CN102207491B - Method for measuring low-temperature oxidation reaction rate of light crude oil - Google Patents
Method for measuring low-temperature oxidation reaction rate of light crude oil Download PDFInfo
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- CN102207491B CN102207491B CN 201010136507 CN201010136507A CN102207491B CN 102207491 B CN102207491 B CN 102207491B CN 201010136507 CN201010136507 CN 201010136507 CN 201010136507 A CN201010136507 A CN 201010136507A CN 102207491 B CN102207491 B CN 102207491B
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- 239000010779 crude oil Substances 0.000 title claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000003921 oil Substances 0.000 claims abstract description 32
- 238000002474 experimental method Methods 0.000 claims abstract description 7
- 238000007872 degassing Methods 0.000 claims abstract description 6
- 238000005070 sampling Methods 0.000 claims description 38
- 238000003556 assay Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 238000010926 purge Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims 1
- 230000036284 oxygen consumption Effects 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract description 2
- 238000009533 lab test Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 230000001590 oxidative effect Effects 0.000 description 8
- 238000011084 recovery Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000011157 data evaluation Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000012332 laboratory investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method for measuring a low-temperature oxidation reaction rate of a light crude oil in laboratory experiment research for improving yield of an oil field. In the method, a sample mixing device is used as a reaction container; the amount of solution gas is calculated according to a gas-oil ratio which is obtained through single degassing experiments of the crude oil at different reaction stages; gas cap gas amounts at different reaction stages, and the crude oil amount and oxygen consumption amount in the oxidation reaction are calculated according to the mass conservation law and constitution change situations of the gas cap gas and the solution gas; and the average low-temperature reaction rate of the crude oil at different reaction stages is calculated on the basis of the gas cap gas amount and the crude oil amount and oxygen consumption amount. According to the method in the invention, the average oxidation reaction rate values of the crude oil at different stages are exactly measured so as to provide foundation data for calculating crude oil oxidation reaction kinetic parameters and comparing reaction activities between different crude oils.
Description
Technical field
The present invention relates to a kind of assay method of light crude low-temperature oxidation reaction rate, belong to agent for improving oilfield recovery in-house laboratory investigation technical field.
Background technology
Before implementing light oil reservoirs high pressure air injection and air injection foam and improving the recovery ratio project, need to carry out resident fluid laboratory study and data evaluation, in order to help to determine, operation conditions optimization.Wherein, the mensuration of crude oil low-temperature oxidation reaction rate is the basis of calculating crude oil oxidation reaction kinetics parameter, can its size fully consume oxygen before not only being related to air arrival producing well, oxygen concentration is reduced under the critical dissolved oxygen concentration, guarantee production safety, and be related to the complexity of the spontaneous formation of combustion front, the raising of recovery ratio there is material impact.At present, there is bibliographical information to adopt the Pressure Drop method to measure the low-temperature oxidation reaction rate of crude oil both at home and abroad, such as article " air injection foam low temperature oxidation technology improves recovery test " (China University Of Petroleum Beijing's journal, the 4th phase in 2009: 94-98) described, usually in the test duration scope, the pressure decreased that the dissolving of air in the stratum causes is far longer than because the pressure decreased that oxygen expenditure causes, and the method is not considered in pressure decreased that the dissolving of air in in-place oil causes and the course of reaction because gaseous component forms and changes the pressure that causes and change, and the reaction rate value and the actual value deviation that cause the method to be measured are excessive; Simultaneously, because the dissolution degree difference of air in different crude oils lacks comparability between the different crude oils oxidizing reaction rate that the method is measured.The change calculations low-temperature oxidation reaction rate that is also formed by monitoring core flowing experiment outlet output gas component by bibliographical information, such as article " the solidifying oily air-injected low-temperature oxidation thing mould research of Cao Taigao " (drilling technique, o. 11th in 2008: 113-115) described, the method is not considered the impact that the difference of the variation of gas phase saturation in the dissolving of air in crude oil, the core and oxygen and nitrogen solubility forms output gas component, and measurement result and actual value have relatively large deviation.
Summary of the invention
The objective of the invention is the defective that the oxidizing reaction rate measurement result that exists for above-mentioned technology and actual value have relatively large deviation, a kind of assay method that can Accurate Determining light crude low-temperature oxidation reaction rate is provided.
The assay method of light crude low-temperature oxidation reaction rate provided by the present invention, carry out in accordance with the following steps:
(1) the dead oil sample of the scene being fetched changes in the dehydrating apparatus and dewaters, and dewaters qualified rear for subsequent use;
(2) with air compressing to the sample device, constant temperature is to T
Air, constant voltage is to reservoir pressure P
fMore than 4 hours, stand-by;
The dead oil sample that (3) will dewater qualified changes in the sample device as reaction vessel, the crude quality W that record changes over to
Oil, constant temperature is to temperature of reaction, and constant voltage is to reservoir pressure P
fMore than 4 hours; The dead oil sample mix that adopts the double pump method that ready pressurized air is changed in this sample device and changed over to, the pressurized air volume V that record changes over to
Air
The sample device constant temperature and pressure that (4) will change crude oil and air over to is to temperature of reaction and pressure, stir and writing time t
0
(5) before the sampling, with the air of helium purge sampling system noresidue to the system, record accumulative total reaction time t
mTaking out volume from the sample device is V
CmGas cap gas, utilize gas chromatograph to analyze gas cap gas and form; From the sample device, take out an amount of crude oil and carry out the single degassing experiment, the quality W of record gas-free oil
mVolume V with solution gas
Sm, adopt gas chromatograph to analyze the composition of solution gas; Atmospheric temperature T when recording every sub-sampling
mWith atmospheric pressure P
m
(6) repeating step 5 to reaction finishes;
(7) suppose that quality remains unchanged in the gas-free oil course of reaction, calculate by the following method the low-temperature oxidation reaction rate value of obtaining crude oil:
In the formula:
n
AirChange the amount of the air in the reaction sample device over to, mol;
T
AirCompressed air temperature, K;
P
fReservoir pressure, MPa;
The Z temperature T
Air, pressure P
fThe time air deviation factors;
The R mol gas constant, 8.31451MPamL/(molK);
V
AirChange the volume of air in the reaction sample device over to, mL.
In the formula:
n
CmThe amount of the gas cap gas that takes out during the m sub-sampling, mol;
V
CmThe gas cap gas volume that takes out during the m sub-sampling, mL;
T
mAtmospheric temperature during the m sub-sampling, K;
P
mAtmospheric pressure during the m sub-sampling, MPa.
In the formula:
n
SmThe amount of the solution gas that takes out during the m sub-sampling, mol;
V
SmThe solution gas volume that takes out during the m sub-sampling, mL.
In the formula:
n
StmThe amount of total solution gas before the m sub-sampling, mol;
W
OilChange the gas-free oil quality in the reaction sample device over to, g;
W
mThe gas-free oil quality of discharging during the m sub-sampling, g.
[0008]In the formula:
n
CtmTotal pneumatic jack tolerance before the m sub-sampling, mol;
Y
SmjThe molar content of j component in the m sub-sampling solution gas, %;
Y
CmjThe molar content of j component in the m sub-sampling gas cap gas, %.
(6)
In the formula:
(7)
[0010]In the formula:
ν
mThe average oxygen consumption rate of crude oil between m-1 sub-sampling to the m sub-sampling, mol/ (hg);
t
mThe accumulative total reaction time during to the m sub-sampling, h.
The invention has the beneficial effects as follows the sample device as reaction vessel, calculate the amount of solution gas in the crude oil by the output gas oil ratio of differential responses stage crude oil single degassing experiment acquisition, form situation of change by measure air and crude oil system that the low-temperature oxidation reaction occurs in the sample device in the component of differential responses stage gas top gas and solution gas, calculate the pneumatic jack tolerance of the variant stage of reaction according to law of conservation of mass, participate in former oil mass and the oxygen expenditure amount of oxidation reaction, accurately calculate based on this average response speed of differential responses stage crude oil low-temperature oxidation reaction, for the contrast of reactivity between the calculating of crude oil oxidation reaction kinetics parameter and different crude oils provides basic data.
Specific embodiment
The invention will be further described below by embodiment, but be not the restriction to assay method of the present invention.
Embodiment one: certain crude oil is at temperature 363.15K, the mensuration of low temperature oxidizing reaction rate under the pressure 23.5MPa.
After the dead oil sample dehydration of 1, the scene being fetched is qualified, for subsequent use.
2, with air compressing to the sample device, constant temperature is at 343.15K, constant voltage is to more than 23.5MPa4 hour, and is stand-by.
3, the dead oil after the 291.23g dehydration is changed in the sample device as reaction vessel, constant temperature is to 363.15K, and constant voltage is to more than 23.5MPa4 hour; Adopting the double pump method that the pressurized air (343.15K, 23.5MPa) of 150.95mL is changed in this sample device mixes with crude oil.
The sample device constant temperature that 4, will change crude oil and air over to is at 363.15K, and constant voltage stirs and writing time at 23.5MPa.
5, accumulative total react 48,96,144,192, behind the 240h, take out respectively a small amount of gas cap gas, the gas cap gas volume that record is discharged utilizes gas chromatograph to analyze gas cap gas and forms, and discharges a small amount of crude oil and carries out the single degassing experiment, the quality of record gas-free oil and the volume of solution gas, adopt gas chromatograph to analyze the composition of solution gas, at first use before every sub-sampling more than the helium purge sampling system 5min, the remaining air of nothing in the assurance system, recording reacting time, atmospheric temperature and pressure.Data during each sub-sampling are as shown in table 1:
General data during each sub-sampling of table 1
6, data preparation: by above-mentioned data processing method, the average oxidizing reaction rate that obtains each stage is as shown in table 2:
The average oxidizing reaction rate in each stage of table 2 crude oil
Embodiment two: certain crude oil is at temperature 383.15K, the mensuration of low temperature oxidizing reaction rate under the pressure 23.5MPa.
After the dead oil sample dehydration of 1, the scene being fetched is qualified, for subsequent use.
2, with air compressing to the sample device, constant temperature is at 343.15K, constant voltage is to more than 23.5MPa4 hour, and is stand-by.
The dead oil sample that 3, will dewater qualified changes in the sample device as reaction vessel, and the crude quality that changes over to is 307.64g, and constant temperature is to 383.15K, and constant voltage is to more than 23.5MPa4 hour.Adopting the double pump method that the pressurized air (343.15K, 23.5MPa) of 162.17mL is changed in this sample device mixes with crude oil.
The sample device constant temperature that 4, will change crude oil and air over to is to 383.15K, and constant voltage stirs and writing time to 23.5MPa.
5, accumulative total react 24,48, behind the 72h, take out respectively a small amount of gas cap gas, the gas cap gas volume that record is discharged utilizes gas chromatograph to analyze gas cap gas and forms, and discharges a small amount of crude oil and carries out the single degassing experiment, the quality of record gas-free oil and the volume of solution gas, adopt gas chromatograph to analyze the composition of solution gas, at first use before every sub-sampling more than the helium purge sampling system 5min, the remaining air of nothing in the assurance system, recording reacting time, atmospheric temperature and pressure.Data during each sub-sampling are as shown in table 3:
General data table during each sub-sampling of table 3
6, data preparation: by above-mentioned data processing method, the average oxidizing reaction rate that obtains each stage is as shown in table 4:
The average oxidizing reaction rate in each stage of table 4 crude oil
Claims (4)
1. the assay method of light crude low-temperature oxidation reaction rate is characterized in that described assay method carries out in accordance with the following steps:
(1) the dead oil sample of the scene being fetched changes in the dehydrating apparatus and dewaters, and dewaters qualified rear for subsequent use;
(2) with air compressing to the sample device, constant temperature is to T
Air, constant voltage is to reservoir pressure P
fMore than 4 hours, stand-by;
The dead oil sample that (3) will dewater qualified changes in the sample device as reaction vessel, the crude quality W that record changes over to
Oil, constant temperature is to temperature of reaction, and constant voltage is to reservoir pressure P
fMore than 4 hours; The dead oil sample mix that adopts the double pump method that ready pressurized air is changed in this sample device and changed over to, the pressurized air volume V that record changes over to
Air
The sample device constant temperature and pressure that (4) will change crude oil and air over to is to temperature of reaction and pressure, stir and writing time t
0
(5) before the sampling, purge the air of sampling system noresidue to the system, record accumulative total reaction time t
mTaking out volume from the sample device is V
CmGas cap gas, utilize gas chromatograph to analyze gas cap gas and form; From the sample device, take out an amount of crude oil and carry out the single degassing experiment, the quality W of record gas-free oil
mVolume V with solution gas
Sm, adopt gas chromatograph to analyze the composition of solution gas; Atmospheric temperature T when recording every sub-sampling
mAnd pressure P
m
(6) repeating step 5 to reaction finishes;
(7) suppose that quality remains unchanged in the gas-free oil course of reaction, calculate the pneumatic jack tolerance of the variant stage of reaction, former oil mass and the oxygen expenditure amount of participation oxidation reaction according to law of conservation of mass, calculate based on this average response speed of differential responses stage crude oil low-temperature oxidation reaction.
2. the assay method of light crude low-temperature oxidation reaction rate according to claim 1 is characterized in that adopting helium that the air in the sampling system is purged displacement.
3. the assay method of light crude low-temperature oxidation reaction rate according to claim 1 and 2 is characterized in that in the data handling procedure, and the amount of solution gas is calculated as follows:
In the formula:
n
StmThe amount of total solution gas before the m sub-sampling, mol;
W
OilChange the dead oil quality in the reaction sample device over to, g;
n
SmThe amount of the solution gas that takes out during the m sub-sampling, mol;
W
mThe gas-free oil quality of discharging during the m sub-sampling, g.
4. the assay method of light crude low-temperature oxidation reaction rate according to claim 1 and 2 is characterized in that in the data handling procedure, and the amount of gas cap gas is calculated as follows:
In the formula:
n
CtmTotal pneumatic jack tolerance before the m sub-sampling, mol;
n
AirChange the amount of the air in the reaction sample device over to, mol;
n
CmThe amount of the gas cap gas that takes out during the m sub-sampling, mol;
Y
SmjThe molar content of j component in the m sub-sampling solution gas, %;
Y
CmjThe molar content of j component in the m sub-sampling gas cap gas, %.
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| CN105019889B (en) * | 2014-04-28 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of light oil reservoirs crude oil low-temperature oxidation rate prediction and safe precaution method |
| US11639921B2 (en) | 2021-07-15 | 2023-05-02 | Saudi Arabian Oil Company | Oil API determination of reservoir rocks by oxidation |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101413931A (en) * | 2008-11-25 | 2009-04-22 | 大庆油田有限责任公司 | Biomarker gas chromatograph-high resolved flight time mass spectrographic analysis method in crude oil or sediment |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101413931A (en) * | 2008-11-25 | 2009-04-22 | 大庆油田有限责任公司 | Biomarker gas chromatograph-high resolved flight time mass spectrographic analysis method in crude oil or sediment |
Non-Patent Citations (4)
| Title |
|---|
| OXIDATION KINETICS OF NORTH SEA LIGHT CRUDE OILS AT RESERVOIR TEMPERATURE;S.R.Ren etal;《chemical engineering research and design》;19990731;第77卷(第5期);385-394 * |
| S.R.Ren etal.OXIDATION KINETICS OF NORTH SEA LIGHT CRUDE OILS AT RESERVOIR TEMPERATURE.《chemical engineering research and design》.1999,第77卷(第5期),385-394. |
| 张莉 等.轻质原油低温氧化动力学模型.《油气地质与采收率》.2009,第16卷(第2期),55-57. |
| 轻质原油低温氧化动力学模型;张莉 等;《油气地质与采收率》;20090331;第16卷(第2期);55-57 * |
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