CN110220928B - Spontaneous combustion active ferrous sulfide generation and oxidation experimental system and method - Google Patents
Spontaneous combustion active ferrous sulfide generation and oxidation experimental system and method Download PDFInfo
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- CN110220928B CN110220928B CN201910604182.6A CN201910604182A CN110220928B CN 110220928 B CN110220928 B CN 110220928B CN 201910604182 A CN201910604182 A CN 201910604182A CN 110220928 B CN110220928 B CN 110220928B
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- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 172
- 230000019086 sulfide ion homeostasis Effects 0.000 title claims abstract description 155
- 230000003647 oxidation Effects 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 22
- 230000002269 spontaneous effect Effects 0.000 title claims abstract description 21
- 238000011065 in-situ storage Methods 0.000 claims abstract description 130
- 238000011084 recovery Methods 0.000 claims abstract description 128
- 238000012544 monitoring process Methods 0.000 claims abstract description 71
- 238000002474 experimental method Methods 0.000 claims abstract description 40
- 239000007789 gas Substances 0.000 claims description 465
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 58
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 55
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 51
- 238000007789 sealing Methods 0.000 claims description 33
- 238000001514 detection method Methods 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 238000010521 absorption reaction Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000006096 absorbing agent Substances 0.000 claims description 15
- 238000009434 installation Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 238000009529 body temperature measurement Methods 0.000 claims description 8
- 238000010926 purge Methods 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 7
- 238000004458 analytical method Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- -1 initial temperature Substances 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 description 39
- 238000010586 diagram Methods 0.000 description 24
- 230000001590 oxidative effect Effects 0.000 description 12
- 230000006399 behavior Effects 0.000 description 11
- 230000007613 environmental effect Effects 0.000 description 10
- 238000011160 research Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000005755 formation reaction Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000001483 high-temperature X-ray diffraction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
- G01N23/20008—Constructional details of analysers, e.g. characterised by X-ray source, detector or optical system; Accessories therefor; Preparing specimens therefor
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)
Abstract
The invention provides a spontaneous combustion active ferrous sulfide generation and oxidation experiment system and method, wherein the system comprises the following components: the in-situ observation chamber for ferrous sulfide generation and oxidation reaction is arranged on an XRD diffractometer; the system comprises an air supply subsystem, an environment temperature control subsystem, a temperature and gas parameter monitoring subsystem and a tail gas recovery subsystem, wherein the air supply subsystem, the environment temperature control subsystem, the temperature and gas parameter monitoring subsystem and the tail gas recovery subsystem are all connected with a ferrous sulfide generation and oxidation reaction in-situ observation chamber, and the parameter setting and controlling subsystem is respectively and electrically connected with the air supply subsystem, the environment temperature control subsystem, the temperature and gas parameter monitoring subsystem and the tail gas recovery subsystem, and is used for controlling all the subsystems to complete ferrous sulfide generation and oxidation reaction and monitoring and recording relevant parameters of ferrous sulfide generation and oxidation reaction. The experimental system realizes ferrous sulfide generation under controllable conditions and ferrous sulfide oxidation experiments under different conditions such as atmosphere, initial temperature, gas flow and the like, and can better understand the real change of the internal structure of a sample in the process of ferrous sulfide generation and oxidation and master the deep mechanism.
Description
Technical Field
The invention relates to the field of experimental equipment for ferrous sulfide research, in particular to a spontaneous combustion active ferrous sulfide generation and oxidation experimental system and method.
Background
The oxidative self-heating of iron-sulfur compounds, particularly ferrous sulfide, is a major cause of spontaneous combustion fires in petrochemical plants and stacks of sulfur-containing ores. Although scholars at home and abroad have studied the spontaneous combustion and ignition characteristics of ferrous sulfide, most of them are studied on ferrous sulfide sold in the market or ferrous sulfide after being contacted with oxygen (partially oxidized), mainly focusing on the spontaneous combustion characteristics of ferrous sulfide oxidation, and researches on ferrous sulfide which is not contacted with oxygen are rarely carried out, and researches on crystal structure and phase composition change in the self-heating process of ferrous sulfide oxidation are also rarely reported. Therefore, the ferrous sulfide is synthesized, the oxidation behavior characteristic of the unoxidized ferrous sulfide is directly researched, and the change of the crystal structure and the phase composition in the self-heating oxidation process of the ferrous sulfide is determined to have more guiding significance for preventing and controlling spontaneous combustion accidents of the ferrous sulfide.
The in-situ technology can apply various external environments to the test sample, and form in-situ XRD by combining with XRD, so that the change process of a specific area under the specific environment can be continuously recorded, and the change of the phase components and the crystal structure of the sample can be dynamically monitored, so that the real change process of the internal structure of the sample can be better known, and the deep mechanism can be more directly mastered. Therefore, the in-situ XRD technology is of great significance in researching the oxidation self-heating process of ferrous sulfide. For the conventional XRD detection process, a conventional method for avoiding the sample from contacting air is to coat the detected sample with a liquid solvent or a transparent pasty substance so as to isolate the air. Or a purge with an inert gas such as nitrogen is used to isolate the air. But in situ studies cannot be performed and only specific samples can be tested. Still some scholars design a special device to match with XRD according to the needs to realize in-situ on-line observation of the sample. However, the existing in-situ XRD devices are mostly used in the research fields of battery electrode materials (CN 201310153824, CN201410624775, CN201510906239, CN201521020544, CN201520481704, CN201621022439, CN201710831413, CN201720090217, CN201721303911, CN201810140751 and CN 201821227275), and the processes related to ferrous sulfide generation and oxidation reaction are rarely available, and commercial high-temperature XRD sample platforms provided by certain instrument manufacturers, such as Bruker corporation, germany, can perform XRD detection of samples under vacuum, air or inert gas atmosphere and samples under different temperature conditions, but other needed gases cannot be introduced, and are high in price. The existing in-situ XRD device and ferrous sulfide oxidation self-heating behavior research device can not meet the needs of ferrous sulfide oxidation self-heating behavior research.
In view of this, how to provide an experimental apparatus for studying the formation and oxidation behavior of ferrous sulfide is a problem to be solved.
Disclosure of Invention
Based on the problems existing in the prior art, the invention aims to provide a spontaneous combustion active ferrous sulfide generation and oxidation experimental system and method, which can solve the problem that the existing in-situ XRD device and ferrous sulfide oxidation self-heating behavior research device can not meet the research on ferrous sulfide oxidation self-heating characteristics.
The invention aims at realizing the following technical scheme:
the embodiment of the invention provides an spontaneous combustion active ferrous sulfide generation and oxidation experimental system, which comprises the following components:
the in-situ observation chamber for ferrous sulfide generation and oxidation reaction is provided with an airtight space for observation reaction, and the in-situ observation chamber for ferrous sulfide generation through oxidation reaction is arranged on the XRD diffractometer;
the gas supply subsystem is connected with the ferrous sulfide generation and oxidation reaction in-situ observation chamber through a gas supply manifold;
the environment temperature control subsystem is provided with an air pipe heat tracing temperature controller and a sample platform temperature controller, the air pipe heat tracing temperature controller is arranged on an air supply manifold of the air supply subsystem, and the sample platform temperature controller is arranged on a sample platform of the ferrous sulfide generation and oxidation reaction in-situ observation chamber;
The temperature and gas parameter monitoring subsystem and the tail gas recovery subsystem are respectively connected with the ferrous sulfide generation and oxidation reaction in-situ observation chamber;
the parameter setting and controlling subsystem is respectively and electrically connected with the air supply subsystem, the environment temperature control subsystem, the temperature and gas parameter monitoring subsystem and the tail gas recovery subsystem, and can set parameters of all the subsystems and control the air supply subsystem, the environment temperature control subsystem, the temperature and gas parameter monitoring subsystem and the tail gas recovery subsystem to finish, monitor and record ferrous sulfide generation and oxidation reaction and parameters in the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1).
The embodiment of the invention also provides an experiment method for generating and oxidizing spontaneous combustion active ferrous sulfide, which adopts the experiment for researching ferrous sulfide generation and oxidizing behaviors and comprises the following steps:
step 1) placing a quantitative ferrous sulfide generation sample in an inert environment in an in-situ observation chamber for ferrous sulfide generation and oxidation reaction;
step 2) taking out the in-situ observation chamber for ferrous sulfide generation and oxidation reaction after sample loading from an inert environment, and then installing the in-situ observation chamber on the XRD diffractometer, wherein the in-situ observation chamber is connected with a gas supply manifold of the gas supply subsystem, a tail gas recovery manifold of the tail gas recovery subsystem, a temperature control manifold of the environment temperature control subsystem and a sample temperature detection sensor of the temperature and gas parameter monitoring subsystem;
Step 3) characterizing the initial state of a generated ferrous sulfide sample in the ferrous sulfide generation and oxidation reaction in-situ observation chamber through the XRD diffractometer, and manually opening an air inlet valve and an air outlet valve of the ferrous sulfide generation and oxidation reaction in-situ observation chamber after the characterization is finished;
step 4) setting parameters of in-situ observation indoor gas, initial temperature and reaction time of the ferrous sulfide generation and oxidation reaction through the parameter setting and control subsystem;
step 5) controlling the environment temperature control subsystem through the parameter setting and control subsystem, and controlling the initial temperature of the gas supplied by the ferrous sulfide generation and oxidation reaction in-situ observation chamber and the gas supply subsystem to be set values;
step 6) monitoring and recording each data of the gas components and the temperature in the reaction process through the temperature and gas parameter monitoring subsystem by the parameter setting and control subsystem; the parameter setting and controlling subsystem controls the gas supply subsystem to continuously introduce the set mixed gas for reaction into the ferrous sulfide generation and oxidation reaction in-situ observation chamber, and simultaneously controls the tail gas recovery subsystem to recover the reacted gas to the tail gas recovery subsystem;
After the experiment is finished, stopping storing the data of the gas components and the temperature in the reaction process through the parameter setting and controlling subsystem, closing the environment temperature controlling subsystem, then controlling the gas supplying subsystem to purge nitrogen in the ferrous sulfide generation and oxidation reaction in-situ observation chamber, and purging and recovering harmful gases remained in the gas supplying manifold of the gas supplying subsystem, the ferrous sulfide generation and oxidation reaction in-situ observation chamber and the tail gas recovery manifold of the tail gas recovery subsystem into the tail gas recovery subsystem;
step 8), closing all the electric valves through the parameter setting and control subsystem; and then manually closing an air inlet valve and an air outlet valve of the ferrous sulfide generation and oxidation reaction in-situ observation chamber, disconnecting the connection between the ferrous sulfide generation and oxidation reaction in-situ observation chamber and the air supply subsystem, the tail gas recovery subsystem and the temperature and gas parameter monitoring subsystem, then moving the ferrous sulfide generation and oxidation reaction in-situ observation chamber into an inert environment, preserving a reacted sample and carrying out subsequent analysis and test.
According to the technical scheme provided by the invention, the spontaneous combustion active ferrous sulfide generation and oxidation experimental system and method provided by the embodiment of the invention have the beneficial effects that:
The in-situ observation chamber for ferrous sulfide generation and oxidation reaction is arranged on an XRD diffractometer, and is respectively and organically connected with an air supply subsystem, a tail gas recovery subsystem, an environment temperature control subsystem and a temperature and gas parameter monitoring subsystem, and the air supply subsystem, the tail gas recovery subsystem, the environment temperature control subsystem and the temperature and gas parameter monitoring subsystem are all controlled by the parameter setting and control subsystem, so that ferrous sulfide generation under controllable conditions and ferrous sulfide oxidation experiments under different conditions such as atmosphere, initial temperature, gas flow and the like are realized, and dynamic detection of phase components and crystal structure changes in the ferrous sulfide generation and oxidation process is realized by combining the in-situ observation chamber with the XRD diffractometer. Therefore, the real change process of the internal structure of the sample in the process of ferrous sulfide generation and oxidation can be better known, and the deep mechanism can be more directly mastered.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of an experimental system for spontaneous combustion activated ferrous sulfide formation and oxidation provided by an embodiment of the invention;
FIG. 2 is a schematic view of an in situ observation chamber for ferrous sulfide formation and oxidation reactions provided in an embodiment of the present invention;
FIG. 3 is a cross-sectional view of an in situ observation chamber for ferrous sulfide formation and oxidation reactions provided by an embodiment of the present invention;
FIG. 4 is a schematic diagram of a first sample stage according to an embodiment of the present invention;
FIG. 5 is a schematic view of a second sample stage according to an embodiment of the present invention, wherein (1) is a front view of the second sample stage; (2) is a sectional view at A-A in fig. 1;
FIG. 6 is a schematic view of a hemispherical sealing cap according to an embodiment of the present invention, wherein (1) is a front view of the hemispherical sealing cap; (2) is a top view of the hemispherical seal cap of fig. 1;
FIG. 7 is a schematic view of an in situ observation chamber for generating and oxidizing ferrous sulfide provided by an embodiment of the present invention;
FIG. 8 is a schematic diagram of a mobile integrated box according to an embodiment of the present invention;
FIG. 9 is a schematic diagram of a first component structure of a mobile integrated box according to an embodiment of the present invention;
FIG. 10 is a schematic diagram of a second component structure of the mobile integrated box according to the embodiment of the present invention;
FIG. 11 is a schematic diagram of a first structure of a mobile integrated box according to an embodiment of the present invention;
Fig. 12 is a schematic diagram of a second structure of a mobile integrated box according to an embodiment of the present invention;
fig. 13 is a schematic diagram of a third structure of a mobile integrated box according to an embodiment of the present invention;
FIG. 14 is a schematic diagram of an air supply subsystem and an exhaust gas recovery subsystem according to an embodiment of the present invention;
FIG. 15 is a schematic diagram of an ambient temperature control subsystem according to an embodiment of the present invention;
FIG. 16 is a schematic diagram of a temperature and gas parameter monitoring subsystem according to an embodiment of the present invention;
FIG. 17 is a schematic diagram illustrating the distribution of components in a control device according to an embodiment of the present invention;
the components corresponding to the marks in the figures are: 1-ferrous sulfide generation and oxidation reaction in-situ observation chamber; 11-sample; 12-sample stage; 121-sample cell; 122-an air inlet; 1221-vertical holes; 1222-a horizontal hole; 123-air outlet holes; 1231-vertical hole; 1232-horizontal hole; 124-seal ring mounting groove; 125-nut bolt mounting holes; 126-a thermostat mounting slot; 127-a temperature control oil pipe mounting hole; 128-temperature measuring holes; 129-a thermostat cover mounting slot; 13-hemispherical containment cap; 131-a hemispherical cap; 132-wing plates; 133-bolt mounting holes; 14-sealing a rubber ring; 15-tightening a nut bolt; 151-bolts; 152-nut; 16-an air inlet pipe; 17-an air outlet pipe; 18-an intake valve; 19-an air outlet valve; 110-a temperature controller cover plate; 2-mobile integrated box; 21-a box body; 211-a gas supply zone; 2111-a high-purity nitrogen cylinder tank; 2112-oxygen cylinder tank; 2113—compressed air cylinder tank; 2114-a water vapor generator tank; 212-an exhaust gas absorption zone; 2121-an exhaust gas recovery subsystem tank; 2122-hydrogen sulfide cylinder tank; 213-control region; 2131—a temperature control system mounting slot; 22-cover plate; 23-casters; 24-an air supply subsystem; 241-high purity nitrogen cylinder; 242-oxygen cylinder; 243-compressed air cylinders; 244-hydrogen sulfide cylinders; 245-a water vapor generator; 246-gas supply manifold (manifold refers to a manifold consisting of a plurality of tubes); 2461-pipe; 2462-air supply electric valve; 25-an ambient temperature control subsystem; 251-an oil bath circulation box; 252-tracheal heat tracing temperature controller; 253—sample station temperature controller; 254-Wen Guanhui (manifold means composed of a plurality of tubes); 26-a temperature and gas parameter monitoring subsystem; 261-sample temperature detection sensor; 262-a gas supply parameter analyzer; 263-tail gas parameter analyzer; 264-hydrogen sulfide gas alarm; 265-gas flow monitor; 27-a tail gas recovery subsystem; 271-an off-gas absorber; 272-getter pump; 273-tail gas recovery manifold (manifold means composed of a plurality of pipes); 274-an electric valve for tail gas recovery; 28-a parameter setting and control subsystem; 281-touch display; 282-PLC controller; 283-PLC driver assembly; 284-solid state relay assembly; 285-mechanical relay assembly; 3-XRD diffractometer.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the embodiments of the present invention in conjunction with the specific contents of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention. What is not described in detail in the embodiments of the present invention belongs to the prior art known to those skilled in the art. In addition, unless otherwise indicated, in the present invention, terms of orientation such as "upper, lower, left, right" and the like are used generally to refer to the orientation shown in the drawings and the orientation in practical use, and "inner and outer" are used to refer to the inner and outer of the outline of the component.
As shown in fig. 1, the embodiment of the present invention provides an experiment system for generating and oxidizing spontaneous combustion active ferrous sulfide, which can monitor changes of phase components, crystal structure, temperature, pressure, gas components and solid components in the process of generating and oxidizing ferrous sulfide in a relatively airtight and controllable environment (ambient temperature, atmosphere condition, atmosphere pressure and gas flow rate), and comprises:
The in-situ observation chamber 1 for ferrous sulfide generation and oxidation reaction is provided with an airtight space for observation reaction, and the in-situ observation chamber 1 for ferrous sulfide generation is arranged on the XRD diffractometer 3;
a gas supply subsystem 24 connected to the ferrous sulfide production and oxidation reaction in situ viewing chamber 1 via a gas supply manifold 246;
an environmental temperature control subsystem 25, which is provided with an air pipe heat tracing temperature controller 252 and a sample stage temperature controller 253, wherein the air pipe heat tracing temperature controller 252 is arranged on an air supply manifold 246 of the air supply subsystem 24, and the sample stage temperature controller 253 is arranged on a sample stage 12 of the ferrous sulfide generation and oxidation reaction in-situ observation chamber 1;
the temperature and gas parameter monitoring subsystem 26 and the tail gas recycling subsystem 27 are respectively connected with the ferrous sulfide generation and oxidation reaction in-situ observation chamber 1;
the parameter setting and controlling subsystem 28 is electrically connected with the air supply subsystem 24, the environment temperature control subsystem 25, the temperature and gas parameter monitoring subsystem 26 and the tail gas recycling subsystem 27 respectively, and can set parameters of each subsystem and control the air supply subsystem 24, the environment temperature control subsystem 25, the temperature and gas parameter monitoring subsystem 26 and the tail gas recycling subsystem 27 to finish, monitor and record the ferrous sulfide generation and oxidation reaction and parameters in the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1).
Referring to fig. 1, the experimental system further includes: the gas supply subsystem 24, the ambient temperature control subsystem 25, the temperature and gas parameter monitoring subsystem 26, the exhaust gas recovery subsystem 27 and the parameter setting and controlling subsystem 28 are all arranged in the mobile integrated box 2.
As shown in fig. 8 to 10, in the above-described experiment system, the mobile ic box 2 includes: a case 21 and a cover 22; four casters 23 are arranged at the bottom of the box body 21; as shown in fig. 11 to 13, the interior of the box 21 is divided into a gas supply area 211, a tail gas absorption area 212 and a control area 213, the gas supply subsystem 24 is disposed in the gas supply area 211, the tail gas recovery subsystem 27 is disposed in the tail gas absorption area 212, and the environmental temperature control subsystem 25, the temperature and gas parameter monitoring subsystem 26 and the parameter setting and controlling subsystem 28 are disposed in the control area 213 respectively;
the hydrogen sulfide cylinder 244 of the gas supply subsystem 24 is disposed within the exhaust gas absorption zone 212 and isolated from the oxygen cylinder 242 of the gas supply subsystem 24 within the gas supply zone 211. Further, the hydrogen sulfide gas alarm 264 of the temperature and gas parameter monitoring subsystem 26 is correspondingly disposed in the installation area (i.e. the tail gas absorption area 212) of the hydrogen sulfide gas cylinder 244 of the gas supply subsystem 24, and can alarm after the gas leakage of the hydrogen sulfide gas cylinder 244. The hydrogen sulfide gas alarm 264 is electrically connected with the parameter setting and controlling subsystem 28, and can send an alarm signal to the parameter setting and controlling subsystem 28, and the parameter setting and controlling subsystem 28 controls the tail gas recovering subsystem 27 to absorb the leaked hydrogen sulfide gas in the tail gas absorbing region 212, so that the safety of the experiment system is ensured to the greatest extent in the state that the hydrogen sulfide gas bottle 244 leaks.
Specifically, a gas supply subsystem, an ambient temperature control subsystem, a temperature and gas parameter monitoring subsystem, a tail gas recovery subsystem and a parameter setting and controlling subsystem are arranged in the box body of the movable integrated box; four casters capable of rolling are arranged at the bottom of the box body, and each caster is correspondingly arranged at four corners of the box body; the box body comprises three areas: the device comprises a gas supply area, a tail gas absorption area and a control area; wherein the gas supply area is provided with a high-purity nitrogen cylinder groove, an oxygen cylinder groove, an air cylinder groove and a water vapor generator groove which are respectively used for installing the high-purity nitrogen cylinder, the oxygen cylinder, the air cylinder and the water vapor generator; the tail gas absorption zone is provided with a tail gas recovery subsystem groove, a hydrogen sulfide gas cylinder groove and a hydrogen sulfide gas alarm; the tail gas recovery subsystem groove is provided with one tail gas recovery subsystem; the hydrogen sulfide cylinder groove is provided with one hydrogen sulfide cylinder. The hydrogen sulfide gas in the hydrogen sulfide gas cylinder is inflammable and explosive toxic gas which cannot be put together with the combustion improver oxygen, so that the hydrogen sulfide gas is placed in the tail gas absorption zone to be isolated from the oxygen, and if the hydrogen sulfide gas leaks, the tail gas recovery subsystem in the tail gas absorption zone can directly absorb the leaked hydrogen sulfide gas; the control area is provided with an environment temperature control subsystem, a temperature and gas parameter monitoring subsystem, an air outlet pipe of the air supply manifold and a heat tracing temperature controller of the air outlet pipe; the parameter setting and control subsystem is arranged on a cover plate of the movable integrated box.
As shown in fig. 2 and 3, in the above experimental system, the in-situ observation chamber 1 for ferrous sulfide formation and oxidation reaction comprises: the sample table 12, the upper surface of the sample table 12 is buckled and provided with a hemispherical sealing cover 13 through a sealing rubber ring 14 and a fastening nut bolt 15 to form a closed space for observing reaction;
the hemispherical sealing cover 13 is respectively connected with an air inlet pipeline provided with an air inlet valve 18 and an air outlet pipeline provided with an air outlet valve 19;
the sample stage 12 and the hemispherical seal cap 13 thereon are integrally mounted on the XRD diffractometer 3.
As shown in fig. 4, 5 and 6, preferably, the upper end of the sample stage 12 has a sample groove for holding a sample to be characterized, the sample groove is a circular shallow groove located at the central part of the sample stage, a groove is located at the outer side of the sample stage for installing the sealing rubber ring, the sample stage and the hemispherical sealing cover are provided with four nut bolt installing holes circumferentially spaced apart, the bolts of the sample stage are hexagon socket head bolts, each group of bolt holes is respectively provided with one fastening nut bolt, and the left side and the right side of the sample stage are symmetrically provided with an air inlet and an air outlet; an air inlet valve and an air outlet valve are respectively arranged on the air inlet and the air outlet; the bottom end of the sample stage is provided with a temperature controller mounting groove for mounting a temperature controller of the sample stage. The right side of the front of the sample stage is also provided with a hole for installing the temperature control oil pipe of the temperature controller of the sample stage. The front center part of the sample table is provided with a temperature measuring hole for installing a sample temperature detection sensor, the temperature measuring hole is positioned between the sample groove of the sample table and the installation groove of the temperature controller, and the distance between the bottom of the sample groove and the top of the installation groove of the temperature controller is about 1mm, so that the accuracy of temperature measurement is ensured. The sealing cover is a hemispherical transparent cover plate, and the spherical center of the sealing cover is concentric with the movement track of the XRD diffractometer after the sealing cover is installed, so that the X-ray generated by the XRD diffractometer is ensured to be injected and the characteristic X-ray generated after the X-ray irradiates the sample to be characterized is ensured to be emitted.
In the experimental system, the XRD diffractometer is a common commercial XRD diffractometer, and can realize the emission of X-rays and the receiving record of the diffracted characteristic rays.
As shown in fig. 9 and 14, in the above experimental system, the air supply subsystem 24 includes: a high purity nitrogen cylinder 241, an oxygen cylinder 242, an air cylinder 243, a hydrogen sulfide cylinder 244, a water vapor generator 245, and the air supply manifold 246; the high-purity nitrogen cylinder 241, the oxygen cylinder 242, the air cylinder 243, the hydrogen sulfide cylinder 244 and the water vapor generator 245 are all connected with the in-situ observation chamber 1 for ferrous sulfide generation and oxidation reaction through the air supply manifold 246, and can mix the gases of the air sources and then supply the mixed gases into the in-situ observation chamber 1 for ferrous sulfide generation and oxidation reaction.
Specifically, the high-purity nitrogen cylinder, the oxygen cylinder, the air cylinder, the hydrogen sulfide cylinder and the water vapor generator in the upper air supply subsystem are connected through an air supply manifold. The gas flow monitors are controlled by the parameter setting and controlling subsystem, and the required gas with different component parameters can be provided through the monitoring and the adjusting control of the gas flow monitors. The gas supply manifold is connected with a gas inlet of the ferrous sulfide generation and oxidation reaction in-situ observation chamber, and is used for uniformly mixing and then conveying nitrogen, oxygen, air, hydrogen sulfide gas and steam provided by the high-purity nitrogen gas cylinder, the oxygen gas cylinder, the air cylinder, the hydrogen sulfide gas cylinder and the steam generator to the ferrous sulfide generation and oxidation reaction in-situ observation chamber. By arranging the air supply subsystem, parameters such as flow, temperature, humidity and the like of the input air can be controlled, and the behavior mechanism of ferrous sulfide generation and oxidation can be studied more strictly; the tail gas recovery subsystem can be used for specially detecting toxic and harmful gases possibly generated in the experiment process, so that the experiment process is safe and reliable.
As shown in fig. 15, in the above experimental system, the environmental temperature control subsystem 25 includes: an oil bath circulation tank 251, a control Wen Guanhui 254, the sample stage temperature controller 253 and the air pipe heat tracing temperature controller 252; wherein, the oil bath circulation box 251 is respectively connected with the air pipe heat tracing temperature controller 252 and the sample platform temperature controller 253 through the control Wen Guanhui 254; the gas pipe heat tracing temperature controller 252 can control the temperature of the gas in the gas supply manifold 246; the sample stage temperature controller 253 is installed at the bottom of the sample stage 12 of the ferrous sulfide generation and oxidation reaction in-situ observation chamber 1, and can control the temperature of the sample stage 12.
Specifically, the oil bath circulation box of the environment temperature control subsystem circularly conveys temperature-controlled oil with set temperature into the air pipe heat tracing temperature controller and the sample table temperature controller through the temperature control manifold, and controls the initial temperature of the sample table and the temperature of gas in the gas supply pipeline to be within a set range through oil bath circulation for a certain time, so that the control of the environment temperature of the ferrous sulfide generation and oxidation reaction in-situ observation chamber is realized.
As shown in fig. 9, 14 and 16, in the above experimental system, the temperature and gas parameter monitoring subsystem 26 includes: a sample temperature detection sensor 261, a supply gas parameter analyzer 262, an exhaust gas parameter analyzer 263, and a set of gas flow monitors 265; wherein,
The sample temperature detection sensor 261 is arranged in a temperature measurement hole 128 below the sample stage 12 of the ferrous sulfide generation and oxidation reaction in-situ observation chamber 1, and the temperature measurement sensitive end of the temperature measurement hole 128 is 1-2 mm away from the bottom of the sample groove 121 of the sample stage 12;
the gas supply parameter analyzer 262 is installed on the gas supply manifold 246 of the gas supply subsystem 24 and is positioned in front of the gas inlet valve 18 of the ferrous sulfide production and oxidation reaction in-situ observation chamber 1, and can analyze the temperature, pressure, flow and component parameters of the gas introduced into the ferrous sulfide production and oxidation reaction in-situ observation chamber 1;
the tail gas parameter analyzer 263 is installed on a tail gas recovery manifold 273 of the in-situ observation chamber 1 for ferrous sulfide production and oxidation reaction, which is connected to the tail gas recovery subsystem 27, and is located behind the gas outlet valve 19 of the in-situ observation chamber 1 for ferrous sulfide production and oxidation reaction, and is capable of analyzing the parameters of temperature, pressure, flow and composition of the gas discharged from the in-situ observation chamber 1 for ferrous sulfide production and oxidation reaction; the monitoring of the gas phase component change in the process of ferrous sulfide generation and oxidation can be realized by comparing and analyzing the difference of the detection data of the gas supply gas parameter analyzer 262 and the tail gas parameter analyzer 263;
The group of gas flow monitors 265 are respectively installed on the gas supply manifold 246 of the gas supply subsystem 24 and the tail gas recovery subsystem 27 connected to the tail gas recovery manifold 273 of the in-situ monitoring chamber 1 for ferrous sulfide production and oxidation reaction, and can respectively monitor the gas flow in the gas supply manifold 246 and the gas flow in the tail gas recovery manifold 273.
In the above experimental system, the temperature and gas parameter monitoring subsystem 26 further includes:
the hydrogen sulfide gas alarm 264 is correspondingly arranged at the installation area of the hydrogen sulfide gas cylinder 244 of the gas supply subsystem 24, and can alarm after the gas of the hydrogen sulfide gas cylinder 244 leaks. Further, the hydrogen sulfide gas alarm 264 is electrically connected with the parameter setting and controlling subsystem 28, and can send an alarm signal to the parameter setting and controlling subsystem 28, and the parameter setting and controlling subsystem 28 controls the tail gas recovering subsystem 27 to absorb the leaked hydrogen sulfide gas, so that the safety of the experiment system is ensured to the greatest extent in the state that the hydrogen sulfide gas bottle 244 leaks.
Specifically, the sample temperature detection sensor of the temperature and gas parameter monitoring subsystem is arranged in a temperature measuring hole of the sample table and used for monitoring the temperature change of the sample; the hydrogen sulfide gas alarm is arranged on the side wall of the tail gas recovery zone of the box body and is used for monitoring the concentration of the hydrogen sulfide gas in the tail gas recovery zone, alarming is started when the concentration of the hydrogen sulfide gas in the tail gas recovery zone exceeds a set value, and then the tail gas recovery subsystem is triggered to work so as to absorb harmful gas in the tail gas recovery zone; the gas supply parameter analyzer is arranged on the gas supply manifold and is positioned behind the gas pipe heat tracing temperature controller and in front of the gas inlet valve, and monitors parameters such as components, flow and temperature of gas entering the in-situ observation chamber for ferrous sulfide generation and oxidation reaction. The tail gas parameter analyzer is arranged on the tail gas recovery manifold and is positioned behind the gas outlet valve, and monitors parameters such as components, flow and temperature of the gas exhausted from the in-situ observation chamber for ferrous sulfide generation and oxidation reaction.
As shown in fig. 9 and 14, in the above experimental system, the exhaust gas recovery subsystem 27 includes: a tail gas absorber 271, a suction pump 272, a tail gas recovery manifold 273, and two tail gas recovery motor valves 274; the suction pump 272 is installed on the exhaust gas absorber 271, the suction pump 272 is connected with the in-situ observation chamber 1 for ferrous sulfide generation and oxidation reaction through the exhaust gas recovery manifold 273, and two exhaust gas recovery electric valves 274 are installed on the exhaust gas recovery manifold 273.
Specifically, the tail gas absorber of the tail gas recovery subsystem is arranged in the groove of the tail gas recovery subsystem, and the tail gas absorber is provided with a suction port and an exhaust port; the suction pump is arranged on the suction port of the tail gas absorber; the exhaust port of the exhaust absorber discharges the treated harmless exhaust into the atmosphere. And the suction pump is provided with a tail gas recovery manifold. The suction pump can suck the gas in the tail gas recovery manifold into the tail gas absorber for absorption treatment. The tail gas absorber is internally provided with a sufficient amount of alkaline liquid which can fully absorb the gas in the hydrogen sulfide gas cylinder, so that the safety under extreme conditions is ensured. One end of the tail gas recovery manifold is connected with a gas outlet of the ferrous sulfide generation and oxidation reaction in-situ observation chamber and a tail gas absorption area of the movable integrated box body; and (3) pumping harmful gases possibly existing in the ferrous sulfide generation and oxidation reaction in-situ observation chamber and the tail gas absorption zone into the tail gas absorber for absorption treatment under the cooperation of the suction pump.
As shown in fig. 17, in the experimental system, the parameter setting and controlling subsystem 28 includes: a touch display 281, a PLC controller 282, a PLC driver assembly 283, a mechanical relay assembly 284, and a solid state relay assembly 285; wherein,
the touch display 281 is electrically connected with the PLC controller 282;
the PLC controller 282 is electrically connected to the PLC driver assembly 283, the solid state relay assembly 284, the mechanical relay assembly 285, the gas supply motor valve 2462 on the gas supply manifold 246 of the gas supply subsystem 24, the gas recovery motor valve 274 on the gas recovery manifold 273 of the gas recovery subsystem 27, the sample temperature detection sensor 261 of the temperature and gas parameter monitoring subsystem 26, the gas supply gas parameter analyzer 262 of the temperature and gas parameter monitoring subsystem 26, the gas parameter analyzer 263 of the temperature and gas parameter monitoring subsystem 26, and the gas flow monitor 265 of the temperature and gas parameter monitoring subsystem 26, respectively;
the solid state relay assembly 284 is electrically connected to the getter pump 272 of the exhaust gas recovery subsystem 27, the temperature and gas parameter monitoring subsystem 26, and the water vapor generator 245 of the gas supply subsystem 24, respectively;
The mechanical relay assembly 285 is electrically connected to the air supply electric valve 2462 on the air supply manifold 246 of the air supply subsystem 24 and the exhaust gas recovery electric valve 274 on the exhaust gas recovery manifold 273 of the exhaust gas recovery subsystem 27, respectively.
Specifically, among the PLC controller, the PLC driver component, the mechanical relay component and the solid-state relay component of the parameter setting and controlling subsystem, the PLC controller is respectively electrically connected with the PLC driver component, the mechanical relay component, the solid-state relay component, the electric valve, the sample temperature detection sensor, the hydrogen sulfide gas alarm, the gas supply gas parameter analyzer and the tail gas parameter analyzer, the solid-state relay component is respectively electrically connected with the air pump, the environment temperature control subsystem and the water vapor generator, and the mechanical relay component is electrically connected with the electric valve.
According to the experimental system, the in-situ observation chamber for ferrous sulfide generation and oxidation reaction is arranged on the XRD diffractometer, and is respectively and organically connected with the gas supply subsystem, the tail gas recovery subsystem, the environment temperature control subsystem and the temperature and gas parameter monitoring subsystem, and the gas supply subsystem, the tail gas recovery subsystem, the environment temperature control subsystem and the temperature and gas parameter monitoring subsystem are controlled by the parameter setting and controlling subsystem, so that the experimental system can be realized: synthesizing ferrous sulfide; oxidizing ferrous sulfide; controlling environmental parameters in the process of ferrous sulfide generation and oxidation; dynamic detection of phase components and crystal structure changes in the ferrous sulfide generation and oxidation process; monitoring basic parameters such as sample temperature, gas phase products and the like in the ferrous sulfide generation and oxidation process; and (3) recycling toxic and harmful gases in the process of ferrous sulfide generation and oxidation. The experimental system realizes ferrous sulfide generation under controllable conditions and ferrous sulfide oxidation experiments under different conditions such as atmosphere, initial temperature, gas flow and the like, and realizes dynamic detection of phase components and crystal structure changes in the ferrous sulfide generation and oxidation processes by combining with an XRD diffractometer. Therefore, the real change process of the internal structure of the sample in the process of ferrous sulfide generation and oxidation can be better known, and the deep mechanism can be more directly mastered.
The embodiment of the invention also provides an experiment method for generating and oxidizing the spontaneous combustion active ferrous sulfide, which adopts the experiment system for generating and oxidizing the spontaneous combustion active ferrous sulfide and comprises the following steps:
step 1, placing a quantitative ferrous sulfide generation sample 11 in an inert environment in the ferrous sulfide generation and oxidation reaction in-situ observation chamber 1; specifically, a quantitative sample 11 (ferrous sulfide generation experiment: one or more mixtures of iron powder, ferric oxide and ferroferric oxide; ferrous sulfide oxidation experiment: ferrous sulfide sample synthesized by the device or synthesized by other methods) is placed in the sample groove 121 in an inert environment (the glove box is taken as an example in the invention, and the internal inert gas is nitrogen), the sealing rubber ring 14 and the hemispherical sealing cover 13 are installed, the fastening nut bolt 15 is used for fastening and sealing, and the air inlet valve 18 and the air outlet valve 19 are closed;
step 2, taking out the in-situ observation chamber 1 for ferrous sulfide generation and oxidation reaction after sample loading from an inert environment, and then installing the in-situ observation chamber 1 on the XRD diffractometer 3, wherein the in-situ observation chamber is connected with a gas supply manifold 246 of the gas supply subsystem 24, a tail gas recovery manifold 273 of the tail gas recovery subsystem 27, a control Wen Guanhui 254 of the environment temperature control subsystem 25 and a sample temperature detection sensor 261 of the temperature and gas parameter monitoring subsystem 26;
Step 3, characterizing the initial state of the generated ferrous sulfide sample 11 in the ferrous sulfide generation and oxidation reaction in-situ observation chamber 1 through the XRD diffractometer 3, and manually opening an air inlet valve 18 and an air outlet valve 19 of the ferrous sulfide generation and oxidation reaction in-situ observation chamber 1 after the characterization is finished;
step 4, setting parameters of gas in the in-situ observation chamber 1 for generating and oxidizing ferrous sulfide, initial temperature and reaction time through the parameter setting and control subsystem 28;
step 5, controlling the environmental temperature control subsystem 25 through the parameter setting and control subsystem 28, and controlling the initial temperature of the gas supplied by the ferrous sulfide generating and oxidizing reaction in-situ observation chamber 1 and the gas supply subsystem 24 to be set value;
step 6, monitoring and recording and storing each data of the gas components and the temperature in the reaction process through the temperature and gas parameter monitoring subsystem 26 by the parameter setting and control subsystem 28; the parameter setting and controlling subsystem 28 controls the gas supply subsystem 24 to continuously supply the set mixed gas for reaction into the ferrous sulfide generation and oxidation reaction in-situ observation chamber 1, and simultaneously controls the tail gas recovery subsystem 27 to recover the reacted gas to the tail gas recovery subsystem 27; specifically, the parameter setting and controlling system 28 monitors, records and stores data such as gas components and temperatures in the reaction process through the temperature and gas parameter monitoring system 26; the parameter setting and controlling system 28 controls the gas supply system 24 to continuously supply a set gas (ferrous sulfide generation experiment: one or more mixed gases of hydrogen sulfide gas, nitrogen gas and water vapor; ferrous sulfide oxidation experiment: one or more mixed gases of oxygen gas, nitrogen gas and water vapor) into the in-situ observation chamber 1 for ferrous sulfide generation and oxidation reaction, and simultaneously controls the tail gas recovery system 27 to supply the reacted gas into the tail gas recovery system 27 for recovery;
Step 7, after the experiment is finished, stopping storing the data of gas components and temperatures in the reaction process through the parameter setting and control subsystem 28, closing the environmental temperature control subsystem 25, then controlling the gas supply subsystem 24 to purge nitrogen in the ferrous sulfide generation and oxidation reaction in-situ observation chamber 1, and purging harmful gases remained in the gas supply manifold 246 of the gas supply subsystem 24, the ferrous sulfide generation and oxidation reaction in-situ observation chamber 1 and the tail gas recovery manifold 273 of the tail gas recovery subsystem 27 into the tail gas recovery subsystem 27 for recovery;
step 8, closing all the electric valves through the parameter setting and control subsystem; then, the air inlet valve 18 and the air outlet valve 19 of the ferrous sulfide production and oxidation reaction in-situ observation chamber 1 are manually closed, the connection between the ferrous sulfide production and oxidation reaction in-situ observation chamber 1 and the air supply subsystem 24, the tail gas recovery subsystem 27 and the temperature and gas parameter monitoring subsystem 26 is disconnected, and then the ferrous sulfide production and oxidation reaction in-situ observation chamber 1 is moved into an inert environment, and a reacted sample is stored and subjected to subsequent analysis and test.
According to the spontaneous combustion active ferrous sulfide generation and oxidation experimental system and method, the in-situ monitoring of basic parameters such as environmental parameters, phase component crystal structures, sample temperature and gas phase products in the ferrous sulfide generation and oxidation process is realized by designing a matched ferrous sulfide generation and oxidation reaction in-situ observation chamber by means of a commercial XRD diffraction analyzer. The method can better understand the real change process of the internal structure of the sample in the process of ferrous sulfide generation and oxidation, thereby directly grasping the deep mechanism and providing a good experimental platform for researching ferrous sulfide generation and oxidation behaviors. The experimental system standardizes the flow of ferrous sulfide generation and oxidation behavior research and the operation mode of equipment, so that the experimental result is more stable and reliable, the repeatability is higher, and the experimental system is convenient to compare with other research results. Furthermore, the experimental system and the experimental method can also be used for industrial production, and all subsystems are correspondingly enlarged according to production requirements.
The invention is described in further detail below with reference to the drawings and the specific embodiments.
According to the spontaneous combustion active ferrous sulfide generation and oxidation experimental system and method, the generation and oxidation behaviors of ferrous sulfide are studied by monitoring the changes of parameters such as crystal structure, components, gas phase products, temperature and the like in the generation and oxidation processes of ferrous sulfide.
Referring to the drawings, wherein FIG. 1 is a schematic illustration of an pyrophoric active ferrous sulfide production and oxidation experiment system; FIG. 2 is a schematic illustration of a ferrous sulfide production and oxidation reaction in situ cell; FIG. 3 is a cross-sectional view of an in situ observation chamber for ferrous sulfide formation and oxidation reactions; FIG. 4 is a schematic diagram of a sample stage (I); FIG. 5 is a schematic diagram of a sample stage (II); FIG. 6 is a schematic view of a hemispherical containment cap; FIG. 7 is a schematic view of the installation of a ferrous sulfide production and oxidation reaction in situ observation chamber; FIG. 8 is a schematic diagram of a mobile integrated box; FIG. 9 is a schematic diagram (I) of the structure of the mobile integrated box; FIG. 10 is a schematic diagram of the structure of the mobile integrated box (II); FIG. 11 is a schematic diagram of a mobile integrated box structure (I); FIG. 12 is a schematic diagram of a mobile integrated box structure (II); FIG. 13 is a schematic diagram of a mobile integrated box structure (III); FIG. 14 is a schematic diagram of an air supply subsystem and an exhaust gas recovery subsystem; FIG. 15 is a schematic diagram of an ambient temperature control subsystem. FIG. 16 is a schematic diagram of a temperature and gas parameter monitoring subsystem; FIG. 17 is a schematic diagram of a perspective distribution of components in the parameter setting and control subsystem of the present invention.
As shown in fig. 1, the experimental system for researching the formation and oxidation behavior of ferrous sulfide provided by the invention comprises: ferrous sulfide formation and oxidation reaction in-situ observation chamber 1, mobile integrated box 2, XRD diffractometer 3, wherein:
The XRD diffractometer 3 is a conventional commercial XRD diffractometer, and can realize the emission of X-rays and the reception recording of characteristic rays after diffraction. The in-situ observation chamber 1 for ferrous sulfide generation and oxidation reaction is arranged on a sample stage bracket of the in-situ observation chamber.
The movable integrated box 2 comprises a box body 21 and a cover plate 22, and the movable integrated box 2 is further provided with four casters 23 capable of freely rotating, and each caster 23 is correspondingly arranged at four corners of the box body 21. During assembly, the casters 23 are preferably in threaded connection with the box body 21, and during operation, the movable integrated box can freely move to a proper position near the commercial XRD diffraction analyzer 3 under the cooperation of the casters and then be fixed, so that the connection assembly of an experimental system is facilitated, the experiment is then carried out, and the movable integrated box is conveniently moved away after the experiment is finished without affecting the normal operation of the commercial XRD diffraction analyzer 3;
as shown in fig. 2 and 3, the in-situ observation chamber 1 for ferrous sulfide production and oxidation reaction comprises a sample 11, a sample table 12, a hemispherical sealing cover 13, a sealing rubber ring 14, four sets of fastening nut bolts 15, an air inlet pipe 16, an air outlet pipe 17, an air inlet valve 18 and an air outlet valve 19. The sample table 12 and the hemispherical sealing cover 13 form a closed ferrous sulfide generation and oxidation reaction in-situ observation chamber under the cooperation of a sealing rubber ring 14, a fastening nut bolt 15, an air inlet pipe 16, an air outlet pipe 17, an air inlet valve 18 and an air outlet valve 19;
As shown in fig. 4 and 5, the sample stage 12 includes a sample groove 121, an air inlet hole 122, an air outlet hole 123, a seal ring mounting groove 124, a nut and bolt mounting hole 125, a temperature controller mounting groove 126, a temperature control oil pipe mounting hole 127, a temperature measuring hole 128, and a temperature controller cover plate mounting groove 129; the sample groove 121 is a circular shallow groove and is positioned at the center of the upper end of the sample table 12 and is used for containing a sample 11 to be reacted and characterized; the sample stage 12 is also provided with a circular seal ring mounting groove 124 for mounting the seal rubber ring 14; the seal ring mounting groove 124 is positioned at the upper end of the sample stage 12, concentric with the sample groove 121 and having a radius larger than that of the sample groove 121;
the air inlet hole 122 includes a vertical hole 1221 and a horizontal hole 1222, and the air outlet hole 123 includes a vertical hole 1231 and a horizontal hole 1232; a vertical hole 1221 of the air inlet hole 122 and a vertical hole 1231 of the air outlet hole 123 are located between the sample groove 121 and the seal ring mounting groove 124; the horizontal holes 1222 and 1232 of the air inlet hole 122 and the air outlet hole 123 are respectively positioned at the left and right sides of the sample tank 11;
as shown in fig. 6, the hemispherical sealing cover 13 includes a hemispherical cover 131, a wing plate 132, and a bolt installation hole 133;
As shown in fig. 5 and 6, the sample stage 12 has four nut-bolt mounting holes 125 circumferentially spaced apart, the hemispherical seal cover 13 also has four bolt mounting holes 133 circumferentially spaced apart, and each of the bolt mounting holes 115 and the bolt mounting holes 133 is respectively provided with a set of fastening nut bolts 15;
as shown in fig. 2 and 3, the fastening nut bolt 15 includes a bolt 151 and a nut 152; the bolt 151 is an inner hexagon bolt, and the nut 152 is a hexagon nut; during assembly, the nut 152 is arranged in the nut bolt mounting hole 125 of the sample stage 12, the nut 152 is restrained from rotating by the nut bolt mounting hole 125 of the sample stage 12, the bolt 151 is arranged on the bolt mounting hole 133 of the upper wing plate 132 of the hemispherical sealing cover 13 and can freely rotate, and the hemispherical sealing cover 13 and the sample stage 12 are tightly pressed against the sealing rubber ring 14 in the sealing ring mounting groove 124 under the action of four groups of fastening nut bolts 15, so that the tightness of the ferrous sulfide generation and oxidation reaction in-situ observation chamber 1 is ensured;
the air inlet pipe 16 is arranged on a horizontal hole 1222 of the air inlet hole 122, and the other end of the air inlet pipe 16 is provided with an air inlet valve 18; the other end of the air outlet pipe 17 is provided with an air outlet valve 19 on a horizontal hole 1232 of the air outlet hole 123 of the air outlet pipe 17; the air inlet valve 18 and the air outlet valve 19 are manual valves, and the switch of the air inlet valve and the air outlet valve is manually controlled according to the requirement in the experiment;
As shown in fig. 2 to 5, the bottom end of the sample stage 12 has a temperature controller mounting groove 126 for mounting a sample stage temperature controller 253; a temperature control oil pipe mounting hole 127 for mounting a temperature control pipeline 254 of the sample stage temperature controller 253 is also formed on the front right side of the sample stage 12; a temperature measuring hole 128 is formed in the front center of the sample stage 12 and is used for installing a sample temperature detection sensor 261, the temperature measuring hole 128 is located between the sample tank 121 of the sample stage 12 and the temperature controller installation groove 126, and the temperature measuring sensitive end of the temperature measuring hole 128 is about 1mm away from the bottom of the sample tank 121 and the top of the temperature controller installation groove 126, so that accurate measurement of the temperature of the sample 11 is ensured;
as shown in fig. 7, the hemispherical sealing cover 13 is a hemispherical transparent cover plate, and after the hemispherical sealing cover 13 is installed, the center of sphere of the hemispherical sealing cover 13 is concentric with the monitoring movement track of the XRD diffractometer 3, so that the incidence of the X-rays generated by the commercial XRD diffractometer and the characteristic X-rays generated after the X-rays irradiate the sample to be characterized are ensured;
as shown in fig. 8 to 10, the mobile integrated box 2 includes a box body 21, a cover plate 22, casters 23, a gas supply subsystem 24, an ambient temperature control subsystem 25, a temperature and gas parameter monitoring subsystem 26, an exhaust gas recovery subsystem 27, and a parameter setting and controlling subsystem 28; the air supply subsystem 24, the environment temperature control subsystem 25, the temperature and gas parameter monitoring subsystem 26 and the tail gas recovery subsystem 27 are arranged in the box body 21, and the cover plate 22 is arranged on the box body 21;
As shown in fig. 11 to 13, the case 21 is divided into a supply area 211, an exhaust gas absorption area 212, and a control area 213; the gas supply area 211 is provided with a high-purity nitrogen cylinder tank 2111, an oxygen cylinder tank 2112, an air cylinder tank 2113 and a water vapor generator tank 2114, the tail gas absorption area 212 is provided with a tail gas recovery subsystem tank 2121 and a hydrogen sulfide cylinder tank 2122, and the control area 213 is provided with a temperature control system installation tank 2131; the parameter setting and controlling subsystem 28 is mounted on the cover plate 22 above the control area 213 of the box 21;
as shown in fig. 9 and 14, the air supply subsystem 24 includes a high purity nitrogen cylinder 241, an oxygen cylinder 242, a compressed air cylinder 243, a hydrogen sulfide cylinder 244, a water vapor generator 245, and a set of air supply manifolds 246, and the high purity nitrogen cylinder 241, the oxygen cylinder 242, the compressed air cylinder 243, the hydrogen sulfide cylinder 244, and the water vapor generator 245 are respectively installed in the high purity nitrogen cylinder tank 2111, the oxygen cylinder tank 2112, the compressed air cylinder tank 2113, the hydrogen sulfide cylinder tank 2122, and the water vapor generator tank 2114; the gas supply manifold 246 is connected with the high-purity nitrogen cylinder 241, the oxygen cylinder 242, the compressed air cylinder 243, the hydrogen sulfide cylinder 244 and the water vapor generator 245; the air supply manifold 246 comprises a group of pipelines 2461 and two air supply electric valves 2462, the air supply electric valves 2462 are arranged on the pipelines 2461 to form the air supply manifold 246, and the air supply direction of the air supply manifold 246 can be regulated to be the ferrous sulfide generation and oxidation reaction in-situ observation chamber 1 or the tail gas recovery subsystem 27 by controlling the air supply electric valves 2462;
As shown in fig. 9 and 14, the exhaust gas recovery subsystem 27 includes an exhaust gas absorber 271, a suction pump 272, a set of exhaust gas recovery manifolds 273, and two exhaust gas recovery electrically operated valves 274; the exhaust gas absorber 271 is arranged in an exhaust gas recovery subsystem groove 2121, the suction pump 272 is arranged on the exhaust gas absorber 271, the suction pump 272 is connected with an exhaust gas recovery manifold 273, two exhaust gas recovery electric valves 274 are arranged on the exhaust gas recovery manifold 273, and the exhaust gas recovered by the exhaust gas recovery subsystem 27 can be controlled to come from the ferrous sulfide generation and oxidation reaction in-situ observation chamber 1 or the exhaust gas absorption zone 212 through the two exhaust gas recovery electric valves 274;
the hydrogen sulfide gas in the hydrogen sulfide gas cylinder 244 is a flammable and explosive toxic gas that cannot be put together with the oxidizer oxygen, so the hydrogen sulfide gas cylinder 244 is placed in the tail gas absorbing region 212 so as to be isolated from the oxygen; and when the hydrogen sulfide gas leaks, the tail gas recovery subsystem 27 in the tail gas absorption zone 212 can directly absorb the leaked hydrogen sulfide gas;
as shown in fig. 15, the environmental temperature control subsystem 25 includes an oil bath circulation tank 251, an air pipe heat tracing temperature controller 252, a sample stage temperature controller 253, and a set of controls Wen Guanhui, 254; the oil bath circulation box 251 is installed in the temperature control system installation groove 2131, the air pipe heat tracing temperature controller 252 is installed on the air supply manifold 246, the sample stage temperature controller 253 is installed in the temperature controller installation groove 126, and the air pipe heat tracing temperature controller 252 and the sample stage temperature controller 253 are connected with the oil bath circulation box 251 through a control Wen Guanhui 254; the oil bath circulation box 251 conveys temperature-controlled oil with set temperature into the air pipe heat tracing temperature controller 252 and the sample stage temperature controller 253 through the control Wen Guanhui 254 and recovers the circulated temperature-controlled oil, thereby realizing temperature control;
As shown in fig. 9, 14 and 16, the temperature and gas parameter monitoring subsystem 26 includes a sample temperature detection sensor 261, a supply gas parameter analyzer 262, an exhaust gas parameter analyzer 263, a hydrogen sulfide gas alarm 264 and a set of gas flow monitors 265; the sample temperature detection sensor 261 is installed in the temperature measurement hole 128; the gas supply parameter analyzer 262 is mounted on the gas supply manifold 246 and is positioned in front of the gas inlet valve 18 for analyzing parameters such as temperature, pressure, flow, composition, etc. of the gas introduced into the ferrous sulfide production and oxidation reaction in-situ chamber 1; the tail gas parameter analyzer 263 is installed on the tail gas recovery manifold 273 and located behind the gas outlet valve 19, and is used for analyzing parameters such as temperature, pressure, flow, components and the like of the gas discharged from the in-situ observation chamber 1 for ferrous sulfide generation and oxidation reaction; the hydrogen sulfide gas alarm 264 is installed in the tail gas absorption zone 212 for monitoring the concentration of hydrogen sulfide gas in the tail gas recovery zone 212; the gas flow monitor 265 is installed at the connection part of the high-purity nitrogen cylinder 241, the oxygen cylinder 242, the compressed air cylinder 243, the hydrogen sulfide cylinder 244 and the water vapor generator 245 and the gas supply manifold 246, and the gas flow monitor 265 is used for monitoring and regulating the flow of the gas supplied by each gas source;
As shown in fig. 17, a parameter setting and controlling subsystem 28 is further provided, and the parameter setting and controlling subsystem 28 includes a touch display 281, a PLC controller 282, a PLC driver assembly 283, a set of solid state relay assemblies 284, and a set of mechanical relay assemblies 285; the touch display 281 is electrically connected to the PLC controller 282, the PLC controller 282 is electrically connected to the PLC driver assembly 283, the solid state relay assembly 284, the mechanical relay assembly 285, the gas supply electric valve 2462, the off-gas recovery electric valve 274, the sample temperature detection sensor 261, the gas supply gas parameter analyzer 262, the off-gas parameter analyzer 263, the hydrogen sulfide gas alarm 264, the gas flow monitor 265, the solid state relay assembly 284 is electrically connected to the suction pump 272, the temperature and gas parameter monitoring subsystem 26, and the water vapor generator 245, and the mechanical relay assembly 285 is electrically connected to all of the gas supply electric valve 2462, the off-gas recovery electric valve 274.
The embodiment of the invention also provides an experimental method adopting the spontaneous combustion active ferrous sulfide generation and oxidation experimental system, which comprises the following steps:
Step 1) quantitative sample 11 (iron sulfide formation experiment) was taken in an inert atmosphere (the glove box of the present invention is exemplified by nitrogen as the internal inert gas: one or more mixtures of iron powder, ferric oxide, and ferric oxide; ferrous sulfide oxidation experiment: ferrous sulfide sample, synthesized by the device or synthesized by other methods) is placed in the sample groove 121, the sealing rubber ring 14 and the hemispherical sealing cover 13 are installed, the sealing is fastened and sealed by the fastening nut bolts 15, and the air inlet valve 18 and the air outlet valve 19 are closed;
step 2), taking out the in-situ observation chamber 1 for ferrous sulfide generation and oxidation reaction after sample loading from a glove box, and then installing the in-situ observation chamber on the XRD diffractometer 3, and connecting the air supply manifold 246, the tail gas recovery manifold 273, the control Wen Guanhui 254 and the sample temperature detection sensor 261;
step 3) characterizing the initial sample 11 by means of the XRD diffractometer 3, and manually opening the air inlet valve 18 and the air outlet valve 19 after the characterization is finished;
step 4) setting parameters of the gas, the initial temperature, the reaction time and the like in the parameter setting and controlling subsystem 28;
step 5), the parameter setting and controlling subsystem 28 controls the initial temperature of the gas supplied by the ferrous sulfide generating and oxidizing reaction in-situ observation chamber 1 and the gas supply subsystem 24 to be set by controlling the environmental temperature control subsystem 25;
Step 6), the parameter setting and controlling subsystem 28 monitors, records and stores the data of gas components, temperature and the like in the reaction process through the temperature and gas parameter monitoring subsystem 26; the parameter setting and controlling subsystem 28 controls the gas supply subsystem 24 to continuously supply set gas (ferrous sulfide generation experiment: one or more mixed gas of hydrogen sulfide gas, nitrogen gas and water vapor; ferrous sulfide oxidation experiment: one or more mixed gas of oxygen gas, nitrogen gas and water vapor) into the ferrous sulfide generation and oxidation reaction in-situ observation chamber 1, and simultaneously controls the tail gas recovery subsystem 27 to supply the reacted gas into the tail gas recovery subsystem 27 for recovery;
step 7), after the experiment is finished, the parameter setting and control subsystem stops storing the data such as gas components, temperature and the like in the reaction process, the environmental temperature control subsystem is closed, then the gas supply subsystem is controlled to carry out nitrogen purging on the in-situ observation chamber for ferrous sulfide generation and oxidation reaction, and harmful gases possibly existing in the gas supply manifold, the in-situ observation chamber for ferrous sulfide generation and oxidation reaction and the tail gas recovery manifold are purged into the tail gas recovery subsystem for recovery;
Step 8), the parameter setting and control subsystem closes all the electric valves; and then manually closing the air inlet valve and the air outlet valve, and disconnecting the ferrous sulfide generation and oxidation reaction in-situ observation chamber from the air supply subsystem, the air supply manifold of the tail gas recovery subsystem and the sample temperature detection sensor. And then transferring the in-situ observation chamber for ferrous sulfide generation and oxidation reaction into a glove box, and preserving the reacted sample or carrying out subsequent analysis and test.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (9)
1. An auto-ignition activated ferrous sulfide production and oxidation experiment system, comprising:
the in-situ observation chamber (1) for ferrous sulfide generation and oxidation reaction is provided with a closed space for observation reaction, and the in-situ observation chamber (1) for ferrous sulfide generation through oxidation reaction is arranged on an XRD diffractometer (3);
A gas supply subsystem (24) connected with the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1) through a gas supply manifold (246);
the environment temperature control subsystem (25) is provided with an air pipe heat tracing temperature controller (252) and a sample platform temperature controller (253), the air pipe heat tracing temperature controller (252) is arranged on an air supply manifold (246) of the air supply subsystem (24), and the sample platform temperature controller (253) is arranged on a sample platform (12) of the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1);
the temperature and gas parameter monitoring subsystem (26) and the tail gas recycling subsystem (27) are respectively connected with the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1);
the in-situ observation chamber (1) for ferrous sulfide generation and oxidation reaction comprises: the sample table (12) is provided with a hemispherical sealing cover (13) in a buckling manner through a sealing rubber ring (14) and a fastening nut bolt (15) on the sample table (12) to form a closed space for observing reaction;
the hemispherical sealing cover (13) is respectively connected with an air inlet pipeline provided with an air inlet valve (18) and an air outlet pipeline provided with an air outlet valve (19);
the sample table (12) and the hemispherical sealing cover (13) on the sample table are integrally arranged on the XRD diffractometer (3);
the parameter setting and controlling subsystem (28) is electrically connected with the air supply subsystem (24), the environment temperature control subsystem (25), the temperature and gas parameter monitoring subsystem (26) and the tail gas recycling subsystem (27) respectively, and can set parameters of all the subsystems and control the air supply subsystem (24), the environment temperature control subsystem (25), the temperature and gas parameter monitoring subsystem (26) and the tail gas recycling subsystem (27) to finish, monitor and record ferrous sulfide generation and oxidation reaction and parameters in the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1).
2. The spontaneous combustion activated ferrous sulfide generation and oxidation experiment system of claim 1, further comprising: the movable integrated box (2), the air supply subsystem (24), the environment temperature control subsystem (25), the temperature and gas parameter monitoring subsystem (26), the tail gas recovery subsystem (27) and the parameter setting and controlling subsystem (28) are all arranged in the movable integrated box (2).
3. The spontaneous combustion activated ferrous sulfide generation and oxidation experiment system according to claim 2, wherein the mobile integrated tank (2) comprises: a case (21) and a cover plate (22); four casters (23) are arranged at the bottom of the box body (21); the inside of the box body (21) is divided into an air supply area (211), an exhaust gas absorption area (212) and a control area (213), the air supply area (211) is internally provided with an air supply subsystem (24), the exhaust gas absorption area (212) is internally provided with an exhaust gas recovery subsystem (27), and the control area (213) is internally provided with an environment temperature control subsystem (25), a temperature and gas parameter monitoring subsystem (26) and a parameter setting and controlling subsystem (28);
the hydrogen sulfide cylinder (244) of the gas supply subsystem (24) is arranged in the tail gas absorption zone (212) and is isolated from the oxygen cylinder (242) of the gas supply subsystem (24) in the gas supply zone (211).
4. A pyrophoric activated ferrous sulfide production and oxidation experiment system according to any one of claims 1 to 3, wherein the gas supply subsystem (24) comprises: a high purity nitrogen cylinder (241), an oxygen cylinder (242), an air cylinder (243), a hydrogen sulfide cylinder (244), a water vapor generator (245) and the air supply manifold (246); the high-purity nitrogen cylinder (241), the oxygen cylinder (242), the air cylinder (243), the hydrogen sulfide cylinder (244) and the water vapor generator (245) are all connected with the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1) through the air supply manifold (246), and the gases of all air sources can be mixed and then supplied into the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1);
the ambient temperature control subsystem (25) comprises: an oil bath circulation box (251), a control Wen Guanhui (254), the sample stage temperature controller (253) and the air pipe heat tracing temperature controller (252); wherein, the oil bath circulation box (251) is respectively connected with the air pipe heat tracing temperature controller (252) and the sample stage temperature controller (253) through the control Wen Guanhui (254); the air pipe heat tracing temperature controller (252) can control the temperature of air in the air supply manifold (246); the sample stage temperature controller (253) is arranged at the bottom of the sample stage (12) of the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1) and can control the temperature of the sample stage (12).
5. An pyrophoric activated ferrous sulfide production and oxidation experiment system according to any one of claims 1 to 3, wherein the temperature and gas parameter monitoring subsystem (26) comprises: a sample temperature detection sensor (261), a gas supply gas parameter analyzer (262), an exhaust gas parameter analyzer (263), and a set of gas flow monitors (265); wherein,
the sample temperature detection sensor (261) is arranged in a temperature measurement hole (128) below a sample stage (12) of the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1), and the temperature measurement sensitive end of the temperature measurement hole (128) is 1-2 mm away from the bottom of a sample groove (121) of the sample stage (12);
the gas supply parameter analyzer (262) is arranged on a gas supply manifold (246) of the gas supply subsystem (24) and is positioned in front of an air inlet valve (18) of the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1) and can analyze the temperature, pressure, flow and component parameters of gas introduced into the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1);
the tail gas parameter analyzer (263) is arranged on a tail gas recovery manifold (273) of the tail gas recovery subsystem (27) connected with the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1), and is positioned behind an air outlet valve (19) of the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1) and can analyze the temperature, pressure, flow and components parameters of the gas exhausted from the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1);
The group of gas flow monitors (265) are respectively arranged on a gas supply manifold (246) of the gas supply subsystem (24) and a tail gas recovery manifold (273) of the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1) connected with the tail gas recovery subsystem (27) and can respectively monitor the gas flow in the gas supply manifold (246) and the gas flow in the tail gas recovery manifold (273).
6. The pyrophoric activated ferrous sulfide generation and oxidation experiment system of claim 5, wherein the temperature and gas parameter monitoring subsystem (26) further comprises:
the hydrogen sulfide gas alarm (264) is correspondingly arranged in the installation area of the hydrogen sulfide gas cylinder (244) of the gas supply subsystem (24) and can alarm after the gas of the hydrogen sulfide gas cylinder (244) leaks.
7. A pyrophoric activated ferrous sulfide production and oxidation experiment system according to any one of claims 1 to 3, wherein the tail gas recovery subsystem (27) comprises: an exhaust absorber (271), a suction pump (272), an exhaust recovery manifold (273) and two exhaust recovery electric valves (274); the suction pump (272) is arranged on the tail gas absorber (271), the suction pump (272) is connected with the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1) through the tail gas recovery manifold (273), and two tail gas recovery electric valves (274) are arranged on the tail gas recovery manifold (273).
8. A pyrophoric activated ferrous sulfide production and oxidation experiment system according to any one of claims 1 to 3, wherein the parameter setting and control subsystem (28) comprises: a touch display (281), a PLC controller (282), a PLC driver assembly (283), a mechanical relay assembly (284), and a solid state relay assembly (285); wherein,
the touch display (281) is electrically connected with the PLC (282);
the PLC controller (282) is electrically connected with the PLC driver assembly (283), the solid state relay assembly (284), the mechanical relay assembly (285), a gas supply electric valve (2462) on a gas supply manifold (246) of the gas supply subsystem (24), a gas recovery electric valve (274) on a gas recovery manifold (273) of the gas recovery subsystem (27), a sample temperature detection sensor (261) of the temperature and gas parameter monitoring subsystem (26), a gas supply gas parameter analyzer (262) of the temperature and gas parameter monitoring subsystem (26), a gas parameter analyzer (263) of the temperature and gas parameter monitoring subsystem (26) and a gas flow monitor (265) of the temperature and gas parameter monitoring subsystem (26), respectively;
the solid relay assembly (284) is electrically connected with a suction pump (272) of the tail gas recovery subsystem (27), the temperature and gas parameter monitoring subsystem (26) and a water vapor generator (245) of the gas supply subsystem (24) respectively;
The mechanical relay assembly (285) is electrically connected with an air supply electric valve (2462) on an air supply manifold (246) of the air supply subsystem (24) and an exhaust gas recovery electric valve (274) on an exhaust gas recovery manifold (273) of the exhaust gas recovery subsystem (27) respectively.
9. A method for testing the formation and oxidation of pyrophoric active ferrous sulfide, characterized in that the system for testing the formation and oxidation of pyrophoric active ferrous sulfide according to any one of claims 1 to 8 is used, comprising the steps of:
step 1) placing a quantitative ferrous sulfide generation sample (11) in an inert environment in an in-situ observation chamber (1) for ferrous sulfide generation and oxidation reaction;
step 2) taking the in-situ observation chamber (1) for ferrous sulfide generation and oxidation reaction after sample loading out of an inert environment, and then installing the chamber on the XRD diffractometer (3), wherein the chamber is connected with a gas supply manifold (246) of the gas supply subsystem (24), a tail gas recovery manifold (273) of the tail gas recovery subsystem (27), a control Wen Guanhui (254) of an environment temperature control subsystem (25) and a sample temperature detection sensor (261) of the temperature and gas parameter monitoring subsystem (26);
step 3) representing the initial state of a generated ferrous sulfide sample (11) in the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1) through the XRD diffractometer (3), and manually opening an air inlet valve (18) and an air outlet valve (19) of the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1) after the representation is finished;
Step 4) setting parameters of gas, initial temperature and reaction time in the in-situ observation chamber (1) for ferrous sulfide generation and oxidation reaction through the parameter setting and control subsystem (28);
step 5) controlling the environment temperature control subsystem (25) through the parameter setting and control subsystem (28) to control the initial temperature of the gas supplied by the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1) and the gas supply subsystem (24) to be set values;
step 6) monitoring and recording and storing each data of the gas components and the temperature in the reaction process through the temperature and gas parameter monitoring subsystem (26) by the parameter setting and control subsystem (28); the parameter setting and controlling subsystem (28) controls the gas supply subsystem (24) to continuously introduce the set mixed gas for reaction into the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1), and simultaneously controls the tail gas recovery subsystem (27) to recover the reacted gas to the tail gas recovery subsystem (27);
after the experiment of the step 7) is finished, stopping storing the data of gas components and temperatures in the reaction process through the parameter setting and control subsystem (28), closing the environment temperature control subsystem (25), then controlling the gas supply subsystem (24) to purge nitrogen in the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1), and purging harmful gas remained in the gas supply manifold (246) of the gas supply subsystem (24), the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1) and the tail gas recovery manifold (273) of the tail gas recovery subsystem (27) to the tail gas recovery subsystem (27) for recovery;
Step 8), closing all the electric valves through the parameter setting and control subsystem; then manually closing an air inlet valve (18) and an air outlet valve (19) of the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1), disconnecting the connection between the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1) and the air supply subsystem (24), the tail gas recovery subsystem (27) and the temperature and gas parameter monitoring subsystem (26), and then moving the ferrous sulfide generation and oxidation reaction in-situ observation chamber (1) into an inert environment, and preserving a reacted sample and performing subsequent analysis and test.
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