CN113970588B - Device and method for measuring solubility of elemental sulfur in gas - Google Patents
Device and method for measuring solubility of elemental sulfur in gas Download PDFInfo
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- CN113970588B CN113970588B CN202010721560.1A CN202010721560A CN113970588B CN 113970588 B CN113970588 B CN 113970588B CN 202010721560 A CN202010721560 A CN 202010721560A CN 113970588 B CN113970588 B CN 113970588B
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 319
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000000926 separation method Methods 0.000 claims abstract description 95
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 89
- 239000011593 sulfur Substances 0.000 claims abstract description 89
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 54
- 238000012360 testing method Methods 0.000 claims abstract description 46
- 238000004458 analytical method Methods 0.000 claims abstract description 42
- 238000002360 preparation method Methods 0.000 claims abstract description 37
- 239000007789 gas Substances 0.000 claims description 293
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 98
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 97
- 239000003795 chemical substances by application Substances 0.000 claims description 92
- 239000007788 liquid Substances 0.000 claims description 43
- 238000005259 measurement Methods 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 23
- 230000005540 biological transmission Effects 0.000 claims description 16
- 238000004090 dissolution Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 238000003556 assay Methods 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 5
- 238000004448 titration Methods 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 3
- 238000000691 measurement method Methods 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 238000001819 mass spectrum Methods 0.000 description 8
- 239000003345 natural gas Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- MTCFGRXMJLQNBG-UHFFFAOYSA-N serine Chemical compound OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 2
- 230000019086 sulfide ion homeostasis Effects 0.000 description 2
- 241001522306 Serinus serinus Species 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- MFFMDFFZMYYVKS-SECBINFHSA-N sitagliptin Chemical compound C([C@H](CC(=O)N1CC=2N(C(=NN=2)C(F)(F)F)CC1)N)C1=CC(F)=C(F)C=C1F MFFMDFFZMYYVKS-SECBINFHSA-N 0.000 description 1
- 229960004034 sitagliptin Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 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
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
- G01N5/02—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by absorbing or adsorbing components of a material and determining change of weight of the adsorbent, e.g. determining moisture content
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Abstract
The application provides a device and a method for measuring the solubility of elemental sulfur of gas. The measuring device comprises a to-be-measured gas supply unit, a saturated gas configuration unit, a separation unit and an analysis metering unit which are connected in sequence; the saturated gas configuration unit comprises a plurality of sample preparation devices, wherein each sample preparation device comprises a high-temperature high-pressure sulfur-resistant reaction kettle, a pressure sensor and a metering pump so as to ensure that the pressure in each sample preparation device is constant at the preset pressure of each sample preparation device; and each sample preparation device is respectively connected with the gas supply unit to be tested and the separation unit. The measuring device comprises a plurality of sample preparing devices, and can simultaneously prepare a plurality of to-be-measured gas samples saturated with elemental sulfur under different pressures at the same temperature for testing and analysis, thereby being beneficial to improving the testing efficiency and saving the testing time.
Description
Technical Field
The invention relates to the technical field of petroleum and natural gas exploration and development, in particular to a device and a method for measuring the solubility of elemental sulfur of gas.
Background
The natural gas reserves of the high-sulfur gas reservoirs are rich, and are an important source of global natural gas. The high sulfur gas reservoirs in China are mainly distributed in the Erdos basin, the Tarim basin and the Sichuan basin. In the process of exploiting a high sulfur-containing gas reservoir, formation pressure is continuously reduced as gas is continuously produced, and elemental sulfur is separated from the gas. The separated elemental sulfur can block natural gas seepage channels, reduce the effective pore space and permeability of the stratum, and influence the productivity of a gas well. It is therefore necessary to obtain the solubility of elemental sulfur in natural gas to assist in determining whether the formation or wellbore contains sulfur deposits and the location of the sulfur deposits.
In the aspect of sulfur solubility test, students at home and abroad conduct a great deal of experimental study, so that the solubility of elemental sulfur in mixed gas with various known components is obtained, and main factors influencing the sulfur solubility are analyzed. As early as 1960, kennedy and Wielend et al tested the equilibrium dissolution problem of sulfur in different ratios of H 2S、CO2 and CH 4 gas mixtures and found that the solubility of sulfur was related to gas composition, pressure and temperature. In 1971, roof studied the solubility of sulfur in hydrogen sulfide gas through experiments. In 1976, swift established an empirical relationship that could predict the solubility of sulfur in hydrogen sulfide. In 1980, E.Brunner and W.Woll extended the Kennedy et al study to the 4-component case, investigating the solubility of sulfur in different ratios of H 2S、CO2、CH4 and N 2 gas mixtures at temperatures of 100-160℃and pressures of 10-60 MPa. In 1988, E.Brunner, M.C.Place Jr and W.Woll continued to investigate the solubility of sulfur in 7 groups of simulated acid gases at temperatures of 125-212℃and pressures of 6.7-155MPa, and made P-T phase diagrams of hydrogen sulfide and sulfur. In 1992-1993, P.M. Davis et al have further studied intensively on the basis of Brunner et al, and the dissolution of sulfur in simple multicomponent has been generalized to actual sour gas (up to 90% H 2 S content). The solubility of sulfur in acid gas mixtures of different contents of H 2 S at temperatures of 60, 90, 120, 150 and pressures of 5-55MPa was investigated. In 1993-1994, sitagliptin, rib et al measured the solubility data of solid sulfur in a mixture of pure gas (H 2S、CO2、CH4) and an H 2 S-rich acidic fluid. In 2003 Sun et al studied the solubility of elemental sulfur in gas mixtures of different concentrations of CH 4、H2 S and CO 2 at temperatures of 30-90℃and pressures of 20-45 MP. In 2010 Serin et al acquired the solubility of sulfur in supersaturated carbon dioxide.
The scholars at home and abroad also obtain the solubility of elemental sulfur in natural gas with unspecified components. In 2005, zeng Ping, zhao Jinzhou and the like have studied the solubility of elemental sulfur in natural gas through experimental simulation, and analyzed the main factors affecting the solubility. In 2009-2013, guo Xiao, liu Jianyi, zhangguangdong, li Li, etc. of southwest petroleum university have studied the solubility of triphosgene Tian Shanzhi sulfur in high sulfur-containing gas fields, respectively. Meanwhile, patent document 1 (CN 106124354 a) discloses a sulfur solubility on-line test device and method for a high sulfur-containing gas reservoir. Patent document 2 (CN 109323953 a) discloses a method for measuring the solubility of elemental sulfur in a sulfur-containing gas. Patent document 3 (CN 108474776 a) discloses a method and a system for measuring sulfur solubility in a gas. Patent document 4 (CN 210090232U) discloses an elemental sulfur solubility measuring device.
Some of the above documents disclose devices and methods that can be used to test, analyze the solubility of elemental sulfur in a gas. In the test, the solubility of the elemental sulfur in the gas at different pressures and temperatures is required to be obtained, so that a plurality of gas samples to be tested with saturated elemental sulfur at different pressures and temperatures are required to be configured. And, in the testing process, the time for configuring the sample of the gas to be tested saturated by elemental sulfur is longest.
However, the device only comprises one sample preparing device, and only one sample of the gas to be tested with saturated elemental sulfur can be configured for testing and analysis at a time, so that the testing time is long, and the speed of obtaining the solubility of the elemental sulfur in the gas under different pressures and temperatures is seriously influenced.
Disclosure of Invention
In order to solve the problems in the prior art, the application provides a device and a method for measuring the solubility of elemental sulfur of gas. The device comprises a plurality of sample preparing devices, and can simultaneously configure a plurality of gas samples to be tested, which are saturated by elemental sulfur under different pressures, at the same temperature for testing and analysis, thereby being beneficial to improving the testing efficiency and saving the testing time.
In a first aspect, the present invention provides an apparatus for determining elemental sulphur solubility of a gas, the apparatus comprising: a gas supply unit to be measured for supplying a gas to be measured; a saturated gas configuration unit which contains elemental sulfur and is used for configuring the gas to be detected into a gas sample to be detected saturated by the elemental sulfur; a separation unit which accommodates a sulfur dissolving agent to sufficiently dissolve elemental sulfur in the sample gas to be measured which enters the separation unit; the analysis metering unit is used for obtaining the total amount of elemental sulfur dissolved in the sulfur dissolving agent and the total volume of the gas sample to be detected entering the separation unit; the gas supply unit to be detected, the saturated gas configuration unit, the separation unit and the analysis and measurement unit are connected in sequence; the saturated gas configuration unit comprises a plurality of sample preparation devices, and different preset pressures are arranged in the sample preparation devices; and each sample dispenser is respectively connected with the gas supply unit to be tested and the separation unit. By using the measuring device, a plurality of sample preparing devices are arranged, so that a plurality of gas samples to be tested with saturated elemental sulfur under different pressures can be simultaneously configured at the same temperature for testing and analysis, the testing efficiency is improved, and the testing time is saved.
In one embodiment of the first aspect, the analytical and metering unit comprises a gas-liquid separation device, a condenser, a hydrogen sulfide absorption device and a gas meter connected in sequence. By the embodiment, gas-liquid separation can be realized, and the total volume V 1 of the sample to be detected, which does not contain elemental sulfur and is free of hydrogen sulfide gas, is metered.
In one embodiment of the first aspect, the analytical metering unit further comprises a weight measuring instrument for measuring the mass of the sulfur-dissolving agent separated by the gas-liquid separation device, and a mass spectrometer in communication with the gas-liquid separation device for measuring the content of elemental sulfur in the sulfur-dissolving agent. According to the embodiment, the mass ratio of the elemental sulfur to the sulfur-dissolving agent containing the elemental sulfur is measured by using the mass spectrometer, and compared with a balance weighing method, the total amount of the elemental sulfur is obtained, so that the influence of pipeline vibration, airflow movement and external environment on a balance measurement result is avoided, and the accuracy and the repeatability of the test are improved.
In one embodiment of the first aspect, the separation unit comprises a high pressure elemental sulfur dissolution reactor comprising: a reaction kettle box body; the end cover and the reaction kettle box body are enclosed to form a reaction cavity, the reaction cavity provides a space for the elemental sulfur in the gas sample to be tested entering the reaction cavity to be fully dissolved in the sulfur dissolving agent, a feed inlet is formed in the end cover, and the feed inlet is communicated with the reaction cavity; the piston assembly comprises a piston, a piston cylinder and a built-in transmission shaft of the stirrer, wherein the built-in transmission shaft of the stirrer is arranged in the piston and the piston cylinder; one end of the built-in transmission shaft of the stirrer, which is arranged in the reaction cavity, is provided with a stirring blade connecting port for connecting the stirrer, the other end of the built-in transmission shaft of the stirrer is a servo motor connecting end for connecting a servo motor, and a temperature sensor circuit is arranged in the built-in transmission shaft of the stirrer for connecting a temperature sensor. By the embodiment, the volume of the reaction cavity can be adjusted so as to adjust the air pressure of the air sample to be detected, and the kinetic energy required by stirring can be provided for the stirrer.
In one embodiment of the first aspect, the end cover comprises a cover portion and a side wall, an annular groove is formed in the joint of the cover portion and the side wall, the annular groove portion accommodates the open end of the reaction kettle box body, the outer wall of the open end is in threaded connection with the inner wall of the side wall, and an end cover sulfur-proof sealing device is arranged between the side wall of the cover portion and the inner wall of the open end. Through the embodiment, the double-layer sealing of the end cover and the reaction kettle box body is realized, the escape of gas is effectively avoided, the solubility of elemental sulfur is ensured to be accurately measured, and meanwhile, the escape of toxic and harmful hydrogen sulfide gas is effectively avoided, so that the safety performance of the measuring device is improved.
In one embodiment of the first aspect, a piston sulfur-proof sealing device is installed between the piston and the inner wall of the reaction kettle box body. Through the embodiment, the gas in the reaction cavity can not escape from the piston side, the solubility of elemental sulfur is accurately measured, and meanwhile, the escape of toxic and harmful hydrogen sulfide gas is effectively avoided, so that the safety performance of the measuring device is improved.
In one embodiment of the first aspect, the sample dispensers each comprise a high temperature, high pressure, sulfur resistant reaction vessel, a pressure sensor, and a metering pump. With this embodiment, it is advantageous to maintain the internal pressure of each of the sample dispensers at its preset pressure.
In one embodiment of the first aspect, the assay device further comprises a hydrogen sulfide leak warning system. With this embodiment, it is advantageous to avoid the occurrence of poisoning events and to improve the safety performance of the measurement device.
In one embodiment of the first aspect, the gas supply unit to be measured includes a gas cylinder and a gas booster pump to supply the pressurized elemental sulfur-free gas to be measured to the sample dispenser. According to the embodiment, the pressure of the gas to be detected entering the high-temperature high-pressure sulfur-resistant reaction kettle of the sample preparation device is similar to the preset pressure of the sample preparation device, and a basis is provided for subsequent pressure adjustment, so that the pressure of the gas sample to be detected is consistent with the preset pressure of the sample preparation device.
In one embodiment of the first aspect, the assay device further comprises a vacuum pump. With this embodiment, it is advantageous to improve the accuracy and reproducibility of the test results of the assay device.
In a second aspect, the present invention also provides a method for measuring the elemental sulfur solubility of a gas using the apparatus for measuring the elemental sulfur solubility of a gas in the first aspect and embodiments thereof, comprising the steps of: the gas supply unit to be measured supplies the gas to be measured to the saturated gas configuration unit; in the saturated gas configuration unit, the excessive elemental sulfur and the gas to be detected are fully stirred to form an elemental sulfur saturated gas sample to be detected; the gas sample to be detected enters the separation unit and is fully stirred so that elemental sulfur in the gas sample to be detected is fully dissolved in the sulfur dissolving agent; the analysis metering unit obtains the total amount of the elemental sulfur dissolved in the sulfur dissolving agent and the total volume of the gas sample to be detected entering the separation unit so as to obtain the elemental sulfur solubility of the gas to be detected; the sample preparing devices of the saturated gas configuring unit can simultaneously configure the gas sample to be tested, which is saturated by elemental sulfur under a plurality of different pressures, for testing and analysis. By using the measuring method, as the measuring device with a plurality of sample distributors is adopted, a plurality of gas samples to be measured which are saturated by elemental sulfur under different pressures can be simultaneously configured at the same temperature for testing and analysis, thereby being beneficial to improving the testing efficiency and saving the testing time.
In one embodiment of the second aspect, the internal temperature of each of the sample dispensers is the same. With this embodiment, each of the sample dispensers may share an oven to simplify the construction of the assay device.
In one embodiment of the second aspect, the analytical metering unit obtains the total amount of elemental sulfur dissolved in the sulfur dissolving agent, comprising the steps of: the separation unit guides all substances in the gas-liquid separation device of the analysis and metering unit; the weight measuring instrument measures the weight change m 1 of the gas-liquid separation device; the mass spectrometer acquires the sulfur dissolving agent in the gas-liquid separation device for analysis so as to acquire the mass ratio n of elemental sulfur to the sulfur dissolving agent containing the elemental sulfur; the total amount of elemental sulfur dissolved in the sulfur dissolving agent is equal to m 1 x n. According to the embodiment, the mass ratio of the elemental sulfur to the sulfur-dissolving agent containing the elemental sulfur is measured by using the mass spectrometer, so that the total amount of the elemental sulfur is obtained compared with a balance weighing method, the influence of pipeline vibration, airflow movement and external environment on a balance measurement result is avoided, and the accuracy and the repeatability of the test are improved.
In one embodiment of the second aspect, a mass spectrometer obtains a mass ratio n of elemental sulfur to the sulfur-dissolving agent comprising the elemental sulfur, comprising the steps of: preparing sulfur dissolving agent standard samples with different elemental sulfur contents; measuring mass spectrograms of all sulfur-dissolving agent standard samples by using the mass spectrometer, and obtaining the corresponding relation between the elemental sulfur content and the peak area of each sulfur-dissolving agent standard sample; and measuring a mass spectrogram of the sulfur-dissolving agent by using the mass spectrometer, acquiring a peak area, and calculating the mass ratio n of the elemental sulfur to the sulfur-dissolving agent containing the elemental sulfur according to an interpolation method by using the corresponding relation. According to the embodiment, the mass ratio of the elemental sulfur to the sulfur-dissolving agent containing the elemental sulfur is calculated according to an interpolation method by using a mass spectrogram, so that the accuracy and the repeatability of the test can be improved.
In one embodiment of the second aspect, the analytical metering unit obtains the total volume of the gas sample to be tested entering the separation unit, comprising the steps of: the separation unit guides all substances in the gas-liquid separation device of the analysis and metering unit, the gas-liquid separation device guides the gas sample to be detected with the elemental sulfur removed into the hydrogen sulfide absorption device through the condenser, the gas sample to be detected with the elemental sulfur removed and without the elemental sulfur then enters the gas meter, and the gas meter obtains the volume V 1 of the gas sample to be detected with the elemental sulfur removed and without the elemental sulfur removed; acquiring the ratio y Hydrogen sulfide of the volume of the hydrogen sulfide to the total volume of the gas to be detected; the total volume of the gas sample to be tested entering the separation unit is V 1/(1-y Hydrogen sulfide ). By this embodiment, the provision of the hydrogen sulfide absorbing device is advantageous in avoiding hydrogen sulfide generation during the measurement process and in improving the safety performance of the measurement device.
In one embodiment of the second aspect, obtaining the ratio y Hydrogen sulfide of the volume of hydrogen sulfide to the total volume of the gas to be measured includes: analyzing the gas to be measured from the gas cylinder using a gas chromatograph to obtain y Hydrogen sulfide ; or titrating the liquid in the hydrogen sulfide absorption device by adopting a titration method to obtain the total molar quantity of the hydrogen sulfide gas, and calculating y Hydrogen sulfide according to the total molar quantity of the hydrogen sulfide gas and the volume V 1 of the gas sample to be detected, which is free of elemental sulfur and contains no hydrogen sulfide. With this embodiment, accurate data of the ratio y Hydrogen sulfide is facilitated to be obtained, thereby facilitating subsequent calculation of the solubility.
In one embodiment of the second aspect, in the saturated gas configuration unit, the stirring time of elemental sulfur and the gas to be measured is greater than or equal to 8 hours. By the embodiment, the saturation of elemental sulfur in the gas sample to be detected can be ensured.
In one embodiment of the second aspect, in the separation unit, the stirring time of the gas sample to be tested and the sulfur dissolving agent is greater than or equal to 2 hours. Through the embodiment, the elemental sulfur in the gas sample to be detected can be ensured to be fully dissolved in the sulfur dissolving agent, so that the phenomenon that the elemental sulfur remains in the gas sample to be detected and the measurement result of the solubility is influenced is avoided.
Compared with the prior art, the device and the method for measuring the solubility of the elemental sulfur of the gas have the following beneficial effects.
1. According to the measuring device, through the arrangement of the plurality of sample preparing devices, a plurality of to-be-measured gas samples saturated with elemental sulfur under different pressures can be simultaneously configured at the same temperature for testing and analysis, so that the testing efficiency is improved, and the testing time is saved.
2. The mass ratio of the elemental sulfur to the sulfur-dissolving agent containing the elemental sulfur is measured by using the mass spectrometer, compared with the total amount of the elemental sulfur obtained by a balance weighing method, the method is beneficial to avoiding the influence of pipeline vibration, airflow movement and external environment on the balance measurement result, thereby being beneficial to improving the test precision and repeatability.
3. The measuring device can effectively avoid leakage of hydrogen sulfide, and is beneficial to improving the safety performance of the measuring device.
The above-described features may be combined in various suitable ways or replaced by equivalent features as long as the object of the present invention can be achieved.
Drawings
The invention will be described in more detail hereinafter on the basis of embodiments and with reference to the accompanying drawings, in which:
FIG. 1 is a schematic diagram showing the structure of an apparatus for measuring the solubility of elemental sulfur of a gas according to an embodiment of the present invention;
FIG. 2 shows a schematic structural diagram of a high-pressure elemental sulfur dissolution reactor, according to an embodiment of the invention;
FIG. 3 shows a mass spectrum of a sulfur-dissolving agent standard sample having a elemental sulfur content of 0.001%;
FIG. 4 shows a mass spectrum of a sulfur-dissolving agent standard sample having an elemental sulfur content of 0.003%;
FIG. 5 shows a mass spectrum of a sulfur-dissolving agent standard sample having a elemental sulfur content of 0.001%;
fig. 6 shows the measurement result of the elemental sulfur solubility of a gas according to an embodiment of the present invention.
List of reference numerals:
1-a gas cylinder; 2-valve; 3-a gas booster pump; 5-a high-temperature high-pressure sulfur-resistant reaction kettle; 6-a high-pressure elemental sulfur dissolution reaction kettle; 8-a vacuum pump; 9-hydrogen sulfide leakage alarm system; 12-an oven exhaust hole; 16-a pressure sensor; 19-mass spectrometer; a 20-condenser; 21-a gas meter; 22-hydrogen sulfide absorption means; 23-a gas-liquid separation device; 26-stirring device; 27-a metering pump; 31-a temperature sensor; 35-a general control computer; 601-a feed inlet; 602-end caps; 603-end cap sulfur-proof seal; 604-a reaction kettle box body; 605-a stirrer; 606-piston sulfur-proof seal; 607-piston cylinder; 608-a transmission shaft is arranged in the stirrer; 609—a temperature sensor circuit; 610-servo motor connection end; 611-a piston; 612—stirring vane connection port; 613-a reaction chamber; 614-open ends.
In the drawings, like parts are designated with like reference numerals. The figures are not to actual ratios.
Detailed Description
The invention will be further described with reference to the accompanying drawings.
As shown in fig. 1, the present embodiment provides a device for measuring the solubility of elemental sulfur in a gas, the device comprising: a gas supply unit to be measured for supplying a gas to be measured; a saturated gas configuration unit which contains elemental sulfur and is used for configuring the gas to be detected into a gas sample to be detected saturated by the elemental sulfur; a separation unit which accommodates a sulfur dissolving agent to sufficiently dissolve elemental sulfur in a gas sample to be measured which enters the separation unit; the analysis and metering unit is used for obtaining the total amount of elemental sulfur dissolved in the sulfur dissolving agent and the total volume of the gas sample to be detected entering the separation unit; the gas supply unit to be tested, the saturated gas configuration unit, the separation unit and the analysis and measurement unit are connected in sequence; the saturated gas configuration unit comprises a plurality of sample preparation devices, wherein different preset pressures are arranged in each sample preparation device, and each sample preparation device is respectively connected with the gas supply unit to be tested and the separation unit.
The measuring device aims to obtain the solubility of elemental sulfur of the gas to be measured.
The gas supply unit to be measured supplies the gas to be measured to the saturated gas configuration unit. And adding excessive sulfur simple substances into each sample preparation device of the saturated gas configuration unit, and continuously stirring the sulfur simple substances and the gas to be detected by a stirring device 26 in each sample preparation device so as to enable the simple substance sulfur and the gas to be detected to be sufficiently stirred to form a simple substance sulfur saturated gas sample to be detected under preset pressure.
Firstly, a sample preparation device is communicated with a separation unit, and at least part of the sample to be detected gas sample saturated by elemental sulfur in the sample preparation device enters the separation unit through a valve 2. And adding a sulfur dissolving agent into the separation unit, and fully stirring for a long time to dissolve all elemental sulfur in the gas sample to be tested in the sulfur dissolving agent. And then, introducing all substances entering the separation unit into an analysis and measurement unit, wherein the separation and measurement unit can acquire the total amount of the elemental sulfur entering the separation unit and the total volume of the gas sample to be measured so as to acquire the elemental sulfur solubility of the gas to be measured under the preset pressure of the sample preparation device.
And then cleaning and drying the separation unit and the analysis and measurement unit, then communicating the other sample preparation device with the separation unit, and repeating the steps to obtain the solubility of the elemental sulfur of the gas to be measured under the other pressure until the measurement of the solubility of the elemental sulfur of the gas sample to be measured under each pressure in all the sample preparation devices is completed.
The saturated gas configuration unit comprises a plurality of sample preparation devices, wherein different preset pressures are arranged in each sample preparation device, and each sample preparation device is respectively connected with the gas supply unit to be tested and the separation unit.
Alternatively, the metering pump 27 may be an electric turbine metering pump.
Optionally, the assay device may further comprise a general control computer 35 for enabling automatic control of the assay device.
The measuring device comprises a plurality of sample preparing devices, and can simultaneously configure a plurality of gas samples to be tested, which are saturated by elemental sulfur under different pressures, for testing and analysis, thereby being beneficial to improving the testing efficiency and saving the testing time.
As shown in fig. 1, the analytical and metering unit of the present embodiment optionally includes a gas-liquid separation device 23, a condenser 20, a hydrogen sulfide absorption device 22, and a gas meter 21, which are connected in this order.
All substances entering the separation unit are firstly introduced into the gas-liquid separation device 23 to separate a sulfur dissolving agent dissolved with elemental sulfur and a gas sample to be tested which does not contain elemental sulfur, wherein the sulfur dissolving agent dissolved with elemental sulfur is left in the gas-liquid separation device 23, and the gas sample to be tested which does not contain elemental sulfur enters the hydrogen sulfide absorption device 22 through the condenser 20.
The hydrogen sulfide absorbing device 22 can remove hydrogen sulfide gas in the sample gas without elemental sulfur, and introduce the residual gas into the gas meter 21 through a pipeline to measure the total volume V 1 of the sample gas without elemental sulfur from which the hydrogen sulfide gas is removed.
The gas-liquid separation device 23, the condenser 20, the hydrogen sulfide absorbing device 22 and the gas meter 21 can realize gas-liquid separation, and measure the total volume V 1 of the sample to be detected, which does not contain elemental sulfur and removes hydrogen sulfide gas.
As shown in fig. 1, optionally, the analysis and measurement unit of the present embodiment further includes a weight measuring instrument for measuring the mass of the sulfur dissolving agent dissolved with elemental sulfur separated by the gas-liquid separation device 23, and a mass spectrometer 19, the mass spectrometer 19 being in communication with the gas-liquid separation device 23 to measure the content of elemental sulfur in the sulfur dissolving agent.
Optionally, a weight measuring instrument is located below the gas-liquid separation device 23 for measuring the weight change of the gas-liquid separation device 23.
Before the valve 2 is opened to communicate the separation unit with the analysis and metering unit, the gas-liquid separation device 23 is clean, so that the net weight gain of the gas-liquid separation device 23 is the total mass m 1 of the sulfur-dissolving agent in which elemental sulfur is dissolved.
The mass spectrometer 19 can obtain the sulfur dissolving agent dissolved with the elemental sulfur from the gas-liquid separation device 23, and the mass ratio n of the elemental sulfur to the sulfur dissolving agent containing the elemental sulfur can be obtained through analysis. The total amount of elemental sulfur dissolved in the sulfur dissolving agent is m 1 ×n, which is also the total amount of elemental sulfur in the elemental sulfur-saturated gas sample to be tested that enters the separation unit.
And obtaining the ratio y Hydrogen sulfide of the volume of the hydrogen sulfide to the total volume of the gas to be measured, wherein the ratio is equal to the ratio of the volume of the hydrogen sulfide to the total volume of the gas sample to be measured because the components of the gas are not changed in the test. From V 1 and y Hydrogen sulfide , the total volume of the gas sample to be tested entering the separation unit can be calculated as V 1/(1-y Hydrogen sulfide ).
The total amount of the elemental sulfur in the elemental sulfur saturated to-be-detected gas sample entering the separation unit is m 1 multiplied by n, the total volume of the to-be-detected gas sample entering the separation unit is V 1/(1-y Hydrogen sulfide ), the content of the elemental sulfur in the elemental sulfur saturated to-be-detected gas sample is m 1×n×(1-y Hydrogen sulfide )/V1, and the elemental sulfur solubility of the to-be-detected gas under the preset pressure of the sample preparation device can be obtained by converting the elemental sulfur.
Because the mass ratio of the elemental sulfur to the sulfur-dissolving agent containing the elemental sulfur is measured by using the mass spectrometer 19, compared with the total amount of the elemental sulfur obtained by a balance weighing method, the method is beneficial to avoiding the influence of pipeline vibration, airflow movement and external environment on the balance measurement result, thereby being beneficial to improving the precision and the repeatability of the test.
As shown in fig. 2, alternatively, the separation unit of the present embodiment includes a high-pressure elemental sulfur dissolution reaction vessel 6, and the high-pressure elemental sulfur dissolution reaction vessel 6 includes: a reactor tank 604; the end cover 602, the end cover 602 and the reaction kettle box 604 are enclosed to form a reaction cavity 613, the reaction cavity 613 provides a space for the elemental sulfur in the gas sample to be tested entering the reaction cavity 613 to be fully dissolved in the sulfur dissolving agent, the end cover 602 is provided with a feed inlet 601, and the feed inlet 601 is communicated with the reaction cavity 613; a piston assembly comprising a piston 611, a piston cylinder 607, and a stirrer built-in transmission shaft 608 disposed within the piston 611, the piston cylinder 607; one end of the stirrer built-in transmission shaft 608 in the reaction chamber 613 is provided with a stirring blade connection port 612 to be connected with the stirrer 605, the other end of the stirrer built-in transmission shaft 608 is provided with a servo motor connection end 610 to be connected with a servo motor, and a temperature sensor circuit 609 is arranged in the stirrer built-in transmission shaft 608 to be connected with the temperature sensor 31.
Through the feed inlet 601, the sulfur-dissolving agent and the gas sample to be detected saturated by elemental sulfur enter a reaction cavity 613 in the high-pressure elemental sulfur dissolution reaction kettle 6. The piston assembly can adjust the volume of the reaction chamber 613 to adjust the air pressure of the gas sample to be measured. The temperature sensor 31 may measure the temperature of the reaction chamber 613 to ensure that the temperature of the reaction chamber 613 is equal to the temperature in the high temperature, high pressure sulfur resistant reaction tank 5 of the sample dispenser.
In order to sufficiently dissolve elemental sulfur in the gas sample to be measured in the sulfur dissolving agent, it is necessary to agitate it. One end of the stirrer built-in transmission shaft 608 in the reaction chamber 613 is provided with a stirring blade connection port 612 to be connected with the stirrer 605, and the other end is a servo motor connection port 610 to be connected with a servo motor. The servo motor provides the stirrer 605 with the kinetic energy required for stirring.
By providing the piston assembly, the volume of the reaction chamber 613 can be adjusted to adjust the pressure of the gas sample to be measured, and the stirrer 605 can be provided with kinetic energy required for stirring.
As shown in fig. 2, optionally, the end cover 602 of this embodiment includes a cover portion and a side wall, where an annular groove is formed at a connection portion between the cover portion and the side wall, the annular groove partially accommodates an open end 614 of the reaction kettle case 604, an outer wall of the open end 614 is screwed with an inner wall of the side wall, and an end cover sulfur-proof sealing device 603 is disposed between the side wall of the cover portion and the inner wall of the open end 614.
The outer wall of the open end 614 is in threaded connection with the inner wall of the side wall, and an end cover sulfur-proof sealing device 603 is arranged between the side wall of the cover part and the inner wall of the open end 614, so that double-layer sealing between the end cover 602 and the reaction kettle box 604 is realized, gas escape is effectively avoided, the solubility of elemental sulfur is ensured to be accurately measured, meanwhile, toxic and harmful hydrogen sulfide gas escape is effectively avoided, and the safety performance of the measuring device is improved.
As shown in fig. 2, optionally, a piston sulfur-proof sealing device 606 is installed between the piston 611 and the inner wall of the reaction kettle box 604 in the present embodiment.
The piston sulfur-proof sealing device 606 ensures that the gas in the reaction cavity 613 cannot escape from the side of the piston 611, ensures the accurate measurement of the solubility of elemental sulfur, and simultaneously effectively avoids the escape of toxic and harmful hydrogen sulfide gas, thereby improving the safety performance of the measuring device.
Alternatively, the piston sulfur seal 606 may be a piston sulfur seal.
As shown in fig. 1, optionally, the sample dispensers of the present embodiment each include a high-temperature and high-pressure sulfur-resistant reaction kettle 5, a pressure sensor 16, and a metering pump 27, which are advantageous for maintaining the internal pressure of each sample dispenser at its preset pressure.
As shown in fig. 1, the measurement apparatus of the present embodiment optionally further includes a hydrogen sulfide leakage alarm system 9.
The system detects the hydrogen sulfide gas in real time in the measuring process, and alarms after detecting the hydrogen sulfide gas, so that the occurrence of poisoning events is avoided, and the safety performance of the measuring device is improved.
As shown in fig. 1, alternatively, the gas supply unit to be measured of the present embodiment includes a gas cylinder 1 and a gas booster pump 3 to supply the pressurized elemental sulfur-free gas to be measured to the sample dispenser.
The gas cylinder 1 is used for storing the gas to be measured, and is beneficial to ensuring the stability of the components of the gas to be measured.
The gas booster pump 3 can boost the pressure of the gas to be tested, so that the pressure of the gas to be tested entering the high-temperature high-pressure sulfur-resistant reaction kettle 5 of the sample preparation device is similar to the preset pressure of the sample preparation device, and a basis is provided for subsequent regulation of the pressure, so that the pressure of the gas sample to be tested is consistent with the preset pressure of the sample preparation device.
As shown in fig. 1, the measuring apparatus of the present embodiment may further include a vacuum pump 8.
The vacuum pump 8 is used to ensure that the measuring device is maintained in a vacuum state at the beginning of the test, thereby facilitating improvement of accuracy and repeatability of the test results of the measuring device.
The present embodiment also provides a method for measuring the elemental sulfur solubility of a gas using the apparatus for measuring the elemental sulfur solubility of a gas, comprising the steps of: the gas supply unit to be measured supplies the gas to be measured to the saturated gas configuration unit; in the saturated gas configuration unit, the excessive elemental sulfur and the gas to be detected are fully stirred to form an elemental sulfur saturated gas sample to be detected; the gas sample to be detected enters a separation unit and is fully stirred so that elemental sulfur in the gas sample to be detected is fully dissolved in a sulfur dissolving agent; the analysis and metering unit obtains the total amount of the elemental sulfur dissolved in the sulfur dissolving agent and the total volume of the gas sample to be detected entering the separation unit so as to obtain the elemental sulfur solubility of the gas to be detected; the sample preparing devices of the saturated gas preparing unit can simultaneously prepare a plurality of gas samples to be tested, which are saturated by elemental sulfur under different pressures, for testing and analysis.
According to the measuring method, the measuring device with the plurality of sample preparing devices is adopted, so that a plurality of to-be-measured gas samples saturated with elemental sulfur under different pressures can be simultaneously configured for testing and analysis, the testing efficiency is improved, and the testing time is saved.
Alternatively, the internal temperatures of the respective sample dispensers of the present embodiment are the same. Thus, each of the sample dispensers can share an oven, thereby simplifying the construction of the assay device.
Alternatively, the internal temperatures of the respective sample dispensers of the present embodiment are different from each other. Each sample preparation device is provided with an independent oven, so that the measuring device can simultaneously obtain the gas samples to be tested, which are saturated by elemental sulfur at different temperatures and pressures, for testing and analysis, thereby being beneficial to improving the testing efficiency and saving the testing time.
Alternatively, the analysis and metering unit of the present embodiment acquires the total amount of elemental sulfur dissolved in the sulfur dissolving agent, including the steps of: the separation unit directs all the substances therein to a gas-liquid separation device 23 of the analytical metering unit; the weight measuring instrument measures the weight change m 1 of the gas-liquid separation device 23, namely the total mass of the sulfur-dissolving agent; the mass spectrometer 19 acquires a small amount of sulfur-dissolving agent in the gas-liquid separation device 23 for analysis to acquire the mass ratio n of elemental sulfur to sulfur-dissolving agent containing elemental sulfur; the total amount of elemental sulfur dissolved in the sulfur-dissolving agent is equal to m 1 x n.
With this embodiment, since the mass ratio of elemental sulfur to the sulfur-dissolving agent containing elemental sulfur is measured using the mass spectrometer 19, the total amount of elemental sulfur is obtained in comparison with the balance weighing method, which is advantageous in avoiding the influence of line vibration, air flow movement, external environment on the balance measurement result, thereby being advantageous in improving the accuracy and repeatability of the test.
Alternatively, the mass spectrometer 19 of the present embodiment acquires the mass ratio n of elemental sulfur to the sulfur dissolving agent containing elemental sulfur, including the steps of: preparing sulfur dissolving agent standard samples with different elemental sulfur contents; measuring mass spectrograms of all sulfur-dissolving agent standard samples by using a mass spectrometer 19, and obtaining the corresponding relation between the elemental sulfur content and the peak area of each sulfur-dissolving agent standard sample; mass spectrum of the sulfur-dissolving agent is measured by using a mass spectrometer 19, peak areas are obtained, and the mass ratio n of elemental sulfur to the sulfur-dissolving agent containing elemental sulfur is calculated by using a correspondence method according to interpolation.
According to the embodiment, the mass ratio of the elemental sulfur to the sulfur-dissolving agent containing the elemental sulfur is calculated according to an interpolation method by using a mass spectrogram, so that the accuracy and the repeatability of the test can be improved.
Optionally, the analysis and measurement unit of the present embodiment obtains the total volume of the gas sample to be measured entering the separation unit, and includes the following steps: the separation unit guides all substances in the gas-liquid separation device 23 of the analysis and metering unit, the gas-liquid separation device 23 guides a to-be-detected gas sample with elemental sulfur removed into the hydrogen sulfide absorption device 22 through the condenser 20, the to-be-detected gas sample with hydrogen sulfide removed and without elemental sulfur then enters the gas meter 21, and the gas meter 21 obtains the volume V 1 of the to-be-detected gas sample with hydrogen sulfide removed and without elemental sulfur; acquiring the ratio y Hydrogen sulfide of the volume of hydrogen sulfide to the total volume of the gas to be measured; the total volume of the gas sample to be tested entering the separation unit is V 1/(1-y Hydrogen sulfide ).
The provision of the hydrogen sulfide absorbing means 22 is advantageous in avoiding hydrogen sulfide generation during the measurement process and in improving the safety performance of the measurement apparatus.
Optionally, the ratio y Hydrogen sulfide of the volume of the obtained hydrogen sulfide to the total volume of the gas to be measured in this embodiment includes: analyzing the gas to be measured from the gas cylinder 1 using a gas chromatograph to obtain y Hydrogen sulfide ; or titrating the liquid in the hydrogen sulfide absorbing device 22 by adopting a titration method to obtain the total molar quantity of the hydrogen sulfide gas, and calculating y Hydrogen sulfide according to the total molar quantity of the hydrogen sulfide gas and the volume V 1 of the gas sample to be detected, which is used for removing the hydrogen sulfide and does not contain elemental sulfur.
Alternatively, when the ratio y Hydrogen sulfide is large, a gas chromatograph may be used to analyze the elemental sulfur-free gas to be measured from the gas cylinder 1 to obtain y Hydrogen sulfide ; when the ratio y Hydrogen sulfide is smaller, a titration method can be used to titrate the liquid in the hydrogen sulfide absorbing device 22 to obtain the total molar quantity of the hydrogen sulfide gas, and y Hydrogen sulfide is calculated according to the total molar quantity of the hydrogen sulfide gas and the volume V 1 of the to-be-detected gas sample which removes the hydrogen sulfide and does not contain elemental sulfur.
With this embodiment, accurate data of the ratio y Hydrogen sulfide is facilitated to be obtained, thereby facilitating subsequent calculation of the solubility.
Alternatively, in the saturated gas configuration unit in this embodiment, the stirring time of elemental sulfur and the gas to be measured is longer than or equal to 8 hours. By the embodiment, the saturation of elemental sulfur in the gas sample to be detected can be ensured.
Optionally, in the separation unit in this embodiment, the stirring time of the gas sample to be tested and the sulfur dissolving agent is greater than or equal to 2 hours. Through the embodiment, the elemental sulfur in the gas sample to be detected can be ensured to be fully dissolved in the sulfur dissolving agent, so that the phenomenon that the elemental sulfur remains in the gas sample to be detected and the measurement result of the solubility is influenced is avoided.
Embodiment one:
the method for measuring the solubility of the elemental sulfur of the gas to be measured comprises the following steps.
Step S100: and acquiring a small amount of gas to be tested from the gas cylinder 1, recovering temperature and pressure, and testing the components of the gas to be tested, including the content of hydrogen sulfide. The gas to be measured may be natural gas.
Step S200: sulfur dissolving agent standard samples with elemental sulfur content of 0.001%, 0.003% and 0.005% were prepared. Acquiring mass spectrograms of sulfur-dissolving agent standard samples with different contents by using a mass spectrometer 19; wherein, FIG. 3 is a mass spectrum of a sulfur-dissolving agent standard sample with an elemental sulfur content of 0.001%, FIG. 4 is a mass spectrum of a sulfur-dissolving agent standard sample with an elemental sulfur content of 0.003%, and FIG. 5 is a mass spectrum of a sulfur-dissolving agent standard sample with an elemental sulfur content of 0.005%. And obtaining the corresponding relation between the elemental sulfur content and the peak area of each sulfur-dissolving agent standard sample from the mass spectrogram. The elemental sulfur content in the sulfur-dissolving agent standard sample can be adjusted according to the requirement of subsequent interpolation.
Step S300: the measuring apparatus was checked for air tightness and pressure resistance.
Step S400: the excess elemental sulfur is respectively filled into each high-temperature high-pressure sulfur-resistant reaction kettle 5. And pressurizing the gas to be tested by adopting a gas booster pump 3 until the gas pressure reaches a preset pressure, and then introducing the pressurized gas to be tested into a high-temperature high-pressure sulfur-resistant reaction kettle 5. The number of the sample dispensers is set according to the measurement requirement. If it is desired to obtain the solubility of elemental sulfur at the same temperature and at three different pressures, three sample dispensers may be used. Similarly, if it is desired to obtain the solubility of elemental sulfur at the same temperature and four different pressures, four sample dispensers may be used. The valves 2 for sample introduction are closed, the pressure in each high-temperature high-pressure sulfur-resistant reaction kettle 5 is kept at the respective preset pressure, and the pressure is heated to the preset temperature by using an oven. The oven is provided with an oven vent 12. After the preset temperature is reached, stirring is carried out by using a stirring device 26 until a gas sample to be detected with saturated elemental sulfur is formed, and the stirring time is longer than or equal to 8 hours. Under the condition of using three sample preparing devices, the saturated gas configuration unit can simultaneously configure three to-be-detected gas samples saturated by elemental sulfur under different pressures.
Step S500: and selecting a sample to be detected with saturated elemental sulfur in a sample preparation device for measurement. And introducing the sulfur-dissolving agent and the gas sample to be detected, which is saturated by the elemental sulfur in the sample preparation device, into a high-pressure elemental sulfur dissolution reaction kettle 6. When the gas sample to be detected with saturated elemental sulfur is introduced into the high-pressure elemental sulfur dissolution reaction kettle 6, the air pressure in the high-temperature high-pressure sulfur-resistant reaction kettle 5 and the air pressure in the high-pressure elemental sulfur dissolution reaction kettle 6 in the selected sample preparation device are kept as consistent as possible. After the feeding is completed, the pressure in the high-pressure elemental sulfur dissolution reaction kettle 6 is reduced, and the stirring is performed by using a stirrer 605 until the elemental sulfur in the gas sample to be tested is fully dissolved in the sulfur dissolving agent, wherein the stirring time is longer than or equal to 2 hours.
Step S600: after the elemental sulfur is fully dissolved in the sulfur dissolving agent, the high-pressure elemental sulfur dissolution reaction kettle 6 is decompressed, and then the materials in the high-pressure elemental sulfur dissolution reaction kettle 6 are led into the gas-liquid separation device 23 of the analysis metering unit by using the pressure of 0.2 MPa.
Step S700: the sulfur-dissolving agent in which elemental sulfur is dissolved remains in the gas-liquid separation device 23, and the gas phase in the material enters the gas meter 21 through the condenser 20 and the hydrogen sulfide absorbing device 22. The mass spectrometer 19 acquires a mass spectrum of a small amount of sulfur-dissolving agent in which elemental sulfur is dissolved. And calculating the mass ratio n of the elemental sulfur and the sulfur dissolving agent containing the elemental sulfur according to an interpolation method by utilizing the corresponding relation between the elemental sulfur content and the peak area. The weight change m 1 of the gas-liquid separation device 23, i.e., the total mass of the sulfur-dissolving agent, was measured using a weight measuring instrument. The total amount of elemental sulfur dissolved in the sulfur-dissolving agent was then calculated, which is equal to m 1 ×n.
The gas meter 21 acquires the volume V 1 of the gas entering it. And obtaining the ratio y Hydrogen sulfide of the volume of the hydrogen sulfide to the total volume of the gas to be measured. The total volume of the gas sample to be tested entering the separation unit is then calculated, which is equal to V 1/(1-y Hydrogen sulfide ).
The method for obtaining the ratio y Hydrogen sulfide of the volume of the hydrogen sulfide to the total volume of the gas to be measured comprises the following steps: analyzing the gas to be measured which does not contain elemental sulfur from the gas cylinder 1 by using a gas chromatograph to obtain y Hydrogen sulfide ; and/or, titrating the liquid in the hydrogen sulfide absorbing device 22 by adopting a titration method to obtain the total molar quantity of the hydrogen sulfide gas, and calculating y Hydrogen sulfide according to the total molar quantity of the hydrogen sulfide gas and the volume V 1 of the gas sample to be detected, which is used for removing the hydrogen sulfide and does not contain elemental sulfur.
According to the result, the content of the elemental sulfur in the elemental sulfur saturated gas sample to be detected is m 1×n×(1-y Hydrogen sulfide )/V1, and the elemental sulfur solubility of the gas sample to be detected under the preset pressure of the sample preparation device can be obtained by converting the elemental sulfur.
The method is used for respectively measuring the same gas sample to be measured twice, the content of the detected elemental sulfur is respectively 0.091g/m 3 and 0.092g/m 3, and the repeatability of experimental results is good.
S800: and repeating S500-S700 until the solubility of the gas sample to be detected, saturated with elemental sulfur in each sample preparation device, under the preset pressure is obtained. Fig. 6 shows the measurement results.
In the description of the present invention, it should be understood that the terms "upper," "lower," "bottom," "top," "front," "rear," "inner," "outer," "left," "right," and the like indicate or are based on the orientation or positional relationship shown in the drawings, merely to facilitate description of the present invention and to simplify the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be configured and operated in a particular orientation, and thus should not be construed as limiting the present invention.
Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and scope of the present invention as defined by the appended claims. It should be understood that the different dependent claims and the features described herein may be combined in ways other than as described in the original claims. It is also to be understood that features described in connection with separate embodiments may be used in other described embodiments.
Claims (18)
1. A device for measuring the solubility of elemental sulfur in a gas, comprising:
a gas supply unit to be measured for supplying a gas to be measured;
a saturated gas configuration unit which contains elemental sulfur and is used for configuring the gas to be detected into a gas sample to be detected saturated by the elemental sulfur;
A separation unit which accommodates a sulfur dissolving agent to sufficiently dissolve elemental sulfur in the sample gas to be measured which enters the separation unit; and
The analysis metering unit is used for obtaining the total amount of elemental sulfur dissolved in the sulfur dissolving agent and the total volume of the gas sample to be detected entering the separation unit;
the gas supply unit to be detected, the saturated gas configuration unit, the separation unit and the analysis and measurement unit are connected in sequence;
The saturated gas configuration unit comprises a plurality of sample preparation devices, and different preset pressures are arranged in the sample preparation devices; the air inlet of each sample preparation device is connected with the gas supply unit to be tested, and the air outlet of each sample preparation device is connected with the separation unit.
2. The measurement device according to claim 1, wherein the analysis and measurement unit includes a gas-liquid separation device, a condenser, a hydrogen sulfide absorption device, and a gas meter, which are connected in this order.
3. The measurement device according to claim 2, wherein the analysis meter unit further comprises a weight measuring instrument for measuring the mass of the sulfur-dissolving agent separated by the gas-liquid separation device, and a mass spectrometer in communication with the gas-liquid separation device for measuring the content of elemental sulfur in the sulfur-dissolving agent.
4. The measurement device according to claim 1, wherein the separation unit comprises a high-pressure elemental sulfur dissolution reaction vessel including:
A reaction kettle box body;
the end cover and the reaction kettle box body are enclosed to form a reaction cavity, the reaction cavity provides a space for the elemental sulfur in the gas sample to be tested entering the reaction cavity to be fully dissolved in the sulfur dissolving agent, a feed inlet is formed in the end cover, and the feed inlet is communicated with the reaction cavity;
The piston assembly comprises a piston, a piston cylinder and a built-in transmission shaft of the stirrer, wherein the built-in transmission shaft of the stirrer is arranged in the piston and the piston cylinder; one end of the built-in transmission shaft of the stirrer, which is arranged in the reaction cavity, is provided with a stirring blade connecting port for connecting the stirrer, the other end of the built-in transmission shaft of the stirrer is a servo motor connecting end for connecting a servo motor, and a temperature sensor circuit is arranged in the built-in transmission shaft of the stirrer for connecting a temperature sensor.
5. The measuring device according to claim 4, wherein the end cap comprises a cap portion and a side wall, an annular groove is formed at a joint of the cap portion and the side wall, the annular groove portion accommodates an open end of the reaction kettle box, an outer wall of the open end is in threaded connection with an inner wall of the side wall, and an end cap sulfur-proof sealing device is arranged between the side wall of the cap portion and the inner wall of the open end.
6. The measurement device according to claim 4, wherein a piston sulfur-proof sealing device is installed between the piston and the inner wall of the reaction kettle box.
7. The assay device of claim 1, wherein the sample dispensers each comprise a high temperature, high pressure, sulfur resistant reaction vessel, a pressure sensor, and a metering pump.
8. The assay device of claim 1, further comprising a hydrogen sulfide leak warning system.
9. The measurement apparatus according to claim 1, wherein the measurement gas supply unit includes a gas cylinder and a gas booster pump to supply the pressurized measurement gas to the sample dispenser.
10. The assay device of claim 1, further comprising a vacuum pump.
11. A method for measuring the solubility of elemental sulfur in a gas using the measuring device according to any one of claims 1 to 10, comprising the steps of:
the gas supply unit to be measured supplies the gas to be measured to the saturated gas configuration unit;
in the saturated gas configuration unit, the excessive elemental sulfur and the gas to be detected are fully stirred to form an elemental sulfur saturated gas sample to be detected;
the gas sample to be detected enters the separation unit and is fully stirred so that elemental sulfur in the gas sample to be detected is fully dissolved in the sulfur dissolving agent; and
The analysis metering unit obtains the total amount of the elemental sulfur dissolved in the sulfur dissolving agent and the total volume of the gas sample to be detected entering the separation unit so as to obtain the elemental sulfur solubility of the gas to be detected;
the sample preparing devices of the saturated gas configuring unit can simultaneously configure the gas sample to be tested, which is saturated by elemental sulfur under a plurality of different pressures, for testing and analysis.
12. The method according to claim 11, wherein the internal temperature of each of the sample dispensers is the same.
13. The method according to claim 11, wherein the analysis meter unit obtains the total amount of elemental sulfur dissolved in the sulfur dissolving agent, comprising the steps of:
the separation unit guides all substances in the gas-liquid separation device of the analysis and metering unit; the weight measuring instrument measures the weight change m 1 of the gas-liquid separation device;
the mass spectrometer acquires the sulfur dissolving agent in the gas-liquid separation device for analysis so as to acquire the mass ratio n of elemental sulfur to the sulfur dissolving agent containing the elemental sulfur;
The total amount of elemental sulfur dissolved in the sulfur dissolving agent is equal to m 1 x n.
14. The method according to claim 13, wherein a mass spectrometer acquires a mass ratio n of elemental sulfur to the sulfur-dissolving agent containing the elemental sulfur, comprising the steps of:
preparing sulfur dissolving agent standard samples with different elemental sulfur contents;
measuring mass spectrograms of all sulfur-dissolving agent standard samples by using the mass spectrometer, and obtaining the corresponding relation between the elemental sulfur content and the peak area of each sulfur-dissolving agent standard sample;
And measuring a mass spectrogram of the sulfur-dissolving agent by using the mass spectrometer, acquiring a peak area, and calculating the mass ratio n of the elemental sulfur to the sulfur-dissolving agent containing the elemental sulfur according to an interpolation method by using the corresponding relation.
15. The method according to claim 11, wherein the analysis meter unit obtains the total volume of the gas sample to be measured entering the separation unit, comprising the steps of:
The separation unit guides all substances in the gas-liquid separation device of the analysis and metering unit, the gas-liquid separation device guides the gas sample to be detected with the elemental sulfur removed into the hydrogen sulfide absorption device through the condenser, the gas sample to be detected with the elemental sulfur removed and without the elemental sulfur then enters the gas meter, and the gas meter obtains the volume V 1 of the gas sample to be detected with the elemental sulfur removed and without the elemental sulfur removed;
Acquiring the ratio y Hydrogen sulfide of the volume of the hydrogen sulfide to the total volume of the gas to be detected;
The total volume of the gas sample to be tested entering the separation unit is V 1/(1-y Hydrogen sulfide ).
16. The method according to claim 15, wherein obtaining a ratio y Hydrogen sulfide of a volume of hydrogen sulfide to a total volume of the gas to be measured comprises:
Analyzing the gas to be measured from the gas cylinder using a gas chromatograph to obtain y Hydrogen sulfide ; or alternatively
And titrating the liquid in the hydrogen sulfide absorption device by adopting a titration method to obtain the total molar quantity of the hydrogen sulfide gas, and calculating y Hydrogen sulfide according to the total molar quantity of the hydrogen sulfide gas and the volume V 1 of the gas sample to be detected, which is free of elemental sulfur and contains no hydrogen sulfide.
17. The measurement method according to claim 11, wherein in the saturated gas configuration unit, a stirring time of elemental sulfur and the gas to be measured is longer than or equal to 8 hours.
18. The method according to claim 11, wherein the stirring time of the gas sample to be measured and the sulfur dissolving agent in the separation unit is 2 hours or longer.
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