WO2023123969A1 - Method for determining oxidation leading edge in medium-temperature-gas stream drive oil recovery - Google Patents
Method for determining oxidation leading edge in medium-temperature-gas stream drive oil recovery Download PDFInfo
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- WO2023123969A1 WO2023123969A1 PCT/CN2022/102887 CN2022102887W WO2023123969A1 WO 2023123969 A1 WO2023123969 A1 WO 2023123969A1 CN 2022102887 W CN2022102887 W CN 2022102887W WO 2023123969 A1 WO2023123969 A1 WO 2023123969A1
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- oxidation
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- oxidation process
- aldehyde
- temperature coefficient
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 220
- 230000003647 oxidation Effects 0.000 title claims abstract description 211
- 238000000034 method Methods 0.000 title claims abstract description 201
- 238000011084 recovery Methods 0.000 title claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 119
- 150000001299 aldehydes Chemical group 0.000 claims abstract description 88
- 238000005070 sampling Methods 0.000 claims abstract description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 39
- 150000002576 ketones Chemical class 0.000 claims abstract description 31
- 239000003550 marker Substances 0.000 claims abstract description 29
- 238000010795 Steam Flooding Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 238000002835 absorbance Methods 0.000 claims description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 150000002170 ethers Chemical class 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 230000007423 decrease Effects 0.000 claims description 8
- 239000013067 intermediate product Substances 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 28
- 239000003921 oil Substances 0.000 description 21
- 239000010779 crude oil Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 11
- 239000000446 fuel Substances 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003129 oil well Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000017525 heat dissipation Effects 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- FPFSGDXIBUDDKZ-UHFFFAOYSA-N 3-decyl-2-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCCCCCC1=C(O)C(=O)CC1 FPFSGDXIBUDDKZ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006213 oxygenation reaction Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- PHOLIFLKGONSGY-CSKARUKUSA-N (e)-(3-methyl-1,3-benzothiazol-2-ylidene)hydrazine Chemical compound C1=CC=C2S\C(=N\N)N(C)C2=C1 PHOLIFLKGONSGY-CSKARUKUSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012154 double-distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- -1 ketone ethers Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/24—Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B47/00—Survey of boreholes or wells
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B49/00—Testing the nature of borehole walls; Formation testing; Methods or apparatus for obtaining samples of soil or well fluids, specially adapted to earth drilling or wells
Definitions
- the invention relates to the technical field of heavy oil or super-heavy oil recovery, in particular to a method for determining the oxidation front of medium-temperature gas steam drive oil recovery.
- judging the position of the oxidation front and the driving conditions are necessary information for tracking analysis and adjustment of injection-production strategy design.
- the temperature and pressure measurement method of the produced fluid was mainly used to judge whether the high-temperature oxidation front came, that is, to judge whether the high-temperature oxidation occurred according to the wellhead fluid temperature, pressure or its rate of change. For example, if the temperature rises suddenly and the rising speed Soon, the pressure also increases significantly, and it is judged to be a high-temperature oxidation mode.
- the existing temperature-pressure method can only monitor the advancement of the combustion front, but cannot reflect and judge the oxidation state of crude oil in the ignition delay phenomenon in which the temperature is higher than the ignition temperature but not burned. Moreover, the temperature and pressure of the oxidation process are lagged behind by detecting the high temperature oxidation. Therefore, it is difficult to make a timely and accurate judgment on the oxidation mode and the progress of the oxidation front in the reservoir only relying on the temperature-pressure method.
- the purpose of the present invention is to overcome the technical problem that the temperature-pressure method is difficult to make accurate judgments on the oxidation mode in the reservoir and the progress of the oxidation front in time. Timely and accurately judge the oxidation mode in the reservoir and the progress of the oxidation front.
- the present invention provides a method for determining the oxidation front of medium-temperature gas-driven oil recovery, the method uses a marker method, with aldehydes, ketones and ethers as markers, through the detection of medium-temperature gas steam-driven oil recovery wellhead output gas and/or Or the concentration of aldehyde, ketone ether markers in the produced fluid is used to determine the oxidation mode of the oxidation front in the reservoir corresponding to the location of the sampling well.
- the marker method judges whether the oxidation front enters the negative temperature coefficient oxidation process by detecting the concentration of aldehyde in the intermediate product aldehyde ketone ether marker of the negative temperature coefficient oxidation reaction process, if the concentration of the aldehyde is at 0.2mg/ m3 or more, the marker method determines that the oxidation mode of the oxidation front in the reservoir corresponding to the location of the sampling well is a negative temperature coefficient oxidation process, wherein the negative temperature coefficient oxidation process is that the reaction rate increases with the temperature Oxidation process in the interval of high and reduced ignition delay.
- the oxidation front in the reservoir corresponding to the location of the sampling well enters the negative temperature coefficient oxidation process
- the measured aldehyde concentration and aldehyde content are compared with the functional relationship between the negative temperature coefficient oxidation process. The case of the NTC oxidation process is extrapolated.
- the determination method further adopts a temperature-pressure method, and the temperature-pressure method monitors the high-temperature oxidation process by detecting the temperature, pressure or the rate of change of the medium-temperature gas-driven oil recovery wellhead produced fluid.
- the determination method is based on the marker method and the temperature-pressure method to jointly determine the oxidation mode in the reservoir corresponding to the location of the sampling well.
- the present invention proposes the detection of aldehydes, ketones, and ethers for the first time on the basis of the first discovery of the negative temperature coefficient oxidation process between the low temperature oxidation process and the high temperature oxidation process, and that aldehydes, ketones, and ethers are the main intermediate products of the negative temperature coefficient oxidation process.
- Markers are used to determine the oxidation mode of the oxidation front in the reservoir corresponding to the location of the sampling well, and monitor the oxidation process with a negative temperature coefficient, so that the oxidation mode of the oxidation front in the reservoir near the location of the sampling well can be accurately judged, and The oxidation mode is monitored by detecting the high-temperature oxidation process in advance of the temperature-pressure method, so this method can timely and accurately judge the advancement of the oxidation front in the reservoir, and provide a basis for adjusting the operating conditions.
- the present invention further uses the aldehyde, ketone ether marker method as the main method, supplemented by the temperature and pressure method, to determine the oxidation mode of the oxidation front in the reservoir corresponding to/near the location of the sampling well, so as to monitor the whole process of the oxidation reaction.
- the result judged by the marker method is a negative temperature coefficient oxidation process
- the oxidation process if the result of the temperature-pressure method is a high-temperature oxidation process, it is determined that the oxidation mode in the reservoir near the location of the sampling well is a high-temperature oxidation process; if the result of the temperature-pressure method is a non-high-temperature oxidation process, then It is determined that the oxidation mode in the reservoir near the location of the sampling well is a low-temperature oxidation process.
- the inventors found through a lot of research that the front-propelled oxidation of crude oil in the production well includes: low-temperature oxidation process, negative temperature coefficient oxidation process and high-temperature oxidation process.
- the low-temperature oxidation process refers to the oxidation process in which crude oil undergoes a preliminary reaction and has some carbon monoxide products
- the negative temperature coefficient oxidation process refers to the oxidation process in the ignition delay interval where the system reaction rate decreases as the temperature increases, " Make "crude oil have oxidation activity beyond the ignition delay interval, then the crude oil can enter the high-temperature oxidation process beyond the negative temperature coefficient oxidation process
- the high-temperature oxidation process refers to the process of a series of oxidation reactions that occur after the crude oil is ignited. The temperature rises suddenly, and the rising speed is very fast, and the pressure also increases greatly. Compared with the incomplete combustion characteristics in the low temperature oxidation and negative temperature coefficient oxidation process, the combustion in the high temperature oxidation process is more complete.
- the oxidation reaction mechanism of the low temperature oxidation process, negative temperature coefficient oxidation process and high temperature oxidation process in the medium temperature gas drive is described as follows.
- the initial reaction is the dehydrogenation of the fuel molecule R to generate the fuel radical R', and the dehydrogenation reaction between the fuel molecule and the oxygen molecule to generate the fuel radical R', namely
- R' is the fuel base, and HO 2 and O 2 will continue to participate in dehydrogenation to establish a radical pool, which includes O, N, OH, HO 2 , CH 3 , C 2 H 3 , etc.
- Fuel-based R'addition reaction occurs at medium and low temperature; because the potential energy position of R'O2 is low, that is, the activation barrier of this reaction is low, so the reaction is very easy to occur.
- R'O2 undergoes hydrogen atom transfer through the transition state and isomerizes through a hydrogenation reaction to obtain R"OOH. Due to the low activation barrier of the transition state of the six-membered ring, it is easy to occur as follows. Take heptyl fuel as an example The hydrogen atom transfer:
- R " OOH that above-mentioned reaction generates can take place three kinds of reactions, and one of them is exactly the cleavage reaction of R " OOH, as the ⁇ cracking that occurs for above-mentioned two formulas:
- the ether, aldehyde, and alkene produced by the above reaction plus the ketone produced by the following reaction are very good organic solvents. Once a large amount of alkene, aldehyde, and ether are generated during the combustion process, when they are miscible with macromolecular hydrocarbon components, if the system temperature If it is lowered (low temperature reaction or external heat is less than external heat), gelation will occur, and oil flooding will not occur.
- R”OOH undergoes a second oxygen addition reaction to obtain O 2 R”OOH, and continues to add oxygen molecules as in formula (2):
- HOOR"'OOH undergoes a cleavage reaction to generate a ketone and two OH active groups.
- the reaction continues, and as the temperature gradually increases, the rates of reactions (3) and (4) increase, and secondary hydrogenation reactions occur, isomerization
- the rate of reaction decreases, that is, the concentration of OH decreases.
- NTC Negative Temperature Coefficient
- NTC negative Temperature Coefficient
- NTC negative Temperature Coefficient
- NTC negative Temperature Coefficient
- the reaction rate decreases with increasing temperature.
- the fuel base R' can be directly cracked into small molecules of stable unsaturated olefins, which compete with the first hydrogenation reaction, further reducing the reaction rate. If the NTC lasts too long, the temperature drops, and the OH concentration is too low, it will fail to break through the NTC interval, which is the second reason for fire flooding failure.
- NTC interval In the ignition delay interval (NTC interval), if the OH concentration is too low or the reaction heat release is lower than the external heat dissipation, the entire system will not be able to break through the NTC constraint, the chain reaction will be interrupted, and only low-temperature reactions will occur instead of high-temperature reactions. If the NTC duration is suitable, the OH concentration is suitable, or the reaction exotherm is higher than the external heat dissipation, the reaction can enter the high temperature oxidation process.
- 1 is the initial reaction
- 2—7 is the oxygenation and isomerization reaction under medium and low temperature conditions, during which most R"OOH cracks to generate olefins, cyclic ethers, aldehydes and an OH active group, among which 2— 4 is a chain propagation reaction.
- R”OOH undergoes secondary oxygenation and isomerization reaction to generate ketone and 2 OH, which belongs to the chain branching reaction and can accelerate the reaction of the system; as the temperature increases, the reaction 8 and 2 become competitive reactions, the concentration of OH groups in the system decreases, the reaction rate decreases, and the ignition delay phenomenon (also known as the negative temperature coefficient phenomenon, that is, the NTC phenomenon) appears.
- 9—10 are high temperature reactions.
- Reactions 2-8 occur in the negative temperature coefficient oxygen process, and the main reactions 4 and 7 show that the main intermediate products in the negative temperature coefficient oxidation process are aldehydes, ketones, and ethers.
- the invention provides a method for determining the oxidation front of medium-temperature gas-driven oil recovery.
- the method adopts the marker method, using aldehydes, ketones and ethers as markers, and detects the amount of gas and/or produced liquid in the wellhead of medium-temperature gas-driven steam-driven oil recovery.
- the concentration of the aldehyde, ketone ether marker is used to determine the oxidation mode of the oxidation front in the reservoir corresponding to the location of the sampling well.
- aldehydes, ketones, and ethers are used as markers, and the negative temperature coefficient oxidation process is monitored by detecting the concentration of aldehydes in the aldehydes, ketones, and ethers markers to determine whether the oxidation mode of the oxidation front in the reservoir corresponding to the location of the sampling well is Negative temperature coefficient oxidation process.
- the content of aldehyde in the intermediate product aldehyde and ketone ether markers of the negative temperature coefficient oxidation process is the largest and is significantly greater than that of ketones and ethers, and it is easier to detect and the detection results are more accurate. Therefore, The progress of NTC oxidation can be monitored by measuring the concentration of aldehyde in the aldehyde ketone ether intermediate.
- the negative temperature coefficient oxidation process can also be judged by detecting the concentration of ketone or ether in the intermediate product of aldehyde, ketone ether, or the combination of the two or three concentrations, which can be determined according to the specific conditions of the specific oil reservoir.
- the samples produced from the medium-temperature gas steam-flooding oil production wellhead are the produced fluid and/or produced gas from the medium-temperature gas steam-flooded oil production wellhead.
- the concentration of aldehydes, ketones and ethers it is necessary to sample at the wellhead of medium-temperature gas-driven oil production. Samples are subject to change. If the medium-temperature gas drive wellhead produces gas, then detect the concentration of aldehydes, ketones, and ethers in the gas; The gas and liquid mixture is produced from the wellhead of flooding and recovery, and the concentration of aldehyde, ketone, and ether in the gas-liquid mixture is detected.
- the present invention uses aldehydes, ketone ethers, the main product of the negative temperature coefficient oxidation process, as a marker, and uses phenol reagent spectrophotometry to measure the concentration of aldehydes when the aldehyde content is the largest.
- the basic principle is to take the output product of the oxidation process of negative temperature coefficient in the gas and/or the output liquid in the medium-temperature gas steam drive oil production wellhead——aldehyde, ketone ether, as the marker, and the aldehyde in it can react with the phenolic reagent to form oxazine .
- the azine produced by the reaction further reacts in an acidic solution to form a blue-green compound.
- the NTC oxidation process reaction product increases, corresponding to a color change that is a function of the NTC oxidation process conditions.
- Determine whether the oxidation front enters the negative temperature coefficient oxidation process by measuring the concentration of aldehyde and the test of the negative temperature coefficient oxidation process includes the following steps:
- the concentration of the measured aldehyde is outside the interval of the aldehyde content corresponding to the negative temperature coefficient oxidation process, then determine that the oxidation mode in the reservoir corresponding to the location of the sampling well is a non-negative temperature coefficient oxidation process; if the measured aldehyde If the concentration is within the interval of the aldehyde content corresponding to the negative temperature coefficient oxidation process, then it is determined that the oxidation mode in the reservoir corresponding to the location of the sampling well is the negative temperature coefficient oxidation process.
- the measured aldehyde concentration was compared with the functional relationship between the aldehyde content and the negative temperature coefficient oxidation process, and then the negative temperature coefficient oxidation process was inferred from the concentration of aldehyde.
- the invention judges the oxidation mode and the negative temperature coefficient oxidation process in the reservoir near the location of the sampling well by sampling and detecting the medium-temperature gas-steam drive oil production wellhead, and provides a basis for adjusting the operating conditions.
- the marker method judges whether the oxidation front enters the negative temperature coefficient oxidation process by detecting the concentration of aldehyde in the intermediate product aldehyde and ketone ether of the negative temperature coefficient oxidation reaction process, if the concentration of the aldehyde is 0.2 mg/m 3 or more, the marker method determines that the oxidation mode of the oxidation front in the reservoir corresponding to the location of the sampling well is a negative temperature coefficient oxidation process, wherein the negative temperature coefficient oxidation process is that the reaction rate increases with the temperature while reducing the oxidation process in the ignition delay interval.
- the concentration of aldehyde is used to determine whether the oxidation mode of the oxidation front in the reservoir corresponding to the location of the sampling well is an oxidation process with a negative temperature coefficient.
- the oxidation mode of the oxidation front in the reservoir is a negative temperature coefficient oxidation process; if the concentration of aldehyde is less than 0.2mg/m 3 , it is judged that the oxidation mode of the oxidation front in the reservoir corresponding to the location of the sampling well is a non-negative temperature coefficient oxidation process.
- the negative temperature coefficient oxidation process is between a low temperature oxidation process and a high temperature oxidation process.
- the surrounding area and range entering the negative temperature coefficient oxidation process can be estimated.
- the surrounding area and range entering the negative temperature coefficient oxidation process can be estimated. For a specific oil reservoir, if you find the relationship between the aldehyde content and the oxidation of the negative temperature coefficient, you can know how many aldehydes are produced in one oil in this reaction. If the amount of aldehydes is increasing significantly, it means that there is a wider range The region has entered the negative temperature coefficient oxidation process.
- the determination method further adopts the temperature-pressure method, and the temperature-pressure method judges the Oxidation patterns of crude oil oxidation fronts in reservoirs.
- the temperature-pressure method determines whether the oxidation front of crude oil in the reservoir enters the high-temperature oxidation process by measuring the temperature, pressure, and rate of change of temperature or pressure of the produced fluid; for example, if the temperature of the produced fluid in the sampling well is high Above 350°C, it is considered to enter high temperature oxidation.
- the detection method of the concentration of the aldehyde is measured by a phenol reagent method combined with a spectrophotometer, comprising the following steps:
- the water used in this method is double distilled water or deionized water; the purity of the reagents used is generally analytical pure.
- Absorbing solution Measure 5mL of the original absorbing solution and add 95mL of water to obtain the absorbing solution. When sampling, it is ready-to-use.
- ferric ammonium sulfate solution weigh 1.0 g of ferric ammonium sulfate [NH 4 Fe(SO 4 ) 2 ⁇ 12H 2 O], dissolve it with 0.1 mol/L hydrochloric acid, and dilute to 100 mL.
- Step 1 Draw a standard curve: draw the standard curve of the absorbance value of the blue-green compound corresponding to different concentrations of standard aldehydes and the aldehyde content, the formaldehyde content is the abscissa, the absorbance is the ordinate, and calculate the regression slope, and use the reciprocal of the slope as the calculation of the sample determination Factor Bg (mg/absorbance);
- Sampling volume is converted into sampling volume under the standard state by formula (1);
- V 0 V t ⁇ T 0 /(273+t) ⁇ P/P 0 ........... briefly(I)
- V 0 sampling volume under standard state, L;
- Formaldehyde concentration is calculated by formula (II) in the sample
- V 0 converted into the sampling volume under the standard state, L.
- the medium temperature gas flooding oil recovery method proposed by the present invention is to inject air into the ignition, and control the conditions to promote the crude oil to cross the negative temperature coefficient oxidation process and successfully enter the high temperature oxidation process, using the heat generated by the chemical reaction It is a method of reducing the viscosity of crude oil and modifying it, mixing the injected fluid with gas generated by chemical reactions, and displacing crude oil.
- the negative temperature coefficient oxidation process refers to the oxidation in the ignition delay interval where the reaction rate of the system decreases with the increase of temperature. process, the negative temperature coefficient oxidation process is between the low temperature oxidation process and the high temperature oxidation process.
- the reagents involved in the examples of the present invention are all commercially available products, which can be purchased through commercial channels.
- a method for determining the oxidation front of medium-temperature gas-flooding oil production well No. 1 in an oilfield, using the marker method to detect aldehydes and ketone-ether markers in the gas and/or liquid samples produced at the medium-temperature gas-flooding oil production wellhead The concentration is 0.3mg/m 3 , and it is judged that the oxidation mode of the oxidation front in the reservoir near the location of No. 1 oil well is negative temperature coefficient oxidation process.
- the method for determining the oxidation front of medium-temperature gas-steam flooding oil production well No. 2 in an oilfield uses the same marker method as in Example 1 to obtain an aldehyde concentration of 0.1 mg/m 3 , and determine the corresponding The oxidation mode of the oxidation front in the reservoir is a non-negative temperature coefficient oxidation process.
- Example 2 On the basis of Example 2, combined with the temperature-pressure method to determine the oxidation mode of the oxidation front, on the basis of judging that the oxidation mode of the oxidation front in the reservoir corresponding to the location of the No. 2 oil well is a non-negative temperature coefficient oxidation process , the temperature and pressure method was used to measure the temperature of the produced fluid in the production well to be 150 °C, and it was further judged to be a non-high-temperature oxidation process, so it can be determined that the oxidation mode of the oxidation front in the reservoir corresponding to the location of the No. 2 oil well is a low-temperature oxidation process.
- the method for determining the oxidation front of medium-temperature gas steam drive oil recovery in No. 3 oil well in an oilfield uses the same marker method as in Example 1 to obtain an aldehyde concentration of 0.15 mg/m 3 , and judges the corresponding
- the oxidation mode of the oxidation front in the reservoir is a non-negative temperature coefficient oxidation process; on this basis, the temperature of the production fluid produced by the production well is determined to be 450 °C by using the temperature-pressure method, and it is further judged as a high-temperature oxidation process, so it can be determined that the No. 3 oil well
- the oxidation mode of the oxidation front in the reservoir corresponding to the location is a high temperature oxidation process.
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- Measuring Fluid Pressure (AREA)
Abstract
Provided is a method for determining an oxidation leading edge in medium-temperature-gas steam drive oil recovery, the method comprising: utilizing a marker method wherein a marker is aldehyde ketone ether; detecting the concentration of aldehyde ketone ether in a gas and/or liquid produced in a medium-temperature-gas steam drive oil recovery wellhead, and using said concentration for determining an oxidation mode of an oxidation leading edge in a reservoir corresponding to the position of a sampling well. The use of an aldehyde ketone ether marker method for monitoring a negative temperature coefficient oxidation process is proposed for the first time, and allows for rapidly and accurately judging the advancement of an oxidation leading edge in a reservoir, and provides a basis for adjusting operating conditions. Moreover, the marker method is combined with a temperature and pressure method so as to determine an oxidation mode in a reservoir near the position of the sampling well, so as to monitor the entire process of an oxidation reaction.
Description
相关申请的交叉引用Cross References to Related Applications
本申请要求2021年12月31日提交的中国专利申请202111665692.8的权益，该申请的内容通过引用被合并于本文。This application claims the benefit of Chinese patent application 202111665692.8 filed on December 31, 2021, the contents of which are incorporated herein by reference.
本发明涉及稠油或特、超稠油开采技术领域，具体涉及中温气汽驱采油氧化前缘的确定方法。The invention relates to the technical field of heavy oil or super-heavy oil recovery, in particular to a method for determining the oxidation front of medium-temperature gas steam drive oil recovery.
在中温气汽驱现场实施中，判断氧化前缘的位置及推进工况，是跟踪分析和注采策略设计调整的必要信息。前期现场试验中，主要采用产出液测温压方式判断高温氧化前缘是否到来，即根据井口出液温度、压力或其变化速率判断是否发生高温氧化，例如若温度陡然升高，并且上升速度很快，压力也随之大幅增加，则判断为高温氧化模式。现有温压法只能监测燃烧前缘的推进情况，但无法反映和判断原油在温度高于着火温度而未燃烧的着火延迟现象内的氧化状态。而且通过检测高温氧化检测氧化进程的温压是滞后的。因此，仅依靠温压方式很难对储层中的氧化模式及氧化前缘的推进情况及时做出准确判断。In the field implementation of medium-temperature gas steam flooding, judging the position of the oxidation front and the driving conditions are necessary information for tracking analysis and adjustment of injection-production strategy design. In the early field test, the temperature and pressure measurement method of the produced fluid was mainly used to judge whether the high-temperature oxidation front came, that is, to judge whether the high-temperature oxidation occurred according to the wellhead fluid temperature, pressure or its rate of change. For example, if the temperature rises suddenly and the rising speed Soon, the pressure also increases significantly, and it is judged to be a high-temperature oxidation mode. The existing temperature-pressure method can only monitor the advancement of the combustion front, but cannot reflect and judge the oxidation state of crude oil in the ignition delay phenomenon in which the temperature is higher than the ignition temperature but not burned. Moreover, the temperature and pressure of the oxidation process are lagged behind by detecting the high temperature oxidation. Therefore, it is difficult to make a timely and accurate judgment on the oxidation mode and the progress of the oxidation front in the reservoir only relying on the temperature-pressure method.
发明内容Contents of the invention
本发明的目的是为了克服温压法很难对储层中的氧化模式及氧化前缘推进情况及时做出准确判断的技术问题，本发明提供中温气汽驱采油氧化前缘的确定方法，能够及时、准确判断储层中的氧化模式及氧化前缘推进情况。The purpose of the present invention is to overcome the technical problem that the temperature-pressure method is difficult to make accurate judgments on the oxidation mode in the reservoir and the progress of the oxidation front in time. Timely and accurately judge the oxidation mode in the reservoir and the progress of the oxidation front.
为了实现上述目的，本发明提供一种中温气汽驱采油氧化前缘的确定方法，该方法采用标志物法，以醛酮醚作为标志物，通过检测中温气汽驱采油井口产出气和/或产出液中的醛酮醚标志物的浓度，用于确定取样井所在位置对应的储层中氧化前缘的氧化模式。In order to achieve the above object, the present invention provides a method for determining the oxidation front of medium-temperature gas-driven oil recovery, the method uses a marker method, with aldehydes, ketones and ethers as markers, through the detection of medium-temperature gas steam-driven oil recovery wellhead output gas and/or Or the concentration of aldehyde, ketone ether markers in the produced fluid is used to determine the oxidation mode of the oxidation front in the reservoir corresponding to the location of the sampling well.
优选地，所述标志物法通过检测负温度系数氧化反应进程的中间产物醛酮醚标志物中醛的浓度判断氧化前缘是否进入负温度系数氧化进程，若所述醛的浓度在0.2mg/m
3以上时，所述标志物法确定取样井所在位置对应的储层中氧化前缘的氧化模式为负温度系数氧化进程，其中，所述负温度系数氧化进程为反应速率随着温度的升高而降低的着火延迟区间的氧化过程。
Preferably, the marker method judges whether the oxidation front enters the negative temperature coefficient oxidation process by detecting the concentration of aldehyde in the intermediate product aldehyde ketone ether marker of the negative temperature coefficient oxidation reaction process, if the concentration of the aldehyde is at 0.2mg/ m3 or more, the marker method determines that the oxidation mode of the oxidation front in the reservoir corresponding to the location of the sampling well is a negative temperature coefficient oxidation process, wherein the negative temperature coefficient oxidation process is that the reaction rate increases with the temperature Oxidation process in the interval of high and reduced ignition delay.
优选地，若确定取样井所在位置对应的储层中氧化前缘进入所述负温度系数氧化进程，则通过将测定的醛的浓度与醛含量与负温度系数氧化进程情况的函数关系比对，推断所述负温度系数氧化进程的情况。Preferably, if it is determined that the oxidation front in the reservoir corresponding to the location of the sampling well enters the negative temperature coefficient oxidation process, then by comparing the measured aldehyde concentration and aldehyde content with the functional relationship between the negative temperature coefficient oxidation process, The case of the NTC oxidation process is extrapolated.
优选地，所述的确定方法进一步采用温压法，所述温压法通过检测中温气汽驱采油井口产出液的温度、压力或其变化速度监测高温氧化进程。Preferably, the determination method further adopts a temperature-pressure method, and the temperature-pressure method monitors the high-temperature oxidation process by detecting the temperature, pressure or the rate of change of the medium-temperature gas-driven oil recovery wellhead produced fluid.
优选地，所述的确定方法基于所述标志物法和温压法，联合确定 取样井所在位置对应的储层中的氧化模式。Preferably, the determination method is based on the marker method and the temperature-pressure method to jointly determine the oxidation mode in the reservoir corresponding to the location of the sampling well.
通过上述技术方案，本发明在首次发现低温氧化进程与高温氧化进程之间的负温度系数氧化进程，以及醛酮醚为负温度系数氧化进程的主要中间产物的基础上，首次提出检测醛酮醚标志物以确定取样井所在位置对应的储层中氧化前缘的氧化模式，监测出负温度系数氧化进程，从而能够准确的判断取样井所在位置附近的储层中氧化前缘的氧化模式，而且提前于温压法通过检测高温氧化进程监测氧化模式，因此本方法能够及时、准确的判断储层内氧化前缘的推进情况，为调整操控工况提供依据。Through the above technical scheme, the present invention proposes the detection of aldehydes, ketones, and ethers for the first time on the basis of the first discovery of the negative temperature coefficient oxidation process between the low temperature oxidation process and the high temperature oxidation process, and that aldehydes, ketones, and ethers are the main intermediate products of the negative temperature coefficient oxidation process. Markers are used to determine the oxidation mode of the oxidation front in the reservoir corresponding to the location of the sampling well, and monitor the oxidation process with a negative temperature coefficient, so that the oxidation mode of the oxidation front in the reservoir near the location of the sampling well can be accurately judged, and The oxidation mode is monitored by detecting the high-temperature oxidation process in advance of the temperature-pressure method, so this method can timely and accurately judge the advancement of the oxidation front in the reservoir, and provide a basis for adjusting the operating conditions.
本发明进一步以醛酮醚标志物法为主，以温压法为辅，确定取样井所在位置对应/附近的储层中氧化前缘的氧化模式，以监控氧化反应全过程。当所述标志物法判断的结果为负温度系数氧化进程，则确定取样井所在位置附近储层中的氧化模式为负温度系数氧化模式；当所述标志物法判断的结果为非负温度系数氧化进程时，若所述温压法的结果为高温氧化进程，则确定取样井所在位置附近储层中的氧化模式为高温氧化进程；若所述温压法的结果为非高温氧化进程，则确定取样井所在位置附近储层中的氧化模式为低温氧化进程。The present invention further uses the aldehyde, ketone ether marker method as the main method, supplemented by the temperature and pressure method, to determine the oxidation mode of the oxidation front in the reservoir corresponding to/near the location of the sampling well, so as to monitor the whole process of the oxidation reaction. When the result judged by the marker method is a negative temperature coefficient oxidation process, it is determined that the oxidation mode in the reservoir near the location of the sampling well is a negative temperature coefficient oxidation mode; when the result judged by the marker method is a non-negative temperature coefficient During the oxidation process, if the result of the temperature-pressure method is a high-temperature oxidation process, it is determined that the oxidation mode in the reservoir near the location of the sampling well is a high-temperature oxidation process; if the result of the temperature-pressure method is a non-high-temperature oxidation process, then It is determined that the oxidation mode in the reservoir near the location of the sampling well is a low-temperature oxidation process.
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.
在本发明中，发明人经过大量的研究发现，采油井内原油的前缘推进氧化情况包括：低温氧化进程、负温度系数氧化进程和高温氧化进程。In the present invention, the inventors found through a lot of research that the front-propelled oxidation of crude oil in the production well includes: low-temperature oxidation process, negative temperature coefficient oxidation process and high-temperature oxidation process.
在本发明中，低温氧化进程是指原油发生初步反应且有一些一氧化碳产物的氧化过程；负温度系数氧化进程是指系统反应速率随着温度的升高而降低的着火延迟区间的氧化过程，“使”原油具有跨越所述着火延迟区间的氧化活性，则原油可越过所述负温度系数氧化进程进入所述高温氧化进程；高温氧化进程是指原油着火后发生的一系列氧化反应的进程，具有温度陡然升高，并且上升速度很快，压力也随之大幅增加的特性，相对于低温氧化和负温度系数氧化进程内的不完全燃烧特性，高温氧化进程内的燃烧更充分。In the present invention, the low-temperature oxidation process refers to the oxidation process in which crude oil undergoes a preliminary reaction and has some carbon monoxide products; the negative temperature coefficient oxidation process refers to the oxidation process in the ignition delay interval where the system reaction rate decreases as the temperature increases, " Make "crude oil have oxidation activity beyond the ignition delay interval, then the crude oil can enter the high-temperature oxidation process beyond the negative temperature coefficient oxidation process; the high-temperature oxidation process refers to the process of a series of oxidation reactions that occur after the crude oil is ignited. The temperature rises suddenly, and the rising speed is very fast, and the pressure also increases greatly. Compared with the incomplete combustion characteristics in the low temperature oxidation and negative temperature coefficient oxidation process, the combustion in the high temperature oxidation process is more complete.
中温气汽驱中发生的低温氧化进程、负温度系数氧化进程和高温氧化进程内发生的氧化反应机理描述如下。The oxidation reaction mechanism of the low temperature oxidation process, negative temperature coefficient oxidation process and high temperature oxidation process in the medium temperature gas drive is described as follows.
原油中存在大量的直链和支链烷烃、环烷烃、烯烃、芳香烃等多种成份，且碳原子数目不可知，不同成份的氧化反应路径及其宏观表征也不相同。总体来看，作为碳氢燃料混合物，原油的氧化反应可分为以下几类反应：There are a large number of straight-chain and branched-chain alkanes, cycloalkanes, olefins, aromatics and other components in crude oil, and the number of carbon atoms is unknown. The oxidation reaction pathways and macroscopic characterizations of different components are also different. In general, as a hydrocarbon fuel mixture, the oxidation reaction of crude oil can be divided into the following types of reactions:
起始反应为燃料分子R脱氢生成燃料基R’，以及燃料分子与氧分子发生脱氢反应生成燃料基R’，即The initial reaction is the dehydrogenation of the fuel molecule R to generate the fuel radical R', and the dehydrogenation reaction between the fuel molecule and the oxygen molecule to generate the fuel radical R', namely
①RH→H+R’；RH+O
2→R’+HO
2
①RH→H+R'; RH+O 2 →R'+HO 2
其中，R’为燃料基，HO
2和O
2会继续参与脱氢，建立根池(radical pool)，根池包括O、N、OH、HO
2、CH
3、C
2H
3等。
Among them, R' is the fuel base, and HO 2 and O 2 will continue to participate in dehydrogenation to establish a radical pool, which includes O, N, OH, HO 2 , CH 3 , C 2 H 3 , etc.
②R’+O
2→R’O
2
②R'+O 2 →R'O 2
燃料基R’在中低温度下发生加成反应；由于R’O
2的势能位置较低，即该反应的活化势垒低，因此反应极易发生。
Fuel-based R'addition reaction occurs at medium and low temperature; because the potential energy position of R'O2 is low, that is, the activation barrier of this reaction is low, so the reaction is very easy to occur.
③R’O
2→R”OOH
③R'O 2 →R"OOH
在中低温度下，R’O
2通过过渡态发生氢原子转移经一次加氢反应异构得到R”OOH，由于六元环过渡态活化势垒较低，容易发生如下以庚基燃料为例的氢原子转移：
At medium and low temperatures, R'O2 undergoes hydrogen atom transfer through the transition state and isomerizes through a hydrogenation reaction to obtain R"OOH. Due to the low activation barrier of the transition state of the six-membered ring, it is easy to occur as follows. Take heptyl fuel as an example The hydrogen atom transfer:
④R”OOH→烯烃、环醚、醛+OH④R”OOH→alkene, cyclic ether, aldehyde+OH
在上述反应生成的R”OOH可以发生三类反应，其一就是R”OOH的裂解反应，如对于上述两式发生的β裂解：The R " OOH that above-mentioned reaction generates can take place three kinds of reactions, and one of them is exactly the cleavage reaction of R " OOH, as the β cracking that occurs for above-mentioned two formulas:
或者：or:
上述反应生成的醚、醛、烯加上下面反应生成的酮是非常好的有机溶剂，在燃烧过程中一旦生成大量的烯、醛、醚，他们与大分子碳氢成分互溶时，如果系统温度降低(低温反应或外加热量少于对外放热量)，则发生结胶现象，油驱不能发生。The ether, aldehyde, and alkene produced by the above reaction plus the ketone produced by the following reaction are very good organic solvents. Once a large amount of alkene, aldehyde, and ether are generated during the combustion process, when they are miscible with macromolecular hydrocarbon components, if the system temperature If it is lowered (low temperature reaction or external heat is less than external heat), gelation will occur, and oil flooding will not occur.
⑤R”OOH+O
2→O
2R”OOH
⑤R”OOH+O 2 →O 2 R”OOH
R”OOH发生二次加氧反应得到O
2R”OOH，如式(2)继续加氧分子：
R”OOH undergoes a second oxygen addition reaction to obtain O 2 R”OOH, and continues to add oxygen molecules as in formula (2):
⑥O
2R”OOH→HOOR”’OOH
⑥O 2 R"OOH→HOOR"'OOH
O
2R”OOH发生二次加氢反应异构生成HOOR”’OOH；
O 2 R"OOH undergoes secondary hydrogenation reaction isomerization to generate HOOR"'OOH;
⑦HOOR”’OOH→OR”’O+2OH⑦HOOR"'OOH→OR"'O+2OH
HOOR”’OOH发生裂解反应生成酮和2个OH活性基。HOOR"'OOH undergoes a cleavage reaction to generate a ketone and two OH active groups.
在上述①-⑦的系列反应中，生成3个OH和醛、酮、醚。一方面 OH的活性较强可继续发生系统反应，使反应加速，燃料进一步氧化，释放热量，使系统温度升高；而对于实际的反应过程，醚、醛溶解高分子原油成分，系统散热量增加。如果低温放热量和/或系统注入热量小于散热量，温度降低，油层结胶。这是驱油失败的第一个原因。In the above series of ①-⑦ reactions, 3 OH and aldehydes, ketones, and ethers are generated. On the one hand, the strong activity of OH can continue the system reaction, which accelerates the reaction, further oxidizes the fuel, releases heat, and raises the temperature of the system; while in the actual reaction process, ether and aldehyde dissolve the polymer crude oil components, and the heat dissipation of the system increases . If the heat released at low temperature and/or the heat injected into the system is less than the heat released, the temperature drops and the oil layer gels. This is the number one cause of flooding failure.
⑧R’→小分子⑧R'→Small molecule
如果上述反应中，系统的放热量大于对外的散热量，则反应继续进行，随着温度逐渐升高，反应(3)和(4)的速率增加，而发生二次加氢反应，异构化反应的速率降低，即OH的浓度降低，此时进入负温度系数反应进程，即负温度系数(Negative Temperature Coefficient,NTC)区间，也称着火延迟区间，在该负温度系数(NTC)区间内，反应速率随着温度的升高而降低。此外，在此期间，温度升高后，燃料基R’可以直接裂解成小分子稳定不饱和烯烃，它与第一次加氢反应成为竞争反应，进一步降低反应速率。如果NTC持续时间过长，温度降低，OH浓度太低，会导致无法突破NTC区间，这是火驱失败的第二个原因。If in the above reaction, the heat release of the system is greater than the external heat dissipation, the reaction continues, and as the temperature gradually increases, the rates of reactions (3) and (4) increase, and secondary hydrogenation reactions occur, isomerization The rate of reaction decreases, that is, the concentration of OH decreases. At this time, it enters the negative temperature coefficient reaction process, that is, the negative temperature coefficient (Negative Temperature Coefficient, NTC) interval, also known as the ignition delay interval. In this negative temperature coefficient (NTC) interval, The reaction rate decreases with increasing temperature. In addition, during this period, after the temperature rises, the fuel base R' can be directly cracked into small molecules of stable unsaturated olefins, which compete with the first hydrogenation reaction, further reducing the reaction rate. If the NTC lasts too long, the temperature drops, and the OH concentration is too low, it will fail to break through the NTC interval, which is the second reason for fire flooding failure.
⑨H+O
2→O+OH
⑨H+O 2 →O+OH
⑩CO+O→CO
2
⑩CO+O→CO 2
在着火延迟区间(NTC区间)，如果OH浓度过低或反应放热低于对外散热，那么整个系统将不能突破NTC约束，链反应中断，只发生低温反应而无法发生高温反应。如果NTC持续时间适应，OH浓度适宜或反应放热高于对外散热，则反应可进入高温氧化进程。In the ignition delay interval (NTC interval), if the OH concentration is too low or the reaction heat release is lower than the external heat dissipation, the entire system will not be able to break through the NTC constraint, the chain reaction will be interrupted, and only low-temperature reactions will occur instead of high-temperature reactions. If the NTC duration is suitable, the OH concentration is suitable, or the reaction exotherm is higher than the external heat dissipation, the reaction can enter the high temperature oxidation process.
上述反应中，①为起始反应；②—⑦为中低温条件下的加氧和异 构反应，期间大部分R”OOH发生裂解生成烯烃、环醚、醛以及一个OH活性基，其中②—④为链传播反应，⑤－⑦反应中，R”OOH发生二次加氧和异构反应生成酮和2个OH，属于链分支反应，可以对系统反应加速；随着温度的升高，反应⑧与②成为竞争性反应，系统中OH基浓度降低、反应速率降低，出现着火延迟现象(又称为负温度系数现象，即NTC现象)。⑨—⑩为高温反应。Among the above reactions, ① is the initial reaction; ②—⑦ is the oxygenation and isomerization reaction under medium and low temperature conditions, during which most R"OOH cracks to generate olefins, cyclic ethers, aldehydes and an OH active group, among which ②— ④ is a chain propagation reaction. In the ⑤-⑦ reaction, R”OOH undergoes secondary oxygenation and isomerization reaction to generate ketone and 2 OH, which belongs to the chain branching reaction and can accelerate the reaction of the system; as the temperature increases, the reaction ⑧ and ② become competitive reactions, the concentration of OH groups in the system decreases, the reaction rate decreases, and the ignition delay phenomenon (also known as the negative temperature coefficient phenomenon, that is, the NTC phenomenon) appears. ⑨—⑩ are high temperature reactions.
负温度系数氧进程内发生反应②-⑧，主要反应④和⑦可知：负温度系数氧化进程内的主要中间产物为醛、酮、醚。Reactions ②-⑧ occur in the negative temperature coefficient oxygen process, and the main reactions ④ and ⑦ show that the main intermediate products in the negative temperature coefficient oxidation process are aldehydes, ketones, and ethers.
本发明提供一种中温气汽驱采油氧化前缘的确定方法，该方法采用标志物法，以醛酮醚作为标志物，通过检测中温气汽驱采油井口产出气和/或产出液中的醛酮醚标志物的浓度，用于确定取样井所在位置对应的储层中氧化前缘的氧化模式。The invention provides a method for determining the oxidation front of medium-temperature gas-driven oil recovery. The method adopts the marker method, using aldehydes, ketones and ethers as markers, and detects the amount of gas and/or produced liquid in the wellhead of medium-temperature gas-driven steam-driven oil recovery. The concentration of the aldehyde, ketone ether marker is used to determine the oxidation mode of the oxidation front in the reservoir corresponding to the location of the sampling well.
在本发明中，以醛酮醚作为标志物，通过检测醛酮醚标志物中醛的浓度监测负温度系数氧化进程，以判断取样井所在位置对应的储层中氧化前缘的氧化模式是否为负温度系数氧化进程。In the present invention, aldehydes, ketones, and ethers are used as markers, and the negative temperature coefficient oxidation process is monitored by detecting the concentration of aldehydes in the aldehydes, ketones, and ethers markers to determine whether the oxidation mode of the oxidation front in the reservoir corresponding to the location of the sampling well is Negative temperature coefficient oxidation process.
由于在现场试验时发现负温度系数氧化模式下，负温度系数氧化进程的中间产物醛酮醚标志物中醛的含量最大且明显大于酮和醚，且更易于检测，检测结果更准确，因此，可通过测量醛酮醚中间产物中醛的浓度来监测负温度系数氧化进程。当然，也可通过检测醛酮醚中间产物中的酮或醚的浓度，或者其中两者或三者浓度的结合来判断负温度系数氧化进程，可以根据具体油藏的具体情况而定。Since it was found in the field test that under the negative temperature coefficient oxidation mode, the content of aldehyde in the intermediate product aldehyde and ketone ether markers of the negative temperature coefficient oxidation process is the largest and is significantly greater than that of ketones and ethers, and it is easier to detect and the detection results are more accurate. Therefore, The progress of NTC oxidation can be monitored by measuring the concentration of aldehyde in the aldehyde ketone ether intermediate. Of course, the negative temperature coefficient oxidation process can also be judged by detecting the concentration of ketone or ether in the intermediate product of aldehyde, ketone ether, or the combination of the two or three concentrations, which can be determined according to the specific conditions of the specific oil reservoir.
需要说明的是，中温气汽驱采油井口采出的样品为中温气汽驱采油井口的产出液和/或产出气。在检测醛酮醚浓度时，需在中温气汽驱采油井口进行采样，本发明并不对采集的样品的形态做具体的限定，会随着反应进程的不同，中温气汽驱采油井口采出的样品会有所变化。若中温气汽驱采油井口采出的是气体，则检测气体中醛酮醚的浓度；若中温气汽驱采油井口采出的是液体，则检测液体中醛酮醚的浓度；若中温气汽驱采油井口采出的是气体和液体的混合物，则检测气液混合物中醛酮醚的浓度。It should be noted that the samples produced from the medium-temperature gas steam-flooding oil production wellhead are the produced fluid and/or produced gas from the medium-temperature gas steam-flooded oil production wellhead. When detecting the concentration of aldehydes, ketones and ethers, it is necessary to sample at the wellhead of medium-temperature gas-driven oil production. Samples are subject to change. If the medium-temperature gas drive wellhead produces gas, then detect the concentration of aldehydes, ketones, and ethers in the gas; The gas and liquid mixture is produced from the wellhead of flooding and recovery, and the concentration of aldehyde, ketone, and ether in the gas-liquid mixture is detected.
具体的，本发明以负温度系数氧化进程的主要产物——醛酮醚为标志物，在醛含量最大的情况下，采用酚试剂分光光度法测定醛的浓度。其基本原理是，以中温气汽驱采油井口产出气和/或产出液中的负温度系数氧化进程产出物——醛酮醚为标志物，其中的醛可与酚试剂反应生成嗪。反应生成的嗪，在酸性溶液中进一步反应生成蓝绿色化合物。负温度系数氧化进程反应产物增加，对应着颜色变化，该变化是负温度系数氧化进程情况的函数。Specifically, the present invention uses aldehydes, ketone ethers, the main product of the negative temperature coefficient oxidation process, as a marker, and uses phenol reagent spectrophotometry to measure the concentration of aldehydes when the aldehyde content is the largest. The basic principle is to take the output product of the oxidation process of negative temperature coefficient in the gas and/or the output liquid in the medium-temperature gas steam drive oil production wellhead——aldehyde, ketone ether, as the marker, and the aldehyde in it can react with the phenolic reagent to form oxazine . The azine produced by the reaction further reacts in an acidic solution to form a blue-green compound. The NTC oxidation process reaction product increases, corresponding to a color change that is a function of the NTC oxidation process conditions.
通过测量醛的浓度确定氧化前缘是否进入负温度系数氧化进程及负温度系数氧化进程情况测试包括如下步骤：Determine whether the oxidation front enters the negative temperature coefficient oxidation process by measuring the concentration of aldehyde and the test of the negative temperature coefficient oxidation process includes the following steps:
(1)绘制不同浓度的标准醛对应的蓝绿色化合物吸光度值与醛含量标准曲线，所述蓝绿色化合物为所述标准醛与酚试剂反应生成的嗪在酸性溶液中进一步反应的产物；(1) Draw the blue-green compound absorbance value corresponding to the standard aldehydes of different concentrations and the aldehyde content standard curve, and the blue-green compound is the product of the further reaction of the oxazine generated by the reaction of the standard aldehyde and the phenol reagent in the acidic solution;
(2)绘制中温气汽驱时，根据醛含量与负温度系数氧化进程情况的函数关系，得到负温度系数氧化进程对应的醛含量的区间；(2) When drawing medium-temperature gas steam drive, according to the functional relationship between aldehyde content and negative temperature coefficient oxidation process, the interval of aldehyde content corresponding to the negative temperature coefficient oxidation process is obtained;
(3)采集中温气汽驱采油井口产出气和/或产出液，采用酚试剂法检测，得到醛的浓度；(3) Collect the produced gas and/or produced liquid at the wellhead of medium-temperature gas-driven steam drive, and detect with the phenol reagent method to obtain the concentration of aldehyde;
(4)若测定的醛的浓度位于负温度系数氧化进程对应的醛含量的区间外，则确定取样井所在位置对应的储层中的氧化模式为非负温度系数氧化进程；若测定的醛的浓度位于负温度系数氧化进程对应的醛含量的区间内，则确定取样井所在位置对应的储层中的氧化模式为负温度系数氧化进程。(4) If the concentration of the measured aldehyde is outside the interval of the aldehyde content corresponding to the negative temperature coefficient oxidation process, then determine that the oxidation mode in the reservoir corresponding to the location of the sampling well is a non-negative temperature coefficient oxidation process; if the measured aldehyde If the concentration is within the interval of the aldehyde content corresponding to the negative temperature coefficient oxidation process, then it is determined that the oxidation mode in the reservoir corresponding to the location of the sampling well is the negative temperature coefficient oxidation process.
进一步地，将测定的醛的浓度与醛含量与负温度系数氧化进程情况的函数关系对比，进而通过醛的浓度来推断负温度系数氧化进程情况。Further, the measured aldehyde concentration was compared with the functional relationship between the aldehyde content and the negative temperature coefficient oxidation process, and then the negative temperature coefficient oxidation process was inferred from the concentration of aldehyde.
本发明通过对中温气汽驱采油井口的取样检测，判断取样井所在位置附近储层中的氧化模式以及负温度系数氧化进程情况，为调整操控工况提供依据。The invention judges the oxidation mode and the negative temperature coefficient oxidation process in the reservoir near the location of the sampling well by sampling and detecting the medium-temperature gas-steam drive oil production wellhead, and provides a basis for adjusting the operating conditions.
根据本发明，所述标志物法通过检测负温度系数氧化反应进程的中间产物醛酮醚中醛的浓度判断氧化前缘是否进入负温度系数氧化进程，若所述醛的浓度在0.2mg/m
3以上时，所述标志物法确定取样井所在位置对应的储层中氧化前缘的氧化模式为负温度系数氧化进程，其中，所述负温度系数氧化进程为反应速率随着温度的升高而降低的着火延迟区间的氧化过程。
According to the present invention, the marker method judges whether the oxidation front enters the negative temperature coefficient oxidation process by detecting the concentration of aldehyde in the intermediate product aldehyde and ketone ether of the negative temperature coefficient oxidation reaction process, if the concentration of the aldehyde is 0.2 mg/m 3 or more, the marker method determines that the oxidation mode of the oxidation front in the reservoir corresponding to the location of the sampling well is a negative temperature coefficient oxidation process, wherein the negative temperature coefficient oxidation process is that the reaction rate increases with the temperature while reducing the oxidation process in the ignition delay interval.
本发明以醛的浓度作为确定取样井所在位置对应的储层中氧化前缘的氧化模式是否为负温度系数氧化进程，若醛的浓度大于等于0.2mg/m
3，则判断取样井所在位置对应的储层中氧化前缘的氧化模式 为负温度系数氧化进程；若醛的浓度小于0.2mg/m
3，则判断取样井所在位置对应的储层中氧化前缘的氧化模式为非负温度系数氧化进程。
In the present invention, the concentration of aldehyde is used to determine whether the oxidation mode of the oxidation front in the reservoir corresponding to the location of the sampling well is an oxidation process with a negative temperature coefficient. The oxidation mode of the oxidation front in the reservoir is a negative temperature coefficient oxidation process; if the concentration of aldehyde is less than 0.2mg/m 3 , it is judged that the oxidation mode of the oxidation front in the reservoir corresponding to the location of the sampling well is a non-negative temperature coefficient oxidation process.
在一些实施方式中，所述负温度系数氧化进程介于低温氧化进程与高温氧化进程之间。In some embodiments, the negative temperature coefficient oxidation process is between a low temperature oxidation process and a high temperature oxidation process.
在本发明中，若确定取样井所在位置对应的储层中氧化前缘进入所述负温度系数氧化进程，则通过将测定的醛的浓度与醛含量与负温度系数氧化进程情况的函数关系比对，推断所述负温度系数氧化进程的情况。In the present invention, if it is determined that the oxidation front in the reservoir corresponding to the location of the sampling well enters the negative temperature coefficient oxidation process, then by comparing the functional relationship between the measured aldehyde concentration and the aldehyde content and the negative temperature coefficient oxidation process Yes, infer the case of the NTC oxidation process.
通过推断所述负温度系数氧化进程的情况，可以推定进入负温度系数氧化进程的周围区域和范围。对于具体油藏来说，找到醛含量与负温度系数氧化情况的关系，就可以知道这个反应中一份油大概产生多少份醛，如果醛数量在大幅的增加，那么就意味着有更大范围的区域已经进入了负温度系数氧化进程。By inferring the conditions of the negative temperature coefficient oxidation process, the surrounding area and range entering the negative temperature coefficient oxidation process can be estimated. For a specific oil reservoir, if you find the relationship between the aldehyde content and the oxidation of the negative temperature coefficient, you can know how many aldehydes are produced in one oil in this reaction. If the amount of aldehydes is increasing significantly, it means that there is a wider range The region has entered the negative temperature coefficient oxidation process.
作为进一步优选的实施方式，所述的确定方法进一步采用温压法，所述温压法通过检测中温气汽驱采油井口产出液的温度、压力、温度的变化速度或压力的变化速度，判断储层内原油氧化前缘的氧化模式。As a further preferred embodiment, the determination method further adopts the temperature-pressure method, and the temperature-pressure method judges the Oxidation patterns of crude oil oxidation fronts in reservoirs.
本发明中，温压法通过测量采出液温度、压力、温度的变化速度或压力的变化速度来确定储层内原油的氧化前缘是否进入高温氧化进程；例如若取样井采出液温度高于350℃以上，则认为进入高温氧化。In the present invention, the temperature-pressure method determines whether the oxidation front of crude oil in the reservoir enters the high-temperature oxidation process by measuring the temperature, pressure, and rate of change of temperature or pressure of the produced fluid; for example, if the temperature of the produced fluid in the sampling well is high Above 350°C, it is considered to enter high temperature oxidation.
在一些实施方式中，所述醛的浓度的检测方法，采用酚试剂法结合分光光度仪进行测量，包括如下步骤：In some embodiments, the detection method of the concentration of the aldehyde is measured by a phenol reagent method combined with a spectrophotometer, comprising the following steps:
本法中所用水均为重蒸馏水或去离子交换水；所用的试剂纯度一般为分析纯。The water used in this method is double distilled water or deionized water; the purity of the reagents used is generally analytical pure.
1.1、吸收液原液：称量0.10g酚试剂[C
6H
4SN(CH
3)C:NNH
2·HCl,简称MBTH]，加水溶解，倾于100mL具塞量筒中，加水到刻度。放冰箱中保存，可稳定三天。
1.1. Absorbent stock solution: Weigh 0.10g of phenol reagent [C 6 H 4 SN(CH 3 )C:NNH 2 ·HCl, referred to as MBTH], add water to dissolve, pour into a 100mL stoppered measuring cylinder, add water to the mark. Stored in the refrigerator, it is stable for three days.
1.2、吸收液：量取吸收原液5mL，加95mL水，即为吸收液。采样时，临用现配。1.2. Absorbing solution: Measure 5mL of the original absorbing solution and add 95mL of water to obtain the absorbing solution. When sampling, it is ready-to-use.
1.3、1％硫酸铁铵溶液：称量1.0g硫酸铁铵[NH
4Fe(SO
4)
2·12H
2O]用0.1mol/L盐酸溶解，并稀释至100mL。
1.3. 1% ferric ammonium sulfate solution: weigh 1.0 g of ferric ammonium sulfate [NH 4 Fe(SO 4 ) 2 ·12H 2 O], dissolve it with 0.1 mol/L hydrochloric acid, and dilute to 100 mL.
步骤1、绘制标准曲线：绘制不同浓度的标准醛对应的蓝绿色化合物吸光度值与醛含量标准曲线，甲醛含量为横坐标，吸光度为纵坐标，并计算回归斜率，以斜率倒数作为样品测定的计算因子Bg(毫克/吸光度)；Step 1. Draw a standard curve: draw the standard curve of the absorbance value of the blue-green compound corresponding to different concentrations of standard aldehydes and the aldehyde content, the formaldehyde content is the abscissa, the absorbance is the ordinate, and calculate the regression slope, and use the reciprocal of the slope as the calculation of the sample determination Factor Bg (mg/absorbance);
取10mL具塞比色管，用醛标准溶液制备不同浓度的标准系列，含有不同浓度的醛标准溶液和吸收液。各管中，加入0.4mL，1％硫酸铁铵溶液，摇匀。放置15min。用1cm比色皿，以在波长625-635nm下，以水参比，采用分光光度仪测定各管溶液的吸光度。以醛含量为横坐标，吸光度为纵坐标，绘制曲线，并计算回归斜率，以斜率倒数作为样品测定的计算因子Bg(毫克/吸光度)。Take a 10mL stoppered colorimetric tube and use aldehyde standard solution to prepare standard series with different concentrations, containing aldehyde standard solution and absorption solution with different concentrations. To each tube, add 0.4 mL of 1% ferric ammonium sulfate solution and shake well. Leave it for 15min. Use a 1cm cuvette to measure the absorbance of the solution in each tube with a spectrophotometer at a wavelength of 625-635nm, using water as a reference. Take the aldehyde content as the abscissa and the absorbance as the ordinate, draw a curve, and calculate the regression slope, and use the reciprocal of the slope as the calculation factor Bg (mg/absorbance) for sample determination.
步骤2、样品测试：Step 2, sample test:
采样后，将样品溶液全部转入比色管中，用少量吸收液洗吸收管，合并使总体积为5mL。按绘制标准曲线的操作步骤测定吸光度(A)， 在每批样品测定的同时，用5mL未采样的吸收液作试剂空白，测定试剂空白的吸光度(A0)。所述样品为中温气汽驱采油井口产出液或产出气。After sampling, transfer all the sample solution into the colorimetric tube, wash the absorption tube with a small amount of absorption solution, and combine to make the total volume 5mL. Measure the absorbance (A) according to the operation steps of drawing the standard curve. While measuring each batch of samples, use 5mL of unsampled absorption solution as the reagent blank, and measure the absorbance (A0) of the reagent blank. The sample is medium-temperature gas-steam flooding wellhead produced fluid or produced gas.
步骤3、醛含量结果计算：Step 3, aldehyde content result calculation:
将采样体积按公式(I)换算成标准状态下采样体积；Sampling volume is converted into sampling volume under the standard state by formula (1);
V
0＝V
t·T
0/(273+t)·P/P
0…………………………(I)
V 0 =V t ·T 0 /(273+t)·P/P 0 ………………………(I)
式(I)中：V
0――标准状态下的采样体积，L；
In formula (I): V 0 —— sampling volume under standard state, L;
Vt――采样体积，L；Vt - sampling volume, L;
t――采样点的气温，℃；t—the air temperature at the sampling point, °C;
T
0――标准状态下的绝对温度273K；
T 0 - the absolute temperature of 273K under the standard state;
P――采样点的大气压力，kPa；P - Atmospheric pressure at the sampling point, kPa;
P
0――标准状态下的大气压力，101kPa。
P 0 ―― Atmospheric pressure under standard conditions, 101kPa.
样品中甲醛浓度按公式(II)计算；Formaldehyde concentration is calculated by formula (II) in the sample;
C＝(A-A
0)×Bg/V
0…………………………(II)
C＝(AA 0 )×Bg/V 0 …………………………(II)
式(II)中：C――空气中甲醛mg/m；In the formula (II): C - mg/m of formaldehyde in the air;
A――样品溶液的吸光度；A - the absorbance of the sample solution;
A
0――空白溶液的吸光度；
A 0 - the absorbance of the blank solution;
Bg――计算因子，毫克/吸光度；Bg—calculation factor, mg/absorbance;
V
0――换算成标准状态下的采样体积，L。
V 0 --- converted into the sampling volume under the standard state, L.
本发明基于原油负温度系数氧化进程特性，提出的中温气汽驱采油方法，是注空气点火，并控制条件促使原油能够跨越负温度系数氧化进程而成功进入高温氧化进程，以化学反应产生的热量使原油降粘 改质、以化学反应产生的气体混同注入流体，驱替原油的开采方法，所述负温度系数氧化进程是指系统反应速率随着温度的升高而降低的着火延迟区间的氧化过程，所述负温度系数氧化进程介于低温氧化进程与高温氧化进程之间。Based on the characteristics of the negative temperature coefficient oxidation process of crude oil, the medium temperature gas flooding oil recovery method proposed by the present invention is to inject air into the ignition, and control the conditions to promote the crude oil to cross the negative temperature coefficient oxidation process and successfully enter the high temperature oxidation process, using the heat generated by the chemical reaction It is a method of reducing the viscosity of crude oil and modifying it, mixing the injected fluid with gas generated by chemical reactions, and displacing crude oil. The negative temperature coefficient oxidation process refers to the oxidation in the ignition delay interval where the reaction rate of the system decreases with the increase of temperature. process, the negative temperature coefficient oxidation process is between the low temperature oxidation process and the high temperature oxidation process.
为了进一步理解本发明，下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to further understand the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them. . Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
如无特殊说明，本发明实施例中所涉及的试剂均为市售产品，均可以通过商业渠道购买获得。Unless otherwise specified, the reagents involved in the examples of the present invention are all commercially available products, which can be purchased through commercial channels.
实施例1Example 1
对某油田1号油井的中温气汽驱采油氧化前缘进行确定的方法，采用标志物法，检测中温气汽驱采油井口采出的气体和/或液体样品中的醛酮醚标志物中醛的浓度为0.3mg/m
3，判断1号油井所在位置附近的储层中氧化前缘的氧化模式为负温度系数氧化进程。
A method for determining the oxidation front of medium-temperature gas-flooding oil production well No. 1 in an oilfield, using the marker method to detect aldehydes and ketone-ether markers in the gas and/or liquid samples produced at the medium-temperature gas-flooding oil production wellhead The concentration is 0.3mg/m 3 , and it is judged that the oxidation mode of the oxidation front in the reservoir near the location of No. 1 oil well is negative temperature coefficient oxidation process.
实施例2Example 2
对某油田2号油井的中温气汽驱采油氧化前缘进行确定的方法，采用与实施例1相同的标志物法，得到醛的浓度为0.1mg/m
3，判断2号油井所在位置对应的储层中氧化前缘的氧化模式为非负温度系数氧化进程。
The method for determining the oxidation front of medium-temperature gas-steam flooding oil production well No. 2 in an oilfield uses the same marker method as in Example 1 to obtain an aldehyde concentration of 0.1 mg/m 3 , and determine the corresponding The oxidation mode of the oxidation front in the reservoir is a non-negative temperature coefficient oxidation process.
实施例3Example 3
在实施例2的基础上，辅以温压法共同确定氧化前缘的氧化模式，在判断2号油井所在位置对应的储层中氧化前缘的氧化模式为非负温度系数氧化进程的基础上，采用温压法测定采油井产出液温度为150℃，进一步判断为非高温氧化进程，则可确定2号油井所在位置对应的储层中氧化前缘的氧化模式为低温氧化进程。On the basis of Example 2, combined with the temperature-pressure method to determine the oxidation mode of the oxidation front, on the basis of judging that the oxidation mode of the oxidation front in the reservoir corresponding to the location of the No. 2 oil well is a non-negative temperature coefficient oxidation process , the temperature and pressure method was used to measure the temperature of the produced fluid in the production well to be 150 °C, and it was further judged to be a non-high-temperature oxidation process, so it can be determined that the oxidation mode of the oxidation front in the reservoir corresponding to the location of the No. 2 oil well is a low-temperature oxidation process.
实施例4Example 4
对某油田3号油井的中温气汽驱采油氧化前缘进行确定的方法，采用与实施例1相同的标志物法，得到醛的浓度为0.15mg/m
3，判断3号油井所在位置对应的储层中氧化前缘的氧化模式为非负温度系数氧化进程；在此基础上，采用温压法测定采油井产出液温度为450℃，进一步判断为高温氧化进程，则可确定3号油井所在位置对应的储层中氧化前缘的氧化模式为高温氧化进程。
The method for determining the oxidation front of medium-temperature gas steam drive oil recovery in No. 3 oil well in an oilfield uses the same marker method as in Example 1 to obtain an aldehyde concentration of 0.15 mg/m 3 , and judges the corresponding The oxidation mode of the oxidation front in the reservoir is a non-negative temperature coefficient oxidation process; on this basis, the temperature of the production fluid produced by the production well is determined to be 450 °C by using the temperature-pressure method, and it is further judged as a high-temperature oxidation process, so it can be determined that the No. 3 oil well The oxidation mode of the oxidation front in the reservoir corresponding to the location is a high temperature oxidation process.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.
Claims (10)
- 一种中温气汽驱采油氧化前缘的确定方法，其特征在于，该方法采用标志物法，以醛酮醚作为标志物，通过检测中温气汽驱采油井口产出气和/或产出液中的醛酮醚标志物的浓度，用于确定取样井所在位置对应的储层中氧化前缘的氧化模式。A method for determining the oxidation front of medium-temperature gas-driven oil production, characterized in that the method uses a marker method, using aldehydes, ketones, and ethers as markers, and detects the gas and/or produced liquid at the wellhead of medium-temperature gas-driven steam-driven oil production The concentration of the aldehyde, ketone ether marker in the sample well is used to determine the oxidation mode of the oxidation front in the reservoir corresponding to the location of the sampling well.
- 根据权利要求1所述的确定方法，其中，所述标志物法通过检测负温度系数氧化反应进程的中间产物醛酮醚标志物中醛的浓度判断氧化前缘是否进入负温度系数氧化进程，若所述醛的浓度在0.2mg/m 3以上时，所述标志物法确定取样井所在位置对应的储层中氧化前缘的氧化模式为负温度系数氧化进程，其中，所述负温度系数氧化进程为反应速率随着温度的升高而降低的着火延迟区间的氧化过程。 The determination method according to claim 1, wherein the marker method judges whether the oxidation front enters the negative temperature coefficient oxidation process by detecting the concentration of aldehydes in the intermediate product aldehyde ketone ether marker of the negative temperature coefficient oxidation reaction process, if When the concentration of the aldehyde is above 0.2mg/ m3 , the marker method determines that the oxidation mode of the oxidation front in the reservoir corresponding to the location of the sampling well is a negative temperature coefficient oxidation process, wherein the negative temperature coefficient oxidation The process is an oxidation process in the ignition delay interval where the reaction rate decreases with increasing temperature.
- 根据权利要求2所述的确定方法，其中，采用酚试剂法测量所述醛的浓度，包括如下步骤：Determination method according to claim 2, wherein, adopt phenol reagent method to measure the concentration of described aldehyde, comprise the steps:(1)绘制不同浓度的标准醛对应的蓝绿色化合物吸光度值与醛含量标准曲线，所述蓝绿色化合物为所述标准醛与酚试剂反应生成的嗪在酸性溶液中进一步反应的产物；(1) Draw the blue-green compound absorbance value corresponding to the standard aldehydes of different concentrations and the aldehyde content standard curve, and the blue-green compound is the product of the further reaction of the oxazine generated by the reaction of the standard aldehyde and the phenol reagent in the acidic solution;(2)绘制中温气汽驱时，根据醛含量与负温度系数氧化进程情况的函数关系，得到负温度系数氧化进程对应的醛含量的区间；(2) When drawing medium-temperature gas steam drive, according to the functional relationship between aldehyde content and negative temperature coefficient oxidation process, the interval of aldehyde content corresponding to the negative temperature coefficient oxidation process is obtained;(3)采集中温气汽驱采油井口产出气和/或产出液，采用酚试剂法检测，得到醛的浓度；(3) Collect the produced gas and/or produced liquid at the wellhead of medium-temperature gas-driven steam drive, and detect with the phenol reagent method to obtain the concentration of aldehyde;(4)若测定的醛的浓度位于负温度系数氧化进程对应的醛含量 的区间外，则确定取样井所在位置对应的储层中的氧化模式为非负温度系数氧化进程；若测定的醛的浓度位于负温度系数氧化进程对应的醛含量的区间内，则确定取样井所在位置对应的储层中的氧化模式为负温度系数氧化进程。(4) If the concentration of the measured aldehyde is outside the interval of the aldehyde content corresponding to the negative temperature coefficient oxidation process, then determine that the oxidation mode in the reservoir corresponding to the location of the sampling well is a non-negative temperature coefficient oxidation process; if the measured aldehyde If the concentration is within the interval of the aldehyde content corresponding to the negative temperature coefficient oxidation process, then it is determined that the oxidation mode in the reservoir corresponding to the location of the sampling well is the negative temperature coefficient oxidation process.
- 根据权利要求3所述的确定方法，其中，若确定取样井所在位置对应的储层中氧化前缘进入所述负温度系数氧化进程，则对照醛含量与负温度系数氧化进程情况的函数关系，推断所述负温度系数氧化进程的情况。The determination method according to claim 3, wherein, if it is determined that the oxidation front in the reservoir corresponding to the location of the sampling well enters the negative temperature coefficient oxidation process, then comparing the functional relationship between the aldehyde content and the negative temperature coefficient oxidation process, The case of the NTC oxidation process is extrapolated.
- 根据权利要求1-4中任意一项所述的确定方法，其中，该方法进一步采用温压法，所述温压法通过检测中温气汽驱采油井口产出液的温度、压力或其变化速度监测高温氧化进程。The determination method according to any one of claims 1-4, wherein the method further adopts the temperature-pressure method, and the temperature-pressure method detects the temperature, pressure or its rate of change of the medium-temperature gas drive oil recovery wellhead production fluid Monitor high temperature oxidation progress.
- 根据权利要求5所述的确定方法，其中，基于所述标志物法和温压法，联合确定取样井所在位置对应的储层中的氧化模式。The determination method according to claim 5, wherein, based on the marker method and the temperature-pressure method, the oxidation mode in the reservoir corresponding to the location of the sampling well is jointly determined.
- 根据权利要求6所述的确定方法，其中，若所述标志物法判断的结果为负温度系数氧化进程，则确定取样井所在位置对应的储层中的氧化模式为负温度系数氧化进程。The determination method according to claim 6, wherein, if the result determined by the marker method is a negative temperature coefficient oxidation process, then it is determined that the oxidation mode in the reservoir corresponding to the location of the sampling well is a negative temperature coefficient oxidation process.
- 根据权利要求6所述的确定方法，其中，若所述标志物法判断的结果为非负温度系数氧化进程，则根据所述温压法确定取样井所在位置对应的储层中的氧化模式是否为高温氧化进程。The determination method according to claim 6, wherein, if the result of the judgment by the marker method is a non-negative temperature coefficient oxidation process, then according to the temperature-pressure method, it is determined whether the oxidation mode in the reservoir corresponding to the location of the sampling well is For the high temperature oxidation process.
- 根据权利要求8所述的确定方法，其中，若所述温压法的结果为高温氧化进程，则确定取样井所在位置附近储层中的氧化模式为高温氧化进程。The determination method according to claim 8, wherein, if the result of the temperature-pressure method is a high-temperature oxidation process, then it is determined that the oxidation mode in the reservoir near where the sampling well is located is a high-temperature oxidation process.
- 根据权利要求8所述的确定方法，其中，若所述温压法的结果为非高温氧化进程，则确定取样井所在位置附近储层中的氧化模式为低温氧化进程。The determination method according to claim 8, wherein, if the result of the temperature-pressure method is a non-high-temperature oxidation process, then it is determined that the oxidation mode in the reservoir near where the sampling well is located is a low-temperature oxidation process.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5488990A (en) * | 1994-09-16 | 1996-02-06 | Marathon Oil Company | Apparatus and method for generating inert gas and heating injected gas |
| CN104612666A (en) * | 2014-12-01 | 2015-05-13 | 中国石油天然气股份有限公司 | Method for monitoring temperature of front edge of live wire |
| CN105019889A (en) * | 2014-04-28 | 2015-11-04 | 中国石油化工股份有限公司 | Low-temperature oxidation rate prediction and safety protection method for light oil reservoir crude oil |
| CN112502680A (en) * | 2020-11-19 | 2021-03-16 | 中国石油天然气股份有限公司 | Method for judging fireflood combustion state |
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2021
- 2021-12-31 CN CN202111665692.8A patent/CN116411902A/en active Pending
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- 2022-06-30 WO PCT/CN2022/102887 patent/WO2023123969A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5488990A (en) * | 1994-09-16 | 1996-02-06 | Marathon Oil Company | Apparatus and method for generating inert gas and heating injected gas |
| CN105019889A (en) * | 2014-04-28 | 2015-11-04 | 中国石油化工股份有限公司 | Low-temperature oxidation rate prediction and safety protection method for light oil reservoir crude oil |
| CN104612666A (en) * | 2014-12-01 | 2015-05-13 | 中国石油天然气股份有限公司 | Method for monitoring temperature of front edge of live wire |
| CN112502680A (en) * | 2020-11-19 | 2021-03-16 | 中国石油天然气股份有限公司 | Method for judging fireflood combustion state |
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