curve that horizontal ordinate is drawn it and molecular weight, specifically sees accompanying drawing 6 with the zero-shear viscosity in the table 1;
2) in EXCEL, select to add Trendline;
3) adopt power rate model fitting curve, obtain the relational expression of zero-shear viscosity and molecular weight:
M w =?A?x
η 0 b
In the formula:
M w ---molecular weight;
The A---regression coefficient;
The b---regression coefficient;
η 0 ---zero-shear viscosity
Can obtain its relational expression from Fig. 6 is:
Mw=?411.26x
η 0 0.7057
In the formula:
M w ---molecular weight;
A---411.26；
b---0.7057；
η 0 ---zero-shear viscosity.
5,Measure the molecular weight of hydro-polyacrylamide sample to be measured:
Get hydro-polyacrylamide to be measured, use the company standard Q/SY 119-2005 method of mentioning in the background technology, measuring its molecular weight is 2,003 ten thousand, and then measures its molecular weight with the inventive method, compares, specific as follows:
1) adopt the method for step 1 to prepare hydro-polyacrylamide solution;
2) method of employing step 2 is measured the rheological curve of this hydro-polyacrylamide, specifically sees accompanying drawing 7;
3) adopting the method for step 3 to calculate its zero-shear viscosity is 9.2519Pa.s;
4) adopt the zero-shear viscosity of step 4 and the relational expression of molecular weight, calculating its mean molecular weight is 1,976 ten thousand.
As can be seen, the result who utilizes the inventive method to record is very approaching with the values for molecular weight of measuring according to company standard Q/SY 119-2005.
Embodiment 2: repeated experiment
Choosing molecular weight is 3,153 ten thousand hydro-polyacrylamide samples, utilize the inventive method to measure three times, obtain three rheological curves, specifically see accompanying drawing 8, its repeatability is better as can be seen from three rheological curves, and the match zero-shear viscosity is respectively 17.4155Pa.s, 17.2.19Pa.s, 16.7211Pa.s.The molecular weight that is calculated is difference 3,089 ten thousand, 3,062 ten thousand, 3,002 ten thousand.Relative deviation is 0.43%, and illustrative experiment repeatability is very good.
Claims (1)
1. method that detects the hydro-polyacrylamide molecular weight, concrete steps are as follows:
One: at first find hydro-polyacrylamide solution zero-shear viscosity
η 0 Relational expression with molecular weight:
1, chooses some different molecular hydrolyzed polyacrylamides, prepare hydro-polyacrylamide solution according to the compound method of the polymer mother liquor in the molecular weight detection method of the hydro-polyacrylamide among the company standard Q/SY 119-2005 of PetroChina Company Ltd.;
2, adopt rotational rheometer, record range of shear rate at 0.001-1000s
-1Step 1 in different molecular hydrolyzed polyacrylamide flow of solution varied curve, and calculate the zero-shear viscosity of variant molecular weight hydro-polyacrylamide solution
η 0 Size;
3, the result according to step 2 draws zero-shear viscosity
η 0 Relation curve with molecular weight;
4, according to the relation curve of step 3, obtain zero-shear viscosity
η 0 Relational expression with molecular weight:
M w =?Ax
η 0 b
In the formula:
M w ---molecular weight;
A, b---regression coefficient;
Two: the molecular weight of measuring hydro-polyacrylamide to be measured
At first prepare hydro-polyacrylamide solution, and test its flow of solution varied curve, use its zero-shear viscosity of Carreu Model Calculation then according to step 2 method according to the method for above-mentioned steps 1
η 0 , with zero-shear viscosity
η 0 Zero-shear viscosity in the substitution step 4
η 0 With the relational expression of molecular weight, calculate the molecular weight of hydro-polyacrylamide to be measured at last by this relational expression.
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Cited By (6)
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| CN105445150A (en) * | 2015-09-15 | 2016-03-30 | 中兴农谷湖北有限公司 | Method for rapidly determining content of biodiesel combined glycerin |
| CN105445148A (en) * | 2015-09-15 | 2016-03-30 | 中兴农谷湖北有限公司 | Method for rapidly determining content of fatty acid methyl ester in biodiesel |
| US9645066B1 (en) | 2015-12-04 | 2017-05-09 | Chevron Phillips Chemical Company Lp | Polymer compositions having improved processability and methods of making and using same |
| US9645131B1 (en) | 2015-12-04 | 2017-05-09 | Chevron Phillips Chemical Company Lp | Polymer compositions having improved processability and methods of making and using same |
| CN111175188A (en) * | 2020-02-24 | 2020-05-19 | 刘白玲 | Method for rapidly detecting average molecular weight of polyhexamethylene guanidine hydrochloride |
| WO2022118554A1 (en) * | 2020-12-04 | 2022-06-09 | 株式会社カネカ | Estimation system, estimation method, and program |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105445150A (en) * | 2015-09-15 | 2016-03-30 | 中兴农谷湖北有限公司 | Method for rapidly determining content of biodiesel combined glycerin |
| CN105445148A (en) * | 2015-09-15 | 2016-03-30 | 中兴农谷湖北有限公司 | Method for rapidly determining content of fatty acid methyl ester in biodiesel |
| US9645066B1 (en) | 2015-12-04 | 2017-05-09 | Chevron Phillips Chemical Company Lp | Polymer compositions having improved processability and methods of making and using same |
| US9645131B1 (en) | 2015-12-04 | 2017-05-09 | Chevron Phillips Chemical Company Lp | Polymer compositions having improved processability and methods of making and using same |
| WO2017095803A1 (en) * | 2015-12-04 | 2017-06-08 | Chevron Phillips Chemical Company Lp | Polymer compositions having improved processability and methods of making and using same |
| US9791358B2 (en) | 2015-12-04 | 2017-10-17 | Chevron Phillips Chemical Company, Lp | Polymer compositions having improved processability and methods of making and using same |
| CN111175188A (en) * | 2020-02-24 | 2020-05-19 | 刘白玲 | Method for rapidly detecting average molecular weight of polyhexamethylene guanidine hydrochloride |
| WO2022118554A1 (en) * | 2020-12-04 | 2022-06-09 | 株式会社カネカ | Estimation system, estimation method, and program |
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Application publication date: 20130724 |