CN103603655B - 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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- CN103603655B CN103603655B CN201310476303.6A CN201310476303A CN103603655B CN 103603655 B CN103603655 B CN 103603655B CN 201310476303 A CN201310476303 A CN 201310476303A CN 103603655 B CN103603655 B CN 103603655B
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- 239000000700 radioactive tracer Substances 0.000 title claims abstract description 134
- 238000012544 monitoring process Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000012530 fluid Substances 0.000 title claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 title abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 43
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 12
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 11
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 11
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 11
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 11
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 11
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 11
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 11
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 11
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 11
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 11
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 11
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims abstract description 11
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims abstract description 11
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 11
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 11
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims abstract description 11
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims abstract description 11
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 11
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 11
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 11
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims abstract description 11
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims abstract description 11
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 36
- -1 hydroxylamine chloride hydroxylamine chloride neodymium Chemical compound 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 8
- 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
- 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
- 238000005660 chlorination reaction Methods 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 3
- HCGJNVCHYPIJLT-UHFFFAOYSA-K [Sm+3].[Cl-].NO.[Cl-].[Cl-] Chemical compound [Sm+3].[Cl-].NO.[Cl-].[Cl-] HCGJNVCHYPIJLT-UHFFFAOYSA-K 0.000 claims description 3
- 239000003129 oil well Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims 1
- 239000008139 complexing agent Substances 0.000 abstract description 13
- 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 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 13
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- 239000000203 mixture Substances 0.000 description 3
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
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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 method of returning discharge opeing returning discharge opeing for monitoring multistage fracturing,
Belong to technical field of petroleum extraction.
Background technology
Tracer monitoring technology is the Dynamic Monitoring that current field use is quite varied, in water drive, non-phase-mixing driving, polymerization
All having application in the various displacement of reservoir oil engineerings such as thing drives, steam drives, SAGD, the connection being mainly used for monitoring between injection-production well is closed
System and inject fluid in the earth formation involve situation.
Tracer monitoring technology is currently also used for monitoring fracturing effect aspect, but is mainly used for evaluating the growth feelings of fracturing fracture
Condition.The method is by using gamma spectrometer and the orientation tester such as gamma instrument or magnetic determining device monitoring radioactivity to show
Track agent distribution situation in the earth formation realizes.Additionally, there is also about using grinding of tracer monitoring fracturing outlet liquid
Study carefully, but be currently limited to the row's of the returning situation using single tracer generally to evaluate fracturing fluid, still can not realize using simultaneously
Multiple tracer layering section evaluates the row's of returning situation of each layer fracturing fluid.Its reason is, although existing tracer kind is very
Many, but can not find out and meet with fracturing fluid compatibility is good, adsorbance is little in stratum, good stability, analysis precision simultaneously
Height, and the most non-interfering multiple tracer.
Therefore, developing a kind of novel tracer returning discharge opeing for monitoring multistage fracturing, to be still this area urgently to be resolved hurrily
One of problem.
Summary of the invention
For solving above-mentioned technical problem, it is an object of the invention to provide a kind of spike returning discharge opeing for monitoring multistage fracturing
Agent and use the method that this tracer monitoring multistage fracturing returns discharge opeing.The tracer of the present invention can overcome existing tracer without
Method meets with fracturing fluid compatibility is good, the technical barriers such as adsorbance is little, good stability, analysis precision are high in stratum simultaneously.
For reaching above-mentioned purpose, the present invention provides a kind of tracer returning discharge opeing for monitoring multistage fracturing, and it includes 12 kinds
12 kinds of tracer element complex solutions that tracer element mixes with complexing agent respectively, wherein, described 12 kinds are shown
Track element includes praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
Above-mentioned for monitoring in the tracer that multistage fracturing returns discharge opeing, it is preferable that described 12 kinds of tracer elements complexing
The mass concentration of the thing aqueous solution is identical, and the mass concentration of described 12 kinds of tracer element complex solutions is
3%-5%。
Above-mentioned for monitoring in the tracer that multistage fracturing returns discharge opeing, it is preferable that each tracer element complex compound water
Tracer element in solution is 1:8 with the mol ratio of complexing agent.
Above-mentioned for monitoring in the tracer that multistage fracturing returns discharge opeing, it is preferable that described complexing agent includes hydroxylamine chloride.
Detailed description of the invention according to the present invention, it is preferable that above-mentioned return the tracer bag of discharge opeing for monitoring multistage fracturing
Include: the hydroxylamine chloride praseodymium aqueous solution with the mass concentration of the mixed in molar ratio of 1:8 as 3%-5% of praseodymium and hydroxylamine chloride,
The hydroxylamine chloride neodymium aqueous solution with the mass concentration of the mixed in molar ratio of 1:8 as 3%-5% of neodymium and hydroxylamine chloride, samarium and
The hydroxylamine chloride hydroxylamine chloride samarium aqueous solution, europium and chlorination with the mass concentration of the mixed in molar ratio of 1:8 as 3%-5%
The azanol hydroxylamine chloride europium aqueous solution, gadolinium and hydroxylamine chloride with the mass concentration of the mixed in molar ratio of 1:8 as 3%-5%
The hydroxylamine chloride gadolinium aqueous solution, terbium and hydroxylamine chloride with the mass concentration of the mixed in molar ratio of 1:8 as 3%-5% are with 1:8
The hydroxylamine chloride terbium aqueous solution, dysprosium and hydroxylamine chloride the rubbing with 1:8 that mass concentration is 3%-5% of mixed in molar ratio
The hydroxylamine chloride dysprosium aqueous solution, holmium and the hydroxylamine chloride that mass concentration is 3%-5% that ratio mixes is with the mol ratio of 1:8
The mass concentration mixed is the hydroxylamine chloride holmium aqueous solution, erbium and the hydroxylamine chloride mixed in molar ratio with 1:8 of 3%-5%
The hydroxylamine chloride erbium aqueous solution, thulium and hydroxylamine chloride that mass concentration is 3%-5% form with the mixed in molar ratio of 1:8
The hydroxylamine chloride thulium aqueous solution, ytterbium and hydroxylamine chloride that mass concentration is 3%-5% with the matter of the mixed in molar ratio of 1:8
Amount concentration is the hydroxylamine chloride ytterbium aqueous solution of 3%-5% and lutetium and the hydroxylamine chloride quality with the mixed in molar ratio of 1:8
Concentration is the hydroxylamine chloride lutetium aqueous solution of 3%-5%.
12 kinds of tracer element complex solutions in the tracer of the present invention can be manufactured separately, and closes in use
And or add one by one to stratum.The consumption of every kind of tracer element complex compound be according to inject stratum concrete condition and
Determine.
In the tracer of the present invention, the computing formula of the consumption of every kind of tracer element complex compound (and then determines and shows as shown in Equation 1
Track element complex amount of aqueous solution used):
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 to eliminate the impact of various natural and artificial unfavorable factor, ensures the tracer injected
Can be detected, its numerical value can be determined according to geology reservoir, background concentration size by those skilled in the art；
MDL is the instrument minimal detectable concentration to tracer element complex compound, and unit is kg/L；
V is stratum maximum dilution volume, and unit is L, and it can be calculated by formula 2:
V=πR2hФSwFormula 2
Wherein: R average dilution radius, unit is m；
H oil reservoir average thickness, unit is m；
Ф oil reservoir average pore；
SwThe average water saturation of oil reservoir.
The preparation method of every kind of tracer element complex solution can be identical, and it may comprise steps of: will be containing showing
After the salt of track element mixes in proportion with complexing agent (hydroxylamine chloride) and water, i.e. can get tracer element complex compound water
Solution.Preferably, the described salt containing tracer element includes the chloride of tracer element, i.e. praseodymium, neodymium, samarium, europium, gadolinium,
The chloride of terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
The present invention also provides for a kind of monitoring the method that multistage fracturing returns discharge opeing, and it monitors multistage fracturing for using above-mentioned being used for
The tracer returning discharge opeing carries out the method that multistage fracturing returns discharge opeing monitoring.
Detailed description of the invention according to the present invention, it is preferable that above-mentioned monitoring multistage fracturing returns the method for discharge opeing and includes following
Step: be used for monitoring multistage fracturing and return the tracer layering section of discharge opeing by described and join and implement the oil of multistage fracturing measure
In well, during fracturing fluid recovery (backflow), periodically fracturing outlet liquid is sampled, to the multiple spike unit in taken sample
The content of element complex compound detects, according to the content of the tracer element complex compound of each interval detected, it is achieved right simultaneously
Multistage fracturing returns the monitoring of discharge opeing.Wherein, when the tracer section of layering being joined in the oil well implementing multistage fracturing measure,
Every interval adds different types of a kind of tracer element complex solution, owing to the price of various tracers is different, therefore
The interval that tracer consumption is big uses the tracer that price is low.The content of tracer element complex compound in taken sample is examined
Survey can use extraction chromatography that the tracer element complex compound in taken sample is carried out separation and concentration, then uses
ICP-MS is analyzed.
Wherein, the method using extraction chromatography to carry out separation and concentration has both liquid-liquid extraction and chromatography advantage, examination
Agent consumption is few, and separation and concentration is effective, and it may comprise steps of: takes 500mL or appropriate amount of sample, uses NH3.H2O
And HNO3Regulate its pH value to 2.5-3.0, then with the flow velocity upper prop of 5mL/min (pillar in advance with pH for 2.6
HCl solution equilibrated)；Elute impurity with the HCl that 10mL pH value is 2.6 after upper prop, then use 50mL
The HCl drip washing tracer of 6mol/L, elution speed is 2.5mL/min；Eluent low-temperature heat on electric hot plate is evaporated
(preventing overdrying), then takes off the addition dense HNO of 1mL3, then put back on electric hot plate after low temperature concentrates and proceed to 5mL capacity
In Ping, it is diluted to scale, can measure after shaking up.Although the method has quick, simple, originally compared with conventional method
The advantage that the end is low, but it fixes compatible being easy to run off, and causes pillar repeat usage the highest, and must first inhale before use
Enter fixing phase, cumbersome.To this, can use P307 extration resin further is fixing phase, with HCl for flowing
Phase, it is possible to overcome the fixing shortcoming being easy to run off mutually, set up one quickly, simple, reagent dosage is few, the separation that background is low
The method of enrichment tracer element complex compound.Detect with Plasma-Mass Spectroscopy after the method separation and concentration, it is possible to successfully measure sample
Tracer element complex compound content in product.
In the methods described above, it is preferable that the cycle being sampled the fracturing outlet liquid of each interval is to take for every 12 hours
Sample is once.
The invention provides and a kind of return the tracer of discharge opeing and use the multistage pressure of this tracer monitoring for monitoring multistage fracturing
Split the method returning discharge opeing.The tracer of the present invention includes 12 kinds that 12 kinds of tracer elements mix with complexing agent respectively and shows
The track element complex aqueous solution.The tracer of the present invention and fracturing fluid compatibility are good, adsorbance is little in stratum, good stability,
It does not interfere with each other between analysis precision height and 12 kinds of tracer elements, it is possible to realize layer each during the multistage fracturing of oil field
The monitoring of fracturing outlet liquid, and then the effect that the most each lamination splits.
Detailed description of the invention
In order to the technical characteristic of the present invention, purpose and beneficial effect are more clearly understood from, the existing technology to the present invention
Scheme carries out described further below, but it is not intended that to the present invention can the restriction of practical range.
Embodiment 1
The present embodiment provides a kind of tracer returning discharge opeing for monitoring multistage fracturing, and it includes that 12 kinds of tracer elements are respectively
The 12 kinds of tracer element complex solutions mixed with hydrogen chloride amine (complexing agent), are respectively as follows: praseodymium and chlorination hydroxyl
The amine hydroxylamine chloride praseodymium aqueous solution, neodymium and hydroxylamine chloride with the mass concentration of the mixed in molar ratio of 1:8 as 3%-5% with
The mass concentration of the mixed in molar ratio of 1:8 is that the hydroxylamine chloride neodymium aqueous solution, samarium and the hydroxylamine chloride of 3%-5% are with 1:8
The hydroxylamine chloride samarium aqueous solution, europium and hydroxylamine chloride the rubbing with 1:8 that mass concentration is 3%-5% of mixed in molar ratio
The hydroxylamine chloride europium aqueous solution, gadolinium and the hydroxylamine chloride that mass concentration is 3%-5% that ratio mixes is with the mol ratio of 1:8
The mass concentration mixed is the hydroxylamine chloride gadolinium aqueous solution, terbium and the hydroxylamine chloride mixed in molar ratio with 1:8 of 3%-5%
The hydroxylamine chloride terbium aqueous solution, dysprosium and hydroxylamine chloride that mass concentration is 3%-5% form with the mixed in molar ratio of 1:8
The hydroxylamine chloride dysprosium aqueous solution, holmium and hydroxylamine chloride that mass concentration is 3%-5% with the matter of the mixed in molar ratio of 1:8
Amount concentration is that the hydroxylamine chloride holmium aqueous solution, erbium and the hydroxylamine chloride of 3%-5% are dense with the quality of the mixed in molar ratio of 1:8
Degree for the hydroxylamine chloride erbium aqueous solution, thulium and the hydroxylamine chloride of 3%-5% with the mass concentration of the mixed in molar ratio of 1:8 is
The hydroxylamine chloride thulium aqueous solution, ytterbium and the hydroxylamine chloride of 3%-5% with the mass concentration of the mixed in molar ratio of 1:8 are
The hydroxylamine chloride ytterbium aqueous solution of 3%-5% and lutetium and hydroxylamine chloride with the mass concentration of the mixed in molar ratio of 1:8 are
The hydroxylamine chloride lutetium aqueous solution of 3%-5%.
In the present embodiment, the preparation method of every kind of complex solution is identical, and it comprises the following steps: by the chlorination of praseodymium
Thing, the chloride of neodymium, the chloride of samarium, the chloride of europium, the chloride of gadolinium, the chloride of terbium, the chloride of dysprosium,
The chloride of the chloride of holmium, the chloride of erbium, the chloride of thulium, the chloride of ytterbium and lutetium respectively with hydroxylamine chloride and water
After mixing in proportion, 12 kinds of tracer element complex solutions can be respectively obtained.
Embodiment 2
The present embodiment provides a kind of and monitors the method that multistage fracturing returns discharge opeing, and it carries out many for using the tracer of embodiment 1
The method of level fracturing outlet liquid monitoring, comprises the following steps: be used for monitoring multistage fracturing return the tracer of discharge opeing by described
Layering section (12 interval) joins in the oil well implementing multistage fracturing measure, and every interval adds different types of a kind of spike
The element complex aqueous solution (interval that tracer consumption is big uses the tracer that price is low), during fracturing fluid recovery (backflow),
Fracturing outlet liquid was sampled in every 12 hours, the content of the multiple tracer element complex compound in taken sample is entered simultaneously
Row detection, according to the content of the tracer element complex compound of each interval detected, it is achieved multistage fracturing returns the monitoring of discharge opeing.
The content of tracer element complex compound in taken sample carries out detection can use extraction chromatography in taken sample
Tracer element complex compound carry out separation and concentration, then use ICP-MS to be analyzed.
Wherein, the step using extraction chromatography to carry out separation and concentration includes: takes 500mL or appropriate amount of sample, uses NH3.H2O
And HNO3Regulate its pH value to 2.5-3.0, then with the flow velocity upper prop of 5mL/min (pillar in advance with pH for 2.6
HCl solution equilibrated)；Elute impurity with the HCl that 10mL pH value is 2.6 after upper prop, then use 50mL
The HCl drip washing tracer of 6mol/L, elution speed is 2.5mL/min；Eluent low-temperature heat on electric hot plate is evaporated
(preventing overdrying), then takes off the addition dense HNO of 1mL3, then put back on electric hot plate after low temperature concentrates and proceed to 5mL capacity
In Ping, it is diluted to scale, can measure after shaking up.
Embodiment 3
The present embodiment provides the properties test of the tracer of the present invention.
(1), heat endurance experiment
Heat endurance experiment is for evaluating the heat endurance of the tracer of the present invention.This heat endurance experiment method include with
Lower step: by 12 kinds of tracer elements (praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium)
In each of tracer element respectively with complexing agent (hydroxylamine chloride) 1:1 in molar ratio, 1:2,1:3,1:4,1:5,1:6,
1:7,1:8 and 1:9 are configured to tracer element complex solution (these tracer element complex compound water that mass concentration is 1%
The preparation method of solution is identical with the preparation method of the tracer element complex solution in embodiment 1), there are 84
Plant tracer element complex solution, these 84 kinds of tracer element complex solutions are separately heated to 350 DEG C, the coldest
But, observing after standing 6 months, experimental result is as shown in table 1.
Table 1 heat endurance experimental result
When the mol ratio of test result indicate that of table 1, tracer element and complexing agent is less than 1:8, just there is heat endurance, but
Amount of complex conference improves the overall consumption of tracer, improves raw material and the construction cost of correspondence, so the present invention is real
The tracer element that border uses is 1:8 with the mol ratio of complexing agent.
(2), pH stability experiment
PH stability experiment is for evaluating the tracer of present invention stability at various ph values.This pH stability is real
The method tested comprises the following steps: by 12 kinds of tracer elements (praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium,
Thulium, ytterbium and lutetium) be configured to that mass concentration is 1% respectively with complexing agent (hydroxylamine chloride) 1:8 in molar ratio 7 groups
12 kinds of tracer element complex solution (preparation method of these tracer element complex solutions and showing in embodiment 1
The preparation method of the track element complex aqueous solution is identical), there are 84 tracer element complex solutions, by this 7
The pH value of group tracer element complex solution is separately adjusted to angularly the pH that 1,2,3,6,9,11 and 14(employings are conventional
The pH value of tracer element complex solution is adjusted by value conditioning agent, example hydrochloric acid and NaOH), stand 6
Observing after Yue, experimental result is as shown in table 2.
Table 2pH stability experiment result
Test result indicate that of table 2,12 kinds of tracer element complex solutions of the tracer of the present invention all can be at pH
Stable existence in the range of value 3 to 14.
(3), compatibility experiment
Compatibility experiment is for measuring the compatibility situation between the tracer of the present invention and fracturing fluid and 12 kinds of tracer elements
Between interfere situation.This compatibility experiment method comprise the following steps: 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) 1:8 in molar ratio
Be configured to 12 kinds of tracer element complex solutions that concentration is 120mg/L (these tracer element complex solutions
Preparation method is identical with the preparation method of the tracer element complex solution in embodiment 1), by these 12 kinds of spike units
After element complex solution is all with identical volume mixture, then press the volume ratio of 1:1000 by 12 kinds of tracer element complex compounds
Mixed liquor mix with conventional aqueous fracturing fluid, measure the concentration of every kind of tracer element complex compound, be calculated as initial concentration,
After standing 6 months under normal temperature, measure the concentration of every kind of tracer element complex compound, be calculated as measuring concentration, it is desirable to initial concentration
And the concentration retention rate measured between concentration is all higher 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 |
From the experimental result of table 3, the concentration retention rate of every kind of tracer element complex compound is both greater than 97%, meets industry
The concentration retention rate requirement more than 90% in standard, the compatibility between tracer and the fracturing fluid of this explanation present invention is very
Good, interfering between 12 kinds of tracer elements is the least.
(4), quiet adsorption experiment
Quiet adsorption experiment is for measuring the tracer of present invention degree of absorption in the earth formation.The method bag of this quiet adsorption experiment
Include following steps:
A, use oil field stratum water, by 12 kinds of tracer elements (praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium,
Thulium, ytterbium and lutetium) 12 kinds of spike units of same concentrations it are configured to respectively with complexing agent (hydroxylamine chloride) 1:8 in molar ratio
Element complex solution (preparation method of these tracer element complex solutions and the tracer element complexing in embodiment 1
The preparation method of the thing aqueous solution is identical), measure the initial of tracer element complex compound in every kind of tracer element complex solution
Concentration C0；
B, respectively weigh 30g pulverize rock sample be placed in 12 containers, by rock sample: tracer element complex solution is
The mass ratio of 1:3, adds 12 kinds of tracer element complex solutions respectively in equipped with the container of rock sample, after stirring,
Measuring the concentration C 1 of tracer element complex compound in every kind of tracer element complex solution, sealed container port, then often
The lower concussion of temperature 6 months；
12 kinds of tracer element complex solutions in c, respectively taking-up container, measure every kind of tracer element complex compound water-soluble
The concentration C of tracer element complex compound in liquid；
D, obtain concentration retention rate C/C0, work as C/C0During more than 80%, meet the requirements.
The experimental result of this quiet adsorption experiment is as shown in table 4.
The quiet Adsorption experimental results of table 4
Test result indicate that of table 4, the quiet adsorbance of 12 kinds of tracer element complex compounds in the tracer of the present invention is the least
In 3%, meet tracer Static Adsorption in SY/T5925 94 " system of selection of oil-field flooding chemical tracer " standard
Requirement less than 20%.
Claims (2)
1. being used for monitoring multistage fracturing and return a tracer for discharge opeing, it is made up of following tracer element complex solution:
The hydroxylamine chloride praseodymium aqueous solution with the mass concentration of the mixed in molar ratio of 1:8 as 3%-5% of praseodymium and hydroxylamine chloride, neodymium and
The hydroxylamine chloride hydroxylamine chloride neodymium aqueous solution, samarium and chlorination with the mass concentration of the mixed in molar ratio of 1:8 as 3%-5%
The azanol hydroxylamine chloride samarium aqueous solution, europium and hydroxylamine chloride with the mass concentration of the mixed in molar ratio of 1:8 as 3%-5%
The hydroxylamine chloride europium aqueous solution, gadolinium and hydroxylamine chloride with the mass concentration of the mixed in molar ratio of 1:8 as 3%-5% are with 1:8
The hydroxylamine chloride gadolinium aqueous solution, terbium and hydroxylamine chloride the rubbing with 1:8 that mass concentration is 3%-5% of mixed in molar ratio
The hydroxylamine chloride terbium aqueous solution, dysprosium and the hydroxylamine chloride that mass concentration is 3%-5% that ratio mixes is with the mol ratio of 1:8
The mass concentration mixed is the hydroxylamine chloride dysprosium aqueous solution, holmium and the hydroxylamine chloride mixed in molar ratio with 1:8 of 3%-5%
The hydroxylamine chloride holmium aqueous solution, erbium and hydroxylamine chloride that mass concentration is 3%-5% form with the mixed in molar ratio of 1:8
The hydroxylamine chloride erbium aqueous solution, thulium and hydroxylamine chloride that mass concentration is 3%-5% with the matter of the mixed in molar ratio of 1:8
Amount concentration is that the hydroxylamine chloride thulium aqueous solution, ytterbium and the hydroxylamine chloride of 3%-5% are dense with the quality of the mixed in molar ratio of 1:8
Degree for the hydroxylamine chloride ytterbium aqueous solution of 3%-5% and lutetium and hydroxylamine chloride with the mass concentration of the mixed in molar ratio of 1:8
The hydroxylamine chloride lutetium aqueous solution for 3%-5%.
2. monitoring the method that multistage fracturing returns discharge opeing, it monitors multistage pressure for using being used for described in claim 1
Splitting and return the tracer of discharge opeing and carry out the method that multistage fracturing returns discharge opeing monitoring, the method comprises the following steps: by described use
The tracer layering section returning discharge opeing in monitoring multistage fracturing joins in the oil well implementing multistage fracturing measure, and every interval adds
Different types of a kind of tracer element complex solution, during fracturing fluid recovery (backflow), is periodically carried out fracturing outlet liquid
Sampling, detects the content of the multiple tracer element complex compound in taken sample, according to the tracer element network detected
The content of compound, it is achieved multistage fracturing is returned the monitoring of discharge opeing.
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