CN111458425A - VOC gas component analysis experimental device in oil tank of oil tanker and use method thereof - Google Patents
VOC gas component analysis experimental device in oil tank of oil tanker and use method thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000007789 gas Substances 0.000 claims abstract description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011521 glass Substances 0.000 claims abstract description 25
- 238000007789 sealing Methods 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- 238000012360 testing method Methods 0.000 claims description 12
- 238000002474 experimental method Methods 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 47
- 239000010779 crude oil Substances 0.000 abstract description 19
- 239000003209 petroleum derivative Substances 0.000 abstract description 4
- 230000002265 prevention Effects 0.000 abstract description 2
- 238000011160 research Methods 0.000 abstract description 2
- 230000008859 change Effects 0.000 description 4
- 238000005070 sampling Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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Abstract
The invention discloses a VOC gas component analysis experimental device in an oil tank of an oil tanker, which is characterized by comprising the following components: nitrogen cylinder, relief pressure valve, first glass pipe, temperature sensor, pressure sensor, first manual stop valve, chromatograph, computer, first manual stop valve, tee bend, the manual stop valve of second, vacuum pump, constant temperature water bath, buchner flask, second glass pipe, sealing plug, the manual stop valve of third and electromagnetism stop valve. The invention can simulate the VOC gas released by various petroleum products under different pressure and temperature working conditions when different crude oil transport ship types are underway, and carries out component analysis research through a chromatograph, thereby providing a data basis for subsequent treatment or pollution prevention.
Description
Technical Field
The invention relates to the technical field of volatile organic pollutant (VOC) component experiments, in particular to an experimental device for VOC gas components in an oil tank of an oil tanker and a using method thereof.
Background
The ship transportation of crude oil is the most important transportation mode of crude oil import in China, and the emission of volatile petroleum gas (VOC) with high concentration and large treatment capacity generated in the transportation and wharf shipment operation of crude oil not only causes huge economic loss, but also causes environmental pollution and brings potential safety hazards to production and life.
The pollution of VOC gas emission of crude oil transportation ships to the environment and the loss of crude oil quality become considerable problems to be solved, so that the identification of the components of the VOC gas in the oil tanks of the crude oil transportation ships is of great significance for the subsequent recovery and treatment of the gases.
The release rate and the total amount of the VOC gas in the transportation process of the crude oil transportation vessel depend on the temperature of the VOC gas in the crude oil and the upper space of the crude oil in the oil tank and the pressure set value or the control value in the oil tank, and are mainly caused by the change of the temperature of the oil tank. Meanwhile, the components of VOC gas released by different petroleum products are different under different pressures and temperatures.
However, at present, relatively few experimental studies are conducted on the VOC gas components in the cargo tanks of the oil ships, and the variation of the VOC gas components at different temperatures and pressures in the cargo tanks cannot be simulated through a set of experimental devices.
Disclosure of Invention
The invention aims to solve the problems and the defects in the prior art, and provides an experimental device for analyzing and identifying VOC gas components in an oil tank of an oil tanker and a using method thereof, so as to solve the problem that the VOC gas components at different temperatures and pressures in the oil tank cannot be analyzed and identified by one set of experimental device in the prior art.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the utility model provides an interior VOC gas composition analysis experimental apparatus of oil ship oil tank, includes: the device comprises a constant-temperature water bath kettle and a filter flask, wherein the filter flask is arranged in the constant-temperature water bath kettle, a sealing plug is plugged in a bottle opening, a first glass tube, a collecting end of a temperature sensor, a collecting end of a pressure sensor and a second glass tube are inserted into the sealing plug, one end of the first glass tube extends into the filter flask, and the other end of the first glass tube is sequentially communicated with a pressure reducing valve and a nitrogen bottle through a pipeline; the other end of the second glass tube is sequentially communicated with a first manual stop valve and a chromatograph through a pipeline;
one side of the bottle mouth of the filter flask is sequentially communicated with a second manual stop valve, an electromagnetic stop valve and a first connector of a three-way valve through pipelines;
a second interface of the three-way valve is communicated with a third manual stop valve through a pipeline to be connected to the atmosphere; a third interface of the tee joint is sequentially communicated with a fourth manual stop valve and a vacuum pump through a pipeline;
and the temperature sensor, the pressure sensor, the chromatograph and the electromagnetic stop valve are connected to a computer through leads.
More preferably, the sealing plug is a rubber sealing plug.
Further preferably, the pipeline is a silica gel hose and/or a tetrafluoroethylene hose.
Further preferably, water is injected into the constant-temperature water bath kettle.
Further preferably, the filter flask is filled with a test oil sample.
The invention relates to a use method of an experimental device for VOC gas components in an oil tank of an oil tanker, which is a use method when the oil sample is classified into a nitrogen-free protection state and a use method when the oil sample is in a nitrogen protection state according to the protection state of a test oil sample,
firstly, when an oil sample is tested to be in a nitrogen-free protection state, the using method comprises the specific steps of:
step 1: injecting a test oil sample into the filter flask, and placing the filter flask into a constant-temperature water bath kettle;
step 2: closing the pressure reducing valve, the first manual stop valve, the fourth manual stop valve and the electromagnetic stop valve, and opening the second manual stop valve and the third manual stop valve;
and step 3: setting a pressure linkage value of the electromagnetic stop valve in a computer according to an experimental working condition;
and 4, step 4: setting the constant temperature water temperature of the constant temperature water bath according to the experimental working condition, and starting the constant temperature water bath;
and 5: when the constant-temperature water bath kettle reaches the constant-temperature water temperature and lasts for the preset constant-temperature time, starting a first manual stop valve to measure the temperature, the pressure and the components of the VOC gas;
step 6: and (5) closing the first manual stop valve after the measurement is finished, and repeating the steps 3-5 according to other experimental working conditions until the experiment is finished.
Secondly, when the oil sample is tested to be in a nitrogen protection state, the using method comprises the following specific steps:
step 1): injecting a test oil sample into the filter flask, and placing the filter flask into a constant-temperature water bath kettle;
step 2): closing the pressure reducing valve, the first manual stop valve and the third manual stop valve, and opening the electromagnetic stop valve, the second manual stop valve and the fourth manual stop valve;
step 3): starting a vacuum pump, slowly opening a pressure reducing valve after the pump is continuously started for preset pump starting time, recovering the pressure in the filter flask to the normal pressure, and keeping the opening of the pressure reducing valve at the moment to keep the pressure in the filter flask to be at the normal pressure all the time;
step 4): after the preset pump stopping time is continued, the vacuum pump, the pressure reducing valve, the fourth manual stop valve, the electromagnetic stop valve and the third manual stop valve are closed;
step 5): setting a pressure linkage value of the electromagnetic stop valve in a computer according to an experimental working condition;
step 6): setting the constant temperature water temperature of the constant temperature water bath according to the experimental working condition, and starting the constant temperature water bath;
step 7): when the constant-temperature water bath kettle reaches the constant-temperature water temperature and lasts for the preset constant-temperature time, starting a first manual stop valve to measure the temperature, the pressure and the components of the VOC gas;
step 8): and (5) closing the first manual stop valve after the measurement is finished, and repeating the steps 5-7 according to other experimental working conditions until the experiment is finished.
Further preferably, the preset pump starting time is 2-3 minutes, and the preset pump stopping time is 4-6 minutes.
Further preferably, the preset constant temperature time is 10-15 minutes.
Compared with the prior art, the technical scheme of the invention has the advantages and beneficial effects that:
the experimental device for the VOC gas components in the oil tank of the oil tanker and the use method thereof can simulate the VOC gas released by various petroleum products under different pressure and temperature working conditions when different crude oil transport vessel types are sailed, and carry out component research through a chromatograph, thereby providing a data base for subsequent treatment or pollution prevention. The pressure setting values of the ventilation valves of the oil tanks of different ship types of the crude oil transport ship are different, and the nitrogen protection gas is added or not. Meanwhile, the device is simple in structure, convenient for operation of testing personnel and convenient to use.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus according to an embodiment of the present invention.
Detailed Description
The technical scheme of the experimental device for analyzing the VOC gas components in the oil tank of the oil tanker is further described in detail with reference to the attached drawing 1.
A VOC gas component analysis experimental device in an oil tank of an oil tanker comprises a nitrogen cylinder 1, a pressure reducing valve 2, a hose 3, a first glass tube 4, a temperature sensor 5, a pressure sensor 6, a temperature signal line 7, a pressure signal line 8, a first manual stop valve 9, a hose 10, a chromatograph 11, a chromatograph signal line 12, a computer 13, an electromagnetic stop valve signal line 14, a third manual stop valve 15, a tee joint 16, a fourth manual stop valve 17, a vacuum pump 18, a constant-temperature water bath 19, water 20, a test oil sample sealing plug 21, a filter flask 22, a second glass tube 23, a hose 24, a hose 25, a second manual stop valve 26 and an electromagnetic stop valve 27;
wherein, the nitrogen gas bottle 1 is connected with one end of a first glass tube 4 through a pressure reducing valve 2 and a hose 3; the other end of the first glass tube 4, the collecting end of the temperature sensor 5, the collecting end of the pressure sensor 6 and one end of the second glass tube 23 are fixed on a sealing plug 24 and extend into the interior of the suction filter bottle 22 through the sealing plug 24; the second glass tube 23 is connected with the chromatograph 11 through a first manual stop valve 9 and a hose 10; the temperature sensor 5 is connected with the calculator 13 through a temperature signal line 7, the pressure sensor is connected with the computer 13 through a pressure signal line 8, the chromatograph 11 is connected with the computer 13 through a chromatograph signal line 12, and the electromagnetic stop valve 27 is connected with the computer 13 through an electromagnetic stop valve signal line 14; the filter flask 22 is connected with the inlet of an electromagnetic stop valve 27 through a hose 25 and a second manual stop valve 26; the outlet of the electromagnetic stop valve 27 is connected with the end A of the tee joint 16 through a hose, the end B of the tee joint 16 is connected with the fourth manual stop valve 17 through a hose, and the fourth manual stop valve 17 is connected with a vacuum pump through a hose; meanwhile, the end C of the tee joint 16 is connected with the inlet of a third manual stop valve 15 through a hose, and the inlet of the third manual stop valve 15 is connected to the atmosphere through a hose; the appropriate amount of test oil sample 21 is contained in the filtered flask 22 and placed in a thermostatted water bath 19 to which is added an appropriate amount of water 20.
In this embodiment, the sealing plug 24 is a rubber sealing plug. Hoses such as the hose 3, the hose 10 and the hose 25 are all silica gel hoses or polytetrafluoroethylene hoses, and corresponding valves, tee joints and glass tube joints are of external thread structures or quick joints, so that the hoses can be quickly connected and air tightness can be guaranteed. Furthermore, the simulated pressure is controlled to vary from 10KPa to 16KPa by the computer 13, the electromagnetic stop valve 27 and other devices according to the actual working conditions of the oil tank, so that the failure of the sealing and the joint cannot be caused.
The nitrogen in the nitrogen cylinder 1 enters the filter flask 22 through the pressure reducing valve 2, the hose 3 and the first glass tube 4, and the pressure reducing valve 2 is used for adjusting the pressure and the dosage of the nitrogen entering the filter flask 22 and simulating the state of nitrogen protection gas in part of oil tanks of oil tankers.
The filter flask 22 simulates an oil tank of an oil tanker, a proper amount of crude oil, namely a test oil sample 21, is placed in the filter flask, and the closed space above the crude oil is the VOC gas to be tested in the experiment. The suction flask 22 is placed in a constant temperature water bath 19, and the water temperature in the constant temperature water bath 19 is uniform and can be accurately adjusted for simulating the change of the VOC gas components of the oil tank of the oil tanker at different temperatures.
The temperature sensor 5, the pressure sensor 6 and the second glass tube 23 are fixed to the sealing plug 24 and enter the inside of the filter flask 22 through the sealing plug 24. The temperature sensor 5 is used to measure the VOC gas temperature and the pressure sensor 6 is used to measure the VOC gas pressure. The second glass tube 23 is connected to the chromatograph 11 as a sampling tube via the first manual shut-off valve 9 and the hose 10, and is used for measuring the VOC gas components.
The side outlet of the filter flask 22 is connected with the electromagnetic cut-off valve 27, the tee joint 16 and the fourth manual cut-off valve 17 through the hose 25 and the second manual cut-off valve 26 and the vacuum pump 18. The initial air above the crude oil in the flask 22 was evacuated by the vacuum pump 18 and nitrogen was injected to simulate the tank conditions with nitrogen blanket.
The filter flask 22 also forms an exhaust passage with the electromagnetic shut-off valve 27, the tee 16 and the third manual shut-off valve 15 through the hose 25 and the second manual shut-off valve 26. The channel is used for simulating the operation of the tank ventilation valve when a ship sails and has the function of keeping the pressure of the tank within a reasonable range (10KPa-16 KPa). The computer 13 controls the opening and closing of the electromagnetic cut-off valve 27 by acquiring and comparing the real-time values of the pressure sensor 6. Further, when the gas pressure in the filter flask 22 is higher than the opening interlocking value (e.g., 16KPa), the electromagnetic cut-off valve 27 is automatically opened, and the VOC gas is discharged through the third manual cut-off valve 15 and the hose through the three-way valve 16. The electromagnetic shut-off valve 27 automatically closes when the gas pressure in the filter flask 22 is lower than the closing linkage value. The outlet of the hose at the rear part of the third manual stop valve 15 is arranged outdoors, so that the generation of indoor potential safety hazards is avoided.
The invention relates to a use method of an experimental device for analyzing VOC gas components in an oil tank of an oil tanker,
firstly, when the oil tank state with nitrogen protection gas needs to be simulated, the experimental steps are as follows:
1) pouring a proper amount of crude oil sample into the suction flask 22;
2) placing the suction flask 22 into the constant temperature water bath 19;
3) the sealing plug 24 is used for tightly plugging the opening of the upper part of the suction bottle 22; a hose 25 is used for connecting the side outlet of the filter flask 22 and a second manual stop valve 26; a first glass tube 4 is connected by a hose 3; the flexible pipe 10 is connected with a glass sampling pipe 23;
4) closing the pressure reducing valve 2, the first manual cut-off valve 9 and the third manual cut-off valve 15, and opening the second manual cut-off valve 26, the electromagnetic cut-off valve 27 and the fourth manual cut-off valve 17;
5) and starting the vacuum pump 18, slowly opening the pressure reducing valve 2 after 2-3 minutes to slowly restore the pressure in the filter flask 22 to the normal pressure, and keeping the opening of the pressure reducing valve 2 at the moment to ensure that the pressure in the filter flask 22 is always around the normal pressure.
6) After 5 minutes, the vacuum pump 18 is closed, and the pressure reducing valve 2 is closed;
7) closing the fourth manual cut-off valve 17, closing the electromagnetic cut-off valve 27, and opening the third manual cut-off valve 15;
8) according to the experimental working condition, setting the pressure linkage value of the electromagnetic stop valve 27 on the computer 13;
9) setting the water temperature of the constant-temperature water bath 19 according to the experimental working conditions, and starting the constant-temperature water bath 19;
10) after the constant-temperature water bath 19 reaches the set temperature and is kept for 15 minutes, the first manual stop valve 9 is opened to measure the temperature, the pressure and the components of the VOC gas;
11) and (5) closing the first manual stop valve 9, and repeating the steps 8, 9 and 10 to obtain the VOC gas component change rule of the crude oil sample under different temperatures and pressures.
Secondly, when the oil tank state with nitrogen protection gas does not need to be simulated, the experimental steps are as follows:
1) pouring a proper amount of crude oil sample into the suction flask 22;
2) placing the suction flask 22 into the constant temperature water bath 19;
3) the sealing plug 24 is used for tightly plugging the opening of the upper part of the suction bottle 22; a hose 25 is used for connecting the side outlet of the filter flask 22 and a second manual stop valve 26; a first glass tube 4 is connected by a hose 3; the flexible pipe 10 is connected with a glass sampling pipe 23;
4) the pressure reducing valve 2, the first manual cut-off valve 9, the electromagnetic cut-off valve 27 and the fourth manual cut-off valve 17 are closed,
5) opening the third manual stop valve 15 and the second manual stop valve 26;
6) according to the experimental working condition, setting the pressure linkage value of the electromagnetic stop valve 27 on the computer 13;
7) setting the water temperature of the constant-temperature water bath 19 according to the experimental working conditions, and starting the constant-temperature water bath 19;
8) after the constant-temperature water bath 19 reaches the set temperature and is kept for 15 minutes, the first manual stop valve 9 is opened to measure the temperature, the pressure and the components of the VOC gas;
9) and (5) closing the first manual stop valve 9, and repeating the steps 6, 7 and 8 to obtain the VOC gas component change rule of the crude oil sample under different temperatures and pressures.
The above embodiments are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modifications made on the basis of the technical scheme according to the technical idea of the present invention fall within the protection scope of the present invention.
Claims (8)
1. The utility model provides an interior VOC gas composition analysis experimental apparatus of oil ship oil tank, includes: the constant-temperature water bath kettle and the filter flask are characterized in that the filter flask is arranged in the constant-temperature water bath kettle, a sealing plug is plugged in a bottle mouth, a first glass tube with one end extending into the filter flask, a collecting end of a temperature sensor, a collecting end of a pressure sensor and a second glass tube are inserted in the sealing plug, and the other end of the first glass tube is sequentially communicated with a pressure reducing valve and a nitrogen bottle through a pipeline; the other end of the second glass tube is sequentially communicated with a first manual stop valve and a chromatograph through a pipeline;
one side of the bottle mouth of the filter flask is sequentially communicated with a second manual stop valve, an electromagnetic stop valve and a first connector of a three-way valve through pipelines;
a second interface of the three-way valve is communicated with a third manual stop valve through a pipeline to be connected to the atmosphere; a third interface of the three-way valve is sequentially communicated with a fourth manual stop valve and a vacuum pump through a pipeline;
and the temperature sensor, the pressure sensor, the chromatograph and the electromagnetic stop valve are connected to a computer through leads.
2. An experimental apparatus for analyzing the VOC gas components in the oil tank of an oil tanker according to claim 1, wherein said sealing plug is a rubber sealing plug.
3. The apparatus according to claim 1, wherein the pipe is a silicone hose or a tetrafluoroethylene hose.
4. An experimental apparatus for analyzing the VOC gas components in the cargo tank of a tanker according to claim 1, wherein said constant temperature water bath is filled with water.
5. An experimental apparatus for analyzing the VOC gas components in the cargo tank of a tanker according to claim 1, wherein said filter flask is filled with a test oil sample.
6. A use method of an experimental device for analyzing VOC gas components in an oil tank of an oil tanker is characterized in that the experimental device is divided into a use method in a nitrogen-free protection state and a use method in a nitrogen protection state according to a test oil sample protection state,
firstly, when an oil sample is tested to be in a nitrogen-free protection state, the using method comprises the specific steps of:
step 1: injecting a test oil sample into the filter flask, and placing the filter flask into a constant-temperature water bath kettle;
step 2: closing the pressure reducing valve, the first manual stop valve, the fourth manual stop valve and the electromagnetic stop valve, and opening the second manual stop valve and the third manual stop valve;
and step 3: setting a pressure linkage value of the electromagnetic stop valve in a computer according to an experimental working condition;
and 4, step 4: setting the constant temperature water temperature of the constant temperature water bath according to the experimental working condition, and starting the constant temperature water bath;
and 5: when the constant-temperature water bath kettle reaches the constant-temperature water temperature and lasts for the preset constant-temperature time, starting a first manual stop valve to measure the temperature, the pressure and the components of the VOC gas;
step 6: closing the first manual stop valve after the measurement is finished, and repeating the steps 3-5 according to other experimental working conditions until the experiment is finished;
secondly, when the oil sample is tested to be in a nitrogen protection state, the using method comprises the following specific steps:
step 1): injecting a test oil sample into the filter flask, and placing the filter flask into a constant-temperature water bath kettle;
step 2): closing the pressure reducing valve, the first manual stop valve and the third manual stop valve, and opening the electromagnetic stop valve, the second manual stop valve and the fourth manual stop valve;
step 3): starting a vacuum pump, slowly opening a pressure reducing valve after the pump is continuously started for preset pump starting time, recovering the pressure in the filter flask to the normal pressure, and keeping the opening of the pressure reducing valve at the moment to keep the pressure in the filter flask to be at the normal pressure all the time;
step 4): after the preset pump stopping time is continued, the vacuum pump, the pressure reducing valve, the fourth manual stop valve, the electromagnetic stop valve and the third manual stop valve are closed;
step 5): setting a pressure linkage value of the electromagnetic stop valve in a computer according to an experimental working condition;
step 6): setting the constant temperature water temperature of the constant temperature water bath according to the experimental working condition, and starting the constant temperature water bath;
step 7): when the constant-temperature water bath kettle reaches the constant-temperature water temperature and lasts for the preset constant-temperature time, starting a first manual stop valve to measure the temperature, the pressure and the components of the VOC gas;
step 8): and (5) closing the first manual stop valve after the measurement is finished, and repeating the steps 5-7 according to other experimental working conditions until the experiment is finished.
7. The use method of the experimental apparatus for analyzing the VOC gas in the oil tank of the oil tanker according to claim 6, wherein said preset pump-on time is 2-3 minutes, and said preset pump-off time is 4-6 minutes.
8. The use method of the experimental apparatus for analyzing the VOC gas in the oil tank of the oil tanker according to claim 6, wherein the preset constant temperature time is 10-15 minutes.
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CN114414722A (en) * | 2022-01-18 | 2022-04-29 | 天脊煤化工集团股份有限公司 | Method for measuring content of carbon dioxide in phosphorite |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN114414722A (en) * | 2022-01-18 | 2022-04-29 | 天脊煤化工集团股份有限公司 | Method for measuring content of carbon dioxide in phosphorite |
CN114414722B (en) * | 2022-01-18 | 2023-09-29 | 天脊煤化工集团股份有限公司 | Method for measuring carbon dioxide content in phosphorite |
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