CN111648765A - Environment-friendly oil-soluble tracer and application thereof - Google Patents
Environment-friendly oil-soluble tracer and application thereof Download PDFInfo
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- CN111648765A CN111648765A CN202010628781.4A CN202010628781A CN111648765A CN 111648765 A CN111648765 A CN 111648765A CN 202010628781 A CN202010628781 A CN 202010628781A CN 111648765 A CN111648765 A CN 111648765A
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- 239000000700 radioactive tracer Substances 0.000 title claims abstract description 110
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 53
- 239000003921 oil Substances 0.000 claims abstract description 48
- -1 organic acid rare earth salt Chemical class 0.000 claims abstract description 28
- 239000010779 crude oil Substances 0.000 claims abstract description 26
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 238000009616 inductively coupled plasma Methods 0.000 claims abstract description 7
- 239000003755 preservative agent Substances 0.000 claims abstract description 7
- 230000002335 preservative effect Effects 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 238000012544 monitoring process Methods 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 229910052772 Samarium Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 8
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 8
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 claims description 7
- QELSKZZBTMNZEB-UHFFFAOYSA-N propylparaben Chemical compound CCCOC(=O)C1=CC=C(O)C=C1 QELSKZZBTMNZEB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 6
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- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 claims description 5
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 claims description 5
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- 235000010446 mineral oil Nutrition 0.000 claims description 5
- 235000010232 propyl p-hydroxybenzoate Nutrition 0.000 claims description 5
- 239000004405 propyl p-hydroxybenzoate Substances 0.000 claims description 5
- QFOHBWFCKVYLES-UHFFFAOYSA-N Butylparaben Chemical compound CCCCOC(=O)C1=CC=C(O)C=C1 QFOHBWFCKVYLES-UHFFFAOYSA-N 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 claims description 4
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 4
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 claims description 4
- 239000004403 ethyl p-hydroxybenzoate Substances 0.000 claims description 4
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
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- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 229940067596 butylparaben Drugs 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- 229960001617 ethyl hydroxybenzoate Drugs 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- 229960002216 methylparaben Drugs 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229960003415 propylparaben Drugs 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 2
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- 239000002537 cosmetic Substances 0.000 claims 1
- 239000003350 kerosene Substances 0.000 abstract description 12
- 238000001514 detection method Methods 0.000 abstract description 11
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000008117 stearic acid Substances 0.000 abstract description 2
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- 239000000047 product Substances 0.000 description 7
- IJEFAHUDTLUXDY-UHFFFAOYSA-J 7,7-dimethyloctanoate;zirconium(4+) Chemical compound [Zr+4].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O IJEFAHUDTLUXDY-UHFFFAOYSA-J 0.000 description 6
- 238000010276 construction Methods 0.000 description 6
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- 231100000419 toxicity Toxicity 0.000 description 5
- 230000001988 toxicity Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003129 oil well Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000001216 Samarium Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 229930195733 hydrocarbon Natural products 0.000 description 2
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- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000003746 yttrium Chemical class 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 1
- SLEMZXQMOMKPCD-UHFFFAOYSA-L 7,7-dimethyloctanoate;iron(2+) Chemical compound [Fe+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O SLEMZXQMOMKPCD-UHFFFAOYSA-L 0.000 description 1
- IFWKLMNFZSMKJH-UHFFFAOYSA-K 7,7-dimethyloctanoate;lanthanum(3+) Chemical compound [La+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O IFWKLMNFZSMKJH-UHFFFAOYSA-K 0.000 description 1
- UZGARMTXYXKNQR-UHFFFAOYSA-K 7,7-dimethyloctanoate;neodymium(3+) Chemical compound [Nd+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O UZGARMTXYXKNQR-UHFFFAOYSA-K 0.000 description 1
- FBEKWOCPHIOZKE-UHFFFAOYSA-L CCCCCCC(C)(C)C(=O)O[Ca]OC(=O)C(C)(C)CCCCCC Chemical compound CCCCCCC(C)(C)C(=O)O[Ca]OC(=O)C(C)(C)CCCCCC FBEKWOCPHIOZKE-UHFFFAOYSA-L 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
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- LBGZJZYQLMTOBU-UHFFFAOYSA-K [Pr+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O Chemical compound [Pr+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O LBGZJZYQLMTOBU-UHFFFAOYSA-K 0.000 description 1
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- FGWBAWJNMYHXMA-UHFFFAOYSA-K cerium(3+);7,7-dimethyloctanoate Chemical compound [Ce+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O FGWBAWJNMYHXMA-UHFFFAOYSA-K 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
The invention discloses an environment-friendly oil-soluble tracer and application thereof, wherein the tracer comprises the following raw materials in percentage by weight: 58.4-73.7% of organic acid rare earth salt, 22-33% of solvent, 4-8% of surfactant and 0.3-0.6% of preservative. The organic acid rare earth salt is at least one of benzoic acid rare earth salt, stearic acid rare earth salt, naphthenic acid rare earth salt and neodecanoic acid rare earth salt. The oil-soluble tracer provided by the invention is environment-friendly, has multiple element types, high flash point, is convenient to transport, has good compatibility with crude oil and kerosene, and does not have precipitate. The inductively coupled plasma mass spectrometer can realize the simultaneous detection of various rare earth elements, can detect the oil yield of each section, has high detection precision, and can reach the ppt level (10)‑12kg/L grade), the usage amount of the oil-soluble tracer can be reduced.
Description
The technical field is as follows:
the invention relates to the field of oil exploitation, and particularly relates to an environment-friendly oil-soluble tracer and application thereof.
Background art:
the tracing monitoring technology is generally used for monitoring the oil production effect of each section of a fractured horizontal well in recent years due to the characteristics of simple construction process, low risk, long monitoring time, no need of underground operation and wide application range (horizontal wells, highly-deviated wells, special tubular columns, high-water-content wells and low-liquid-production wells), and provides a basis for analyzing the fracturing effect in the later period and improving the fracturing process.
The tracer mainly comprises a water-soluble tracer and an oil-soluble tracer, which are respectively used for monitoring the water yield and the oil yield of each fracturing section after the fracturing of an oil well, and the commonly used oil-soluble tracer mainly comprises halohydrocarbon, halobenzene and haloester. Although the types of oil-soluble tracers in the prior art are many, most of the oil-soluble tracers are volatile at room temperature and have certain toxicity, and are harmful to human bodies and the environment, at present, the content of the oil-soluble tracers in crude oil is monitored by a gas chromatograph-mass spectrometer, and the detection precision of most of the oil-soluble tracers is ppb (10 ppb) (generally)-9kg/L) grade. There is room for further reduction in the amount of oil soluble tracer used.
Chinese patent document CN111005714A discloses a method for monitoring oil well yield by using a tracer, wherein the used oil-soluble tracer is halogenated benzene or halogenated toluene, and the oil-soluble tracer has strong toxicity. Chinese patent document CN109931052A discloses a method for monitoring the effect and productivity of an oil well after layering or staged fracturing by using a tracer, wherein the used oil-soluble tracer is halogenated aromatic hydrocarbon, and the oil-soluble tracer has certain toxicity. Chinese patent document CN106014389A discloses a method for testing oil-water contribution of each section of a volume fractured horizontal well by using a chemical tracer, wherein the used oil-soluble tracer is chloro-naphthenic hydrocarbon or bromo-naphthenic hydrocarbon, and the oil-soluble tracer has certain toxicity.
With the stricter requirements of oil fields on the safety and environmental protection of oil field chemical agents, an oil-soluble tracer which is environment-friendly, non-toxic, multiple in types and high in detection precision is urgently needed.
The prior art reports that rare earth elements are used for preparing water-soluble tracers, for example, Chinese patent document CN110685673A (201910988912.7) relates to a preparation method of a water-soluble trace element tracer with high salt and high alkalinity resistance for oil fields. However, this tracer is a water soluble tracer and can only be used to monitor the water production at each stage after fracturing. And the inorganic rare earth salt commonly used in the field can not be applied to the oil-soluble tracer because the inorganic rare earth salt can not be dissolved in crude oil.
The invention content is as follows:
the invention provides an environment-friendly oil-soluble tracer and application thereof in monitoring oil yield of each fracturing section, aiming at solving the problems that the existing oil-soluble tracer in the prior art has certain toxicity and low detection precision.
In order to achieve the purpose, the invention adopts the following technical scheme:
the environment-friendly oil-soluble tracer agent is characterized by comprising the following raw materials in percentage by weight: 58.4-73.7% of organic acid rare earth salt, 22-33% of organic solvent, 4-8% of surfactant and 0.3-0.6% of preservative.
Organic rare earth salts are commonly used as resin stabilizers and rubber catalysts, mainly exist in the form of powder or liquid with high viscosity, and cannot be directly applied to crude oil.
Preferably, the organic acid rare earth salt is one of benzoic acid rare earth salt, stearic acid rare earth salt, naphthenic acid rare earth salt and neodecanoic acid rare earth salt.
Preferably, the rare earth element in the organic acid rare earth salt is one of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium and yttrium.
Preferably, the organic solvent is an oil-soluble solvent such as mineral oil, aromatic hydrocarbons, aliphatic hydrocarbons, ketones, and the like.
Further preferably, the mineral oil is white oil, and comprises at least one of food-grade white oil, cosmetic-grade white oil, industrial white oil and light white oil.
The aliphatic hydrocarbon is one of n-pentane, n-hexane and n-octane;
the aromatic hydrocarbon is one of benzene, toluene and xylene;
the ketone is one of acetone, methyl butanone and methyl isobutyl ketone.
Preferably, the surfactant is at least one of span 20, span 40, span 60 and span 80. The surfactant can improve the dissolving effect of the organic acid rare earth salt and the mineral oil, reduce the viscosity of the solution and improve the stability of the solution.
Preferably, the preservative is at least one of methylparaben, ethylparaben, propylparaben and butylparaben. Without the addition of a preservative, the effective period of the oil-soluble tracer would be shortened. After standing at 90 ℃ for 30 days, the retention rate of the detected metal element concentration is lower than 90%, and then the concentration continues to be gradually reduced. The added preservative component not only has the functions of corrosion prevention and bacteriostasis, but also is beneficial to the stable performance of the tracer, and does not delaminate or deteriorate.
Preferably, the mass percent of the rare earth elements in the tracer is 6-18%. If the mass percent of the rare earth elements in the tracer exceeds 18 percent, the organic rare earth salt is too viscous, so that pumping is inconvenient during site construction, the construction is difficult, and the speed of dissolving in crude oil is reduced. If the mass percentage of the rare earth elements in the tracer is less than 6%, the dosage of the oil-soluble tracer is excessive during field construction. When the mass percent of the rare earth elements is 6-18%, the corresponding oil-soluble tracer agent has moderate viscosity, is convenient to pump and inject, can be dissolved in crude oil within 2 minutes, and has the highest economical efficiency and construction efficiency. More preferably 10 to 17%.
In another aspect, the invention also provides the application of the oil-soluble tracer in monitoring the oil production of each fracturing segment.
The specific application method comprises the following steps: and in the fracturing process, the tracer is injected into the monitoring layer section together with fracturing fluid, oil-soluble tracers containing different rare earth elements are selected in different monitoring sections, sampling is carried out at a well mouth periodically during flowback after fracturing, the concentration of each rare earth element in crude oil is tested by using an inductively coupled plasma mass spectrometer, and the oil production contribution of each section is calculated.
The method for testing the concentration of each rare earth element in crude oil by using the inductively coupled plasma mass spectrometer adopts the prior art, and the concentration of the rare earth element in the crude oil is tested by using the inductively coupled plasma mass spectrometer after a crude oil sample is filtered by common filter paper, incinerated, pressurized and digested, acid-removed, volume-fixed and filtered by a microporous filter membrane.
Preferably, the amount of each rare earth element tracer is one ten million by weight of the fracturing fluid.
Compared with the prior art, the invention has the following beneficial effects:
1) the oil-soluble tracer provided by the invention is environment-friendly, has various element types, high flash point (higher than 60 ℃), is convenient to transport, has good compatibility with crude oil and kerosene, and does not have precipitate;
2) the inductively coupled plasma mass spectrometer can realize the simultaneous detection of various rare earth elements (namely, the oil sample of the return liquid contains more than ten tracers, and the content of the more than ten tracers can be simultaneously detected by detecting 1 oil sample), the oil yield of each section can be detected, the detection precision is high, and the ppt level (10 ppt level) can be reached-12kg/L grade), the usage amount of the oil-soluble tracer can be reduced.
Drawings
Fig. 1 is a concentration curve of lanthanum element analyzed and detected by using the oil-soluble tracer in a specific case of the invention.
Fig. 2 is a concentration curve of cerium detected by analysis using the oil-soluble tracer in an embodiment of the present invention.
Fig. 3 is a concentration curve of samarium element analyzed and detected by using the oil-soluble tracer in a specific embodiment of the present invention.
Fig. 4 is a concentration curve of yttrium element analyzed and detected by using the oil-soluble tracer in a specific embodiment of the invention.
FIG. 5 is a plot of cumulative oil production per interval for example 8 individual wells.
Detailed description of the preferred embodiments
In order to make the person skilled in the art better understand the essence and characteristics of the present invention, the following detailed description will be given by way of specific embodiments and with reference to the accompanying drawings, but not as a limitation to the implementable scope of the present invention.
Example 1
An environment-friendly oil-soluble tracer agent is prepared by uniformly mixing 59g of lanthanum neodecanoate, 32.5g of No. 5 industrial white oil, 8g of span 60 and 0.5g of ethyl p-hydroxybenzoate to obtain the environment-friendly oil-soluble tracer agent, wherein the lanthanum element content in the tracer agent is 17.0%.
Example 2
An environment-friendly oil-soluble tracer agent is prepared by uniformly mixing 70g of cerium neodecanoate, 22g of No. 10 industrial white oil, 7.5g of span 20 and 0.5g of methyl p-hydroxybenzoate to obtain the environment-friendly oil-soluble tracer agent, wherein the content of cerium in the product is 15%.
Example 3
An environment-friendly oil-soluble tracer agent is prepared by uniformly mixing 65g of samarium naphthenate, 27g of No. 15 food-grade white oil, 7.5g of span 40 and 0.5g of methyl p-hydroxybenzoate to obtain the environment-friendly oil-soluble tracer agent, wherein the content of samarium in the product is 14.7%.
Example 4
An environment-friendly oil-soluble tracer agent is prepared by uniformly mixing 68g of yttrium naphthenate, 24g of W1-100 light white oil, 7.4g of span 80 and 0.6g of propyl p-hydroxybenzoate to obtain the environment-friendly oil-soluble tracer agent, wherein the content of yttrium element in the product is 10.0%.
Example 5
An environment-friendly oil-soluble tracer agent is prepared by uniformly mixing 58.4g of neodymium neodecanoate, 33g of No. 10 industrial white oil, 8g of span 80 and 0.6g of ethyl p-hydroxybenzoate to obtain the environment-friendly oil-soluble tracer agent, wherein the content of neodymium element in the product is 12.8%.
Example 6
An environment-friendly oil-soluble tracer agent is prepared by uniformly mixing 73.7g of praseodymium neodecanoate, 22g of No. 15 food-grade white oil, 4g of span 60 and 0.3g of propyl p-hydroxybenzoate to obtain the environment-friendly oil-soluble tracer agent, wherein the content of praseodymium element in the product is 15.9%.
When the content of organic acid rare earth salt in the tracer is less than 50%, the field dosage of the tracer is increased. When the content of the organic acid rare earth salt is more than 75%, the viscosity of the oil-soluble tracer increases, resulting in inconvenience in on-site pumping and an increase in dissolution time with crude oil or kerosene.
The excessive solvent content in the tracer can reduce the amount of rare earth elements in the tracer, increase the using amount of the tracer solution and increase the cost; the solvent content is too low, the effective viscosity reduction effect on organic acid rare earth salt cannot be achieved, pumping and injection are difficult during site construction, and the dissolution time of the tracer and crude oil is prolonged. The content of the surfactant is too high, the amount of rare earth elements in the tracer is reduced, the using amount of a tracer solution is increased, and the cost is increased; too little quality, poor viscosity and poor stability of the tracer solution.
Test example 1 oil solubility test of tracer
And (2) taking 2g of each of the 6 oil-soluble tracers in the embodiments 1-6, respectively adding the 6 oil-soluble tracers into 50g of kerosene and 50g of crude oil, uniformly stirring for 2min, standing in a 90 ℃ oven for 24h, wherein the kerosene is clear and transparent all the time without precipitation, and the crude oil is not precipitated all the time.
Test example 2 mutual interference test of oil-soluble tracer
The results of taking 6 oil-soluble tracers of examples 1 to 6, preparing tracer solutions with a certain rare earth element concentration by using No. 5 industrial white oil, mixing the 6 tracer solutions, and measuring the mutual interference degree of the 6 oil-soluble tracers are shown in Table 1. It can be seen that the concentration retention rates of the 6 tracers are all more than 99% in the detection process, and the mutual interference is negligible.
TABLE 1
| Tracer rare earth element type | Pre-mix concentration (μ g/L) | Concentration after mixing (μ g/L) | Concentration retentionPercentage (%) |
| Lanthanum | 0.1021 | 0.1019 | 99.8 |
| Cerium (Ce) | 0.0998 | 0.0996 | 99.7 |
| Samarium salt | 0.1012 | 0.1009 | 99.7 |
| Yttrium salt | 0.1008 | 0.1006 | 99.8 |
| Neodymium | 0.1023 | 0.1015 | 99.2 |
| Praseodymium (III) | 0.0991 | 0.0987 | 99.6 |
Test example 3 thermal stability test of oil-soluble tracer
Taking 6 oil-soluble tracers in examples 1-6, preparing tracer solutions with certain concentrations by using No. 5 industrial white oil, standing for 90 days at 90 ℃, observing whether the tracer solutions are clear, and determining the tracerAgent concentration retention, results are shown in table 2. It can be seen that the concentration retention of 6 tracers is more than 90%, and the solution is in a clear state. The detection precision can reach 10- 12kg/L grade, i.e. ppt grade.
TABLE 2
Comparative example 1
An environment-friendly oil-soluble tracer agent is prepared by uniformly mixing 65g of samarium naphthenate, 34.5g of No. 15 food-grade white oil and 0.5g of methyl p-hydroxybenzoate to obtain the environment-friendly oil-soluble tracer agent. Respectively adding 2g of oil-soluble tracer into 50L of kerosene and 50L of crude oil, stirring for 15min, and then uniformly mixing the tracer solution with the crude oil and the kerosene, wherein the addition of the surfactant in the tracer can accelerate the dissolution speed of the tracer in the crude oil and the kerosene, and after the tracer is placed in a 90 ℃ oven and stands for 30 days, the mixed solution has a layering phenomenon, which indicates that the stability of the mixed solution is improved to a certain extent by adding the surfactant. The tracer product was taken, a tracer solution of a certain rare earth element concentration was prepared with No. 5 industrial white oil, and allowed to stand at 90 ℃ for 30 days, and the tracer concentration retention rate was determined, with the results shown in Table 3.
TABLE 3
Comparative example 2
An environment-friendly oil-soluble tracer is prepared by uniformly mixing 69g of zirconium neodecanoate, 23g of W1-100 light white oil, 7.4g of span 80 and 0.6g of propyl p-hydroxybenzoate to obtain a zirconium neodecanoate solution. Experiments show that the zirconium neodecanoate solution is easy to mix with the crude oil and the kerosene, the kerosene is always clear and transparent, no precipitate exists, and no precipitate exists during crude oil tracing. Then, the zirconium neodecanoate solution and the 4 kinds of oil-soluble tracers of examples 1 to 4 were prepared into solutions of a predetermined concentration using No. 5 industrial white oil, respectively, and the 4 kinds of tracer solutions and the zirconium neodecanoate solution were mixed to measure the degree of mutual interference between 5 metal ions, and the results are shown in table 4. The concentration retention rates of the 5 metal elements are all lower than 90%, which indicates that zirconium neodecanoate can interfere with other elements and is not suitable for being used as an oil-soluble tracer.
TABLE 4
| Type of metal element | Pre-mix concentration (μ g/L) | Concentration after mixing (μ g/L) | Concentration Retention (%) |
| Lanthanum | 0.1008 | 0.0703 | 69.7 |
| Cerium (Ce) | 0.0989 | 0.0698 | 70.6 |
| Samarium salt | 0.1002 | 0.0734 | 73.2 |
| Yttrium salt | 0.1004 | 0.0602 | 59.9 |
| Zirconium | 0.1012 | 0.0203 | 20.0 |
Comparative example 3
The environment protecting oil soluble tracer has excellent solubility of zinc neodecanoate, copper neodecanoate, iron neodecanoate and calcium neodecanoate solution in crude oil and kerosene, clear and transparent kerosene, no precipitate and no precipitate in crude oil tracing. However, the crude oil is detected by an inductively coupled plasma mass spectrometer, and the crude oil contains zinc ions, copper ions, iron ions and calcium ions in ppm level (namely mg/L level) and is too high, so that the organic acid metal prepared by using the conventional metal ions is not suitable for being used as an oil-soluble tracer.
Comparative example 4
An environment-friendly oil-soluble tracer agent is prepared by uniformly mixing 65g of samarium naphthenate, 27.5g of No. 15 food-grade white oil and 7.5g of span 40 to obtain the environment-friendly oil-soluble tracer agent, wherein the content of samarium in the product is 14.7%. The oil-soluble tracer was tested for thermal stability in the same manner as in test example 3, and the initial concentrations of samarium were 5.0032 and 0.0045. mu.g/L, respectively, and after standing for 30 days, the concentrations were 83.2 and 68.9%, respectively. After standing for 90 days, the concentration retention rates are 58.5 percent and 43.4 percent respectively.
Application example
A certain vertical well is fractured in 4 sections, 4 oil-soluble tracers in cases 1-4 are prepared, the oil-soluble tracers are injected into a stirring pool of a sand mixing truck by a micro pump during fracturing, the oil-soluble tracers are injected into monitoring sections along with fracturing fluid, one oil-soluble tracer is selected from each monitoring section (the oil-soluble tracers with rare earth elements of lanthanum, cerium, samarium and yttrium are respectively added into the first monitoring section to the fourth monitoring section), when the oil-soluble tracers are returned after the fracturing, a well head is periodically sampled and analyzed, collected returned fluid samples are tested, the concentration of the rare earth elements in crude oil is tested by an inductive coupling plasma mass spectrometer, and the sampling period is 30 d. And accumulating the concentration of the tracer agent detected by each monitoring section every day to obtain the contribution rate of each tracer agent and then obtain the oil production contribution rate of each monitoring section. The detection result shows that the 4 th section and the 3 rd section are main oil production layers, the oil production contribution rates are 38.3 percent and 30.9 percent respectively, the 1 st section and the 2 nd section are secondary oil production layers, and the oil production contribution rates are 18.5 percent and 12.3 percent respectively. Fig. 1 to 5 show the results of detection of 4 oil-soluble tracers. The dosage of four oil-soluble tracers containing lanthanum, cerium, samarium and yttrium is 0.52kg, 0.51kg, 0.23kg and 0.34kg respectively, and compared with the existing tracers (the dosage of the common oil-soluble tracers is 5-20 kg/segment), the dosage is reduced by more than 90%.
Claims (10)
1. The environment-friendly oil-soluble tracer agent is characterized by comprising the following raw materials in percentage by weight: 58.4-73.7% of organic acid rare earth salt, 22-33% of solvent, 4-8% of surfactant and 0.3-0.6% of preservative.
2. The tracer of claim 1, wherein the rare earth salt of an organic acid is one of a rare earth benzoate, a rare earth stearate, a rare earth naphthenate, and a rare earth neodecanoate.
3. The tracer of claim 1 or 2, wherein the rare earth element in the organic acid rare earth salt is one of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
4. Tracer according to claim 1, characterized in that the solvent is mineral oil.
5. The tracer of claim 4, wherein the mineral oil is a white oil comprising at least one of a food grade white oil, a cosmetic grade white oil, an industrial white oil, a light white oil.
6. The tracer of claim 1, wherein the surfactant is at least one of span 20, span 40, span 60, span 80.
7. The tracer of claim 1, wherein the preservative is at least one of methylparaben, ethylparaben, propylparaben, and butylparaben.
8. The tracer of claim 1, wherein the tracer comprises 6-18% by weight of rare earth elements.
9. Use of an oil soluble tracer according to any one of claims 1 to 8 for monitoring the amount of oil produced in each stage.
10. Use according to claim 9, characterized in that the tracer is used in a way that: in the fracturing process, a tracer is injected into a monitoring layer section along with fracturing fluid, oil-soluble tracers containing different types of rare earth elements are selected in different monitoring sections, sampling is carried out at a well mouth periodically during flowback after fracturing, the concentration of each rare earth element in crude oil is tested by using an inductively coupled plasma mass spectrometer, and the oil production contribution of each section is calculated. Preferably, the amount of each rare earth element tracer is one ten million by weight of the fracturing fluid.
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| CN114316120A (en) * | 2022-01-13 | 2022-04-12 | 陕西科技大学 | Coated supporting tracer containing rare earth metal elements and preparation method and application thereof |
| CN115288649A (en) * | 2022-05-10 | 2022-11-04 | 西安石油大学 | Tracer system for coal bed gas reservoir and coal bed gas horizontal well fracturing monitoring method |
| CN116465703A (en) * | 2023-04-25 | 2023-07-21 | 大庆信辰油田技术服务有限公司 | Complex tracer and preparation method and application thereof |
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| CN115288649A (en) * | 2022-05-10 | 2022-11-04 | 西安石油大学 | Tracer system for coal bed gas reservoir and coal bed gas horizontal well fracturing monitoring method |
| CN115288649B (en) * | 2022-05-10 | 2024-04-16 | 西安石油大学 | Tracer system for coalbed methane reservoir and coalbed methane horizontal well fracturing monitoring method |
| CN116465703A (en) * | 2023-04-25 | 2023-07-21 | 大庆信辰油田技术服务有限公司 | Complex tracer and preparation method and application thereof |
| CN116465703B (en) * | 2023-04-25 | 2024-01-26 | 大庆信辰油田技术服务有限公司 | Complex tracer and preparation method and application thereof |
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