CN103603655A - Tracer agent for monitoring multistage fracturing flowback fluid and monitoring method - Google Patents
Tracer agent for monitoring multistage fracturing flowback fluid and monitoring method Download PDFInfo
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- CN103603655A CN103603655A CN201310476303.6A CN201310476303A CN103603655A CN 103603655 A CN103603655 A CN 103603655A CN 201310476303 A CN201310476303 A CN 201310476303A CN 103603655 A CN103603655 A CN 103603655A
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- 239000000700 radioactive tracer Substances 0.000 title claims abstract description 154
- 238000012544 monitoring process Methods 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000012530 fluid Substances 0.000 title claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 title abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims abstract description 37
- 239000008139 complexing agent Substances 0.000 claims abstract description 17
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 12
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 12
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 12
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 12
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 12
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 12
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 12
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 12
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 12
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 12
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 12
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims abstract description 12
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims abstract description 12
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 12
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 12
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims abstract description 12
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims abstract description 12
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 12
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 12
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims abstract description 12
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 9
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 46
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 44
- -1 hydroxylamine chloride neodymium Chemical compound 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- RORQMFBWPYVCFR-UHFFFAOYSA-K [Ho+3].[Cl-].NO.[Cl-].[Cl-] Chemical compound [Ho+3].[Cl-].NO.[Cl-].[Cl-] RORQMFBWPYVCFR-UHFFFAOYSA-K 0.000 claims description 4
- NXQFGNFBXRCFRP-UHFFFAOYSA-K [Pr+3].[Cl-].NO.[Cl-].[Cl-] Chemical compound [Pr+3].[Cl-].NO.[Cl-].[Cl-] NXQFGNFBXRCFRP-UHFFFAOYSA-K 0.000 claims description 4
- HCGJNVCHYPIJLT-UHFFFAOYSA-K [Sm+3].[Cl-].NO.[Cl-].[Cl-] Chemical compound [Sm+3].[Cl-].NO.[Cl-].[Cl-] HCGJNVCHYPIJLT-UHFFFAOYSA-K 0.000 claims description 4
- XUTKOYMTZGNELP-UHFFFAOYSA-K [Tm+3].[Cl-].NO.[Cl-].[Cl-] Chemical compound [Tm+3].[Cl-].NO.[Cl-].[Cl-] XUTKOYMTZGNELP-UHFFFAOYSA-K 0.000 claims description 4
- 239000003129 oil well Substances 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 238000004458 analytical method Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000010795 Steam Flooding Methods 0.000 description 1
- 238000010796 Steam-assisted gravity drainage Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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Abstract
The invention provides a tracer for monitoring multistage fracturing flowback fluid and a monitoring method. The tracer comprises 12 tracer element complex aqueous solutions formed by respectively mixing 12 tracer elements with a complexing agent, wherein the 12 tracer elements comprise praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium. The monitoring method is a method for monitoring multistage fracturing flowback fluid by adopting the tracer. The tracer agent has good compatibility with fracturing fluid, small adsorption amount in stratum, good stability and high analysis precision, and 12 tracer elements do not interfere with each other, and can realize monitoring of fracturing flowback fluid of each layer in the multistage fracturing process of an oil field.
Description
Technical field
The present invention relates to a kind of tracer and monitoring multistage fracturing that returns discharge opeing for monitoring multistage fracturing and return the method for discharge opeing, belong to technical field of petroleum extraction.
Background technology
Tracer monitoring technology is current field use Dynamic Monitoring very widely, in the various displacement of reservoir oil engineerings such as water drive, non-phase-mixing driving, polymer flooding, steam flooding, SAGD, all there is application, be mainly used for monitoring the connected relation between injection-production well and inject fluid in the situation that involves on stratum.
Tracer monitoring technology is at present also for monitoring fracturing effect aspect, but is mainly used for evaluating the developmental state of fracturing fracture.The method is by using the distribution situation of the tester monitoring radioactive tracers such as gamma spectrometer and directed gamma instrument or magnetic determining device in stratum to realize.In addition, also exist about using the research of tracer monitoring fracturing outlet liquid, but only limit at present use the of the fracturing fluid row's of the returning situation of the general evaluation of single tracer, still can not realize and use multiple tracer to divide interval to evaluate each layer of of the fracturing fluid row's of returning situation simultaneously.Its reason is, although existing tracer kind is a lot, can not find out simultaneously meet in, stratum good with fracturing fluid compatibility that adsorbance is little, good stability, analysis precision be high, and non-interfering multiple tracer each other.
Therefore, develop a kind of novel tracer that returns discharge opeing for monitoring multistage fracturing and be still one of this area problem demanding prompt solution.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide and a kind ofly for monitoring multistage fracturing, return the tracer of discharge opeing and adopt this tracer monitoring multistage fracturing to return the method for discharge opeing.Tracer of the present invention can overcome existing tracer cannot meet simultaneously with good, the stratum of fracturing fluid compatibility in little, the good stability of adsorbance, an analysis precision high-technology difficult problem.
For reaching above-mentioned purpose, the invention provides a kind of tracer that returns discharge opeing for monitoring multistage fracturing, it comprises 12 kinds of tracer element complex solutions that 12 kinds of tracer elements mix with complexing agent respectively, wherein, 12 kinds of described tracer elements comprise praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
At the above-mentioned tracer of discharge opeing that returns for monitoring multistage fracturing, preferably, the mass concentration of described 12 kinds of tracer element complex solutions is identical, and the mass concentration of described 12 kinds of tracer element complex solutions is 3%-5%.
At the above-mentioned tracer of discharge opeing that returns for monitoring multistage fracturing, preferably, the tracer element in each tracer element complex solution and the mol ratio of complexing agent are 1:8.
At the above-mentioned tracer of discharge opeing that returns for monitoring multistage fracturing, preferably, described complexing agent comprises hydroxylamine chloride.
According to the specific embodiment of the present invention, preferably, the above-mentioned tracer that returns discharge opeing for monitoring multistage fracturing comprises: praseodymium and hydroxylamine chloride be take the hydroxylamine chloride praseodymium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, neodymium and hydroxylamine chloride be take the hydroxylamine chloride neodymium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, samarium and hydroxylamine chloride be take the hydroxylamine chloride samarium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, europium and hydroxylamine chloride be take the hydroxylamine chloride europium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, gadolinium and hydroxylamine chloride be take the hydroxylamine chloride gadolinium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, terbium and hydroxylamine chloride be take the hydroxylamine chloride terbium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, dysprosium and hydroxylamine chloride be take the hydroxylamine chloride dysprosium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, holmium and hydroxylamine chloride be take the hydroxylamine chloride holmium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, erbium and hydroxylamine chloride be take the hydroxylamine chloride erbium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, thulium and hydroxylamine chloride be take the hydroxylamine chloride thulium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, ytterbium and hydroxylamine chloride be take the hydroxylamine chloride ytterbium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5% and lutetium and hydroxylamine chloride and be take the hydroxylamine chloride lutetium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%.
12 kinds of tracer element complex solutions in tracer of the present invention can be prepared separately, merge in use or are added in stratum one by one.The consumption of every kind of tracer element complex compound is to determine according to the concrete condition of injecting stratum.
The design formulas of the consumption of every kind of tracer element complex compound (and then definite tracer element complex solution consumption) as shown in Equation 1 in tracer of the present invention:
A=μ * MDL * V formula 1;
Wherein: A is the consumption of every kind of tracer element complex compound, unit is kg;
μ is assurance coefficient, its objective is the impact of eliminating various natural and artificial unfavorable factors, ensures that the tracer of injection can be detected, its numerical value can be by those skilled in the art according to geology reservoir, background concentration is big or small determine;
MDL is the minimal detectable concentration of instrument to tracer element complex compound, and unit is kg/L;
V is stratum maximum dilution volume, and unit is L, and it can calculate by through type 2:
V=π R
2h Ф S
wformula 2
Wherein: R---on average dilute radius, unit is m;
H---oil reservoir average thickness, unit is m;
Ф---oil reservoir average pore;
S
w---the average water saturation of oil reservoir.
The preparation method of every kind of tracer element complex solution can be identical, and it can comprise the following steps: after the salt that contains tracer element and complexing agent (hydroxylamine chloride) and water are mixed in proportion, can obtain tracer element complex solution.Preferably, the salt that contains tracer element described in comprises the chloride of tracer element, the i.e. chloride of praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
The present invention also provides a kind of method that multistage fracturing returns discharge opeing of monitoring, and it is for adopting the above-mentioned tracer that returns discharge opeing for monitoring multistage fracturing to carry out the method that multistage fracturing returns discharge opeing monitoring.
According to the specific embodiment of the present invention, preferably, the method that above-mentioned monitoring multistage fracturing returns discharge opeing comprises the following steps: divide interval to join the oil well of implementing multistage fracturing measure the described tracer that returns discharge opeing for monitoring multistage fracturing, in fracturing fluid recovery (backflow) process, regularly fracturing outlet liquid is sampled, content to the multiple tracer element complex compound in institute's sample thief detects simultaneously, according to the content of the tracer element complex compound of each interval detecting, realize the monitoring of multistage fracturing being returned to discharge opeing.Wherein, while dividing interval to join in the oil well of implementing multistage fracturing measure tracer, every interval adds different types of a kind of tracer element complex solution, and because the price of various tracers is different, so the large interval of tracer consumption is used the low tracer of price.The content of tracer element complex compound in institute's sample thief is detected and can adopt extraction chromatography to carry out separation and concentration to the tracer element complex compound in institute's sample thief, then use ICP-MS to analyze.
Wherein, the method that adopts extraction chromatography to carry out separation and concentration has both liquid-liquid extraction and chromatography advantage, and reagent dosage is few, and separation and concentration is effective, and it can comprise the following steps: get 500mL or appropriate sample, use NH
3.H
2o and HNO
3regulate its pH value to 2.5-3.0, then take the flow velocity upper prop (the HCl solution equilibria that pillar is 2.6 with pH is in advance crossed) of 5mL/min; The HCl wash-out impurity that is 2.6 by 10mL pH value after upper prop, then uses the HCl drip washing tracer of 50mL6mol/L, and elution speed is 2.5mL/min; By eluent low-temperature heat evaporate to dryness (preventing overdrying) on electric hot plate, then take off and add the dense HNO of 1mL
3, then put back on electric hot plate low temperature and proceed in 5mL volumetric flask after concentrated, being diluted to scale, after shaking up, can measure.Although the method compare with conventional method have advantages of fast, simple, background is low, it is fixing easily runs off mutually, causes pillar repeat usage not high, and must first suck fixedly phase before use, cumbersome.To this, can further adopt P307 extration resin for fixing phase, take HCl as mobile phase, can overcome the fixing shortcoming easily running off mutually, set up one fast, simply, reagent dosage is few, the method for the separation and concentration tracer element complex compound that background is low.After the method separation and concentration, use plasma panel Mass Spectrometer Method, the tracer element complex compound content in can successful working sample.
In above-mentioned method, preferably, the cycle that the fracturing outlet liquid of each interval is sampled is to sample once for every 12 hours.
The invention provides and a kind ofly for monitoring multistage fracturing, return the tracer of discharge opeing and adopt this tracer monitoring multistage fracturing to return the method for discharge opeing.Tracer of the present invention comprises 12 kinds of tracer element complex solutions that 12 kinds of tracer elements mix with complexing agent respectively.Tracer of the present invention and fracturing fluid compatibility are good, little, the good stability of adsorbance in stratum, analysis precision is high and 12 kinds of tracer elements between do not interfere with each other, can realize the monitoring to each layer of fracturing outlet liquid in the multistage fracturing process of oil field, and then the effect split of clear and definite each lamination.
The specific embodiment
For technical characterictic of the present invention, object and beneficial effect being had more clearly, understand, existing technical scheme of the present invention is carried out to following detailed description, but can not be interpreted as restriction that can practical range of the present invention.
Embodiment 1
The present embodiment provides a kind of tracer that returns discharge opeing for monitoring multistage fracturing, it comprises 12 kinds of tracer element complex solutions that 12 kinds of tracer elements mix with hydrogen chloride amine (complexing agent) respectively, be respectively: praseodymium and hydroxylamine chloride be take the hydroxylamine chloride praseodymium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, neodymium and hydroxylamine chloride be take the hydroxylamine chloride neodymium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, samarium and hydroxylamine chloride be take the hydroxylamine chloride samarium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, europium and hydroxylamine chloride be take the hydroxylamine chloride europium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, gadolinium and hydroxylamine chloride be take the hydroxylamine chloride gadolinium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, terbium and hydroxylamine chloride be take the hydroxylamine chloride terbium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, dysprosium and hydroxylamine chloride be take the hydroxylamine chloride dysprosium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, holmium and hydroxylamine chloride be take the hydroxylamine chloride holmium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, erbium and hydroxylamine chloride be take the hydroxylamine chloride erbium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, thulium and hydroxylamine chloride be take the hydroxylamine chloride thulium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, ytterbium and hydroxylamine chloride be take the hydroxylamine chloride ytterbium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5% and lutetium and hydroxylamine chloride and be take the hydroxylamine chloride lutetium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%.
In the present embodiment, the preparation method of every kind of complex solution is identical, it comprises the following steps: after the chloride of the chloride of the chloride of the chloride of the chloride of the chloride of the chloride of the chloride of the chloride of the chloride of the chloride of the chloride of praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium is mixed in proportion with hydroxylamine chloride and water respectively, can obtain respectively 12 kinds of tracer element complex solutions.
Embodiment 2
The present embodiment provides a kind of method that multistage fracturing returns discharge opeing of monitoring, it is for adopting the tracer of embodiment 1 to carry out the method that multistage fracturing returns discharge opeing monitoring, comprise the following steps: divide interval (12 interval) to join the oil well of implementing multistage fracturing measure the described tracer that returns discharge opeing for monitoring multistage fracturing, every interval adds different types of a kind of tracer element complex solution (interval that tracer consumption is large is used the low tracer of price), in fracturing fluid recovery (backflow) process, fracturing outlet liquid was sampled in every 12 hours, content to the multiple tracer element complex compound in institute's sample thief detects simultaneously, according to the content of the tracer element complex compound of each interval detecting, the monitoring of discharge opeing is returned in realization to multistage fracturing.
The content of tracer element complex compound in institute's sample thief is detected and can adopt extraction chromatography to carry out separation and concentration to the tracer element complex compound in institute's sample thief, then use ICP-MS to analyze.
Wherein, the step that adopts extraction chromatography to carry out separation and concentration comprises: get 500mL or appropriate sample, use NH
3.H
2o and HNO
3regulate its pH value to 2.5-3.0, then take the flow velocity upper prop (the HCl solution equilibria that pillar is 2.6 with pH is in advance crossed) of 5mL/min; The HCl wash-out impurity that is 2.6 by 10mL pH value after upper prop, then uses the HCl drip washing tracer of 50mL6mol/L, and elution speed is 2.5mL/min; By eluent low-temperature heat evaporate to dryness (preventing overdrying) on electric hot plate, then take off and add the dense HNO of 1mL
3, then put back on electric hot plate low temperature and proceed in 5mL volumetric flask after concentrated, being diluted to scale, after shaking up, can measure.
Embodiment 3
The present embodiment provides the properties test of tracer of the present invention.
(1), heat stability experiment
Heat stability experiment is for evaluating the heat stability of tracer of the present invention.The method of this heat stability experiment comprises the following steps: by 12 kinds of tracer element (praseodymiums, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium) in each tracer element respectively with complexing agent (hydroxylamine chloride) 1:1 in molar ratio, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, it is 1% tracer element complex solution (preparation method of these tracer element complex solutions is identical with the preparation method of tracer element complex solution in embodiment 1) that 1:8 and 1:9 are mixed with mass concentration, obtain altogether 84 kinds of tracer element complex solutions, these 84 kinds of tracer element complex solutions are heated to respectively to 350 ℃, then cooling, after standing 6 months, observe, experimental result is as shown in table 1.
Table 1 heat stability experimental result
The experimental result of table 1 shows, the mol ratio of tracer element and complexing agent just has heat stability during lower than 1:8, but the conference of complexing agent consumption improves the whole consumption of tracer, improve raw material and corresponding construction cost, so the tracer element of the actual employing of the present invention and the mol ratio of complexing agent are 1:8.
(2), pH stability experiment
PH stability experiment is for evaluating the stability of tracer of the present invention under different pH values.The method of this pH stability experiment comprises the following steps: by 12 kinds of tracer element (praseodymiums, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium) respectively with complexing agent (hydroxylamine chloride) in molar ratio 1:8 to be mixed with mass concentration be 7 groups of 12 kinds of tracer element complex solutions (preparation method of the tracer element complex solution in the preparation method of these tracer element complex solutions and embodiment 1 is identical) of 1%, obtain altogether 84 tracer element complex solutions, the pH value of these 7 groups of tracer element complex solutions is adjusted to respectively to 1, 2, 3, 6, 9, 11 and 14(adopt conventional pH value conditioning agent to adjust the pH value of tracer element complex solution, example hydrochloric acid and NaOH), after standing 6 months, observe, experimental result is as shown in table 2.
Table 2pH stability experiment result
The experimental result of table 2 shows, 12 kinds of tracer element complex solutions of tracer of the present invention all can be in the scope of pH value 3 to 14 stable existence.
(3), compatibility experiment
Compatibility experiment is for measuring compatibility situation between tracer of the present invention and fracturing fluid and the mutual disturbed condition between 12 kinds of tracer elements.The method of this compatibility experiment comprises the following steps: by 12 kinds of tracer element (praseodymiums, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium) respectively with complexing agent (hydroxylamine chloride) in molar ratio 1:8 be mixed with 12 kinds of tracer element complex solutions that concentration is 120mg/L (preparation method of the tracer element complex solution in the preparation method of these tracer element complex solutions and embodiment 1 is identical), by these 12 kinds of tracer element complex solutions all with after identical volume mixture, pressing the volume ratio of 1:1000 mixes the mixed liquor of 12 kinds of tracer element complex compounds again with conventional aqueous fracturing fluid, measure the concentration of every kind of tracer element complex compound, count initial concentration, after standing 6 months at normal temperatures, measure the concentration of every kind of tracer element complex compound, count mensuration concentration, the concentration retention rate that requires initial concentration and measure between concentration is all greater than 90%.
Table 3 compatibility experimental result
| Tracer element complex compound | Initial concentration (μ g/L) | Measure concentration (μ g/L) | Concentration retention rate (%) |
| Hydroxylamine chloride praseodymium | 10.0 | 9.95 | ＞97 |
| Hydroxylamine chloride neodymium | 10.0 | 9.86 | ＞97 |
| Hydroxylamine chloride samarium | 10.0 | 9.92 | ＞97 |
| Hydroxylamine chloride europium | 10.0 | 9.90 | ＞97 |
| Hydroxylamine chloride gadolinium | 10.0 | 9.84 | ＞97 |
| Hydroxylamine chloride terbium | 10.0 | 9.87 | ＞97 |
| Hydroxylamine chloride dysprosium | 10.0 | 9.75 | ＞97 |
| Hydroxylamine chloride holmium | 10.0 | 9.82 | ＞97 |
| Hydroxylamine chloride erbium | 10.0 | 9.79 | ＞97 |
| Hydroxylamine chloride thulium | 10.0 | 9.82 | ＞97 |
| Hydroxylamine chloride ytterbium | 10.0 | 9.81 | ＞97 |
| Hydroxylamine chloride lutetium | 10.0 | 9.84 | ＞97 |
Experimental result from table 3, the concentration retention rate of every kind of tracer element complex compound is all greater than 97%, meet the requirement that in industry standard, concentration retention rate is greater than 90%, this illustrates that the compatibility between tracer of the present invention and fracturing fluid is fine, and the phase mutual interference between 12 kinds of tracer elements is very little.
(4), quiet adsorption experiment
Quiet adsorption experiment is for measuring tracer of the present invention at the degree of absorption on stratum.The method of this quiet adsorption experiment comprises the following steps:
A, employing oil field stratum water, by 12 kinds of tracer elements (praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium) respectively with complexing agent (hydroxylamine chloride) in molar ratio 1:8 be mixed with 12 kinds of tracer element complex solutions (preparation method of the tracer element complex solution in the preparation method of these tracer element complex solutions and embodiment 1 is identical) of same concentrations, measure the initial concentration C of tracer element complex compound in every kind of tracer element complex solution
0;
B, take the rock sample that 30g pulverizes respectively and be placed in 12 containers, by rock sample: the mass ratio that tracer element complex solution is 1:3, in being housed, the container of rock sample adds respectively 12 kinds of tracer element complex solutions, after stirring, measure the concentration C 1 of tracer element complex compound in every kind of tracer element complex solution, sealed container port, then shakes 6 months at normal temperatures;
C, take out 12 kinds of tracer element complex solutions in container respectively, measure the concentration C of tracer element complex compound in every kind of tracer element complex solution;
D, obtain concentration retention rate C/C
0, work as C/C
0while being greater than 80%, meet the requirements.
The experimental result of this quiet adsorption experiment is as shown in table 4.
The quiet adsorption experiment result of table 4
The experimental result of table 4 shows, the quiet adsorbance of 12 kinds of tracer element complex compounds in tracer of the present invention is all less than 3%, meets the requirement that in the system of selection > > standard of SY/T5925-94 < < oil-field flooding chemical tracer, tracer Static Adsorption is less than 20%.
Claims (7)
1. a tracer that returns discharge opeing for monitoring multistage fracturing, it comprises 12 kinds of tracer element complex solutions that 12 kinds of tracer elements mix with complexing agent respectively, wherein, 12 kinds of described tracer elements comprise praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
2. the tracer that returns discharge opeing for monitoring multistage fracturing according to claim 1, wherein, the mass concentration of described 12 kinds of tracer element complex solutions is identical, and the mass concentration of described 12 kinds of tracer element complex solutions is 3%-5%.
3. the tracer that returns discharge opeing for monitoring multistage fracturing according to claim 1 and 2, wherein, the tracer element in each tracer element complex solution and the mol ratio of complexing agent are 1:8.
4. according to returning the tracer of discharge opeing for monitoring multistage fracturing described in claim 1 or 3, wherein, described complexing agent comprises hydroxylamine chloride.
5. the tracer that returns discharge opeing for monitoring multistage fracturing according to claim 1, it comprises: praseodymium and hydroxylamine chloride be take the hydroxylamine chloride praseodymium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, neodymium and hydroxylamine chloride be take the hydroxylamine chloride neodymium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, samarium and hydroxylamine chloride be take the hydroxylamine chloride samarium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, europium and hydroxylamine chloride be take the hydroxylamine chloride europium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, gadolinium and hydroxylamine chloride be take the hydroxylamine chloride gadolinium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, terbium and hydroxylamine chloride be take the hydroxylamine chloride terbium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, dysprosium and hydroxylamine chloride be take the hydroxylamine chloride dysprosium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, holmium and hydroxylamine chloride be take the hydroxylamine chloride holmium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, erbium and hydroxylamine chloride be take the hydroxylamine chloride erbium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, thulium and hydroxylamine chloride be take the hydroxylamine chloride thulium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%, ytterbium and hydroxylamine chloride be take the hydroxylamine chloride ytterbium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5% and lutetium and hydroxylamine chloride and be take the hydroxylamine chloride lutetium aqueous solution that mass concentration that the mixed in molar ratio of 1:8 forms is 3%-5%.
6. monitor multistage fracturing and return the method for discharge opeing, it is for adopting the tracer that returns discharge opeing for monitoring multistage fracturing described in claim 1-5 any one to carry out the method that multistage fracturing returns discharge opeing monitoring.
7. monitoring multistage fracturing according to claim 6 returns the method for discharge opeing, it comprises the following steps: divide interval to join the oil well of implementing multistage fracturing measure the described tracer that returns discharge opeing for monitoring multistage fracturing, in fracturing fluid recovery (backflow) process, regularly fracturing outlet liquid is sampled, content to the multiple tracer element complex compound in institute's sample thief detects, according to the content of the tracer element complex compound detecting, realize the monitoring of multistage fracturing being returned to discharge opeing.
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