CN103278374A - In situ Raman analysis device for representing hydrate and in situ Raman analysis method of hydrate sample - Google Patents
In situ Raman analysis device for representing hydrate and in situ Raman analysis method of hydrate sample Download PDFInfo
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Abstract
The invention discloses an in situ Raman analysis device for representing hydrate and an in situ Raman analysis method of a hydrate sample. The device comprises a stable gas supply unit, a hydrate generation/decomposition unit, a temperature control unit and a data acquisition and analysis unit. A reaction kettle in the hydrate generation/decomposition unit achieves pressure maintaining sealing and rapid sampling of hydrate in the kettle by the aid of three bolts; the reaction kettle is provided with a detachable liquid nitrogen low-temperature jacket which is used for providing a low temperature environment for the hydrate sample in a moving process and an analysis process, and the hydrate structure is guaranteed to be stable; when the hydrate is generated, the liquid nitrogen low-temperature jacket can be detached, the reaction kettle is placed in a water bath for experiment, and the liquid nitrogen low-temperature jacket can be directly formed in a liquid nitrogen environment for experiment; and high-purity quartz glass which allows ultraviolet light to penetrate is mounted on front and rear windows of the reaction kettle and suitable for in situ Raman analysis of the hydrate structure. According to the in situ Raman analysis device for representing the hydrate and the in situ Raman analysis method of the hydrate sample, the problems of decomposition or structure changes of the hydrate sample due to long time sampling are avoided, and at the same time, in situ Raman analysis is introduced, so that the structure changes of the hydrate in a generation/decomposition process can be really reflected.
Description
Technical field
The present invention relates to a kind of hydrate characterization apparatus of in-situ Raman analysis and the analytical approach of hydrate sample in-situ Raman, relate in particular to a kind of thermodynamics and kinetics experimental study that both had been applicable to that gas hydrate generated/decomposes, be applicable to the experimental provision that hydrate structure is analyzed again.
Background technology
Gas hydrate (gas hydrate) is the nonquantitative cage shape crystalline solid that is formed by water and guest molecule, is a kind of compound with cage structure, is present in usually under the condition of cryogenic high pressure.The main body hydrone links to each other by hydrogen bond, forms a series of polyhedron holes that vary in size, and these polyhedron holes link to each other by summit or face, form the hydrate lattice of cage shape to spatial development.Empty hydrate crystalline network instability is equivalent to unsettled ice.Guest molecule is filled in the hydrate lattice by model ylid bloom action power could form stable gas hydrate.According to the difference of guest molecule size, hydrate has three kinds of different structures, is respectively I type, II type, H type.Molecular dimension exists
The mesopore of the guest molecule interstitital texture I type hydrate in the scope, thus structure I type hydrate formed, as CH
4, CO
2And H
2S etc.; Molecular dimension exists
With
Aperture and macropore in the guest molecule difference interstitital texture II type hydrate in the scope, thus structure I I hydrate formed, as N
2, O
2And C
3H
8Form structure I I type hydrate etc. courteous molecule; Mesopore or macropore in large-sized guest molecule (as normal butane, cyclohexane, methylcyclohexane etc.) interstitital texture H type hydrate are at the micromolecular auxiliary structure H type hydrate that forms down; Some hydrate forms the structure that agent (as tetrabutyl ammonium bromide) part-structure participates in the hydrate lattice, and fills the hole jointly with the little molecule of object, thereby forms half cagelike structure hydrate.
The stability of hydrate structure mainly is subjected to the hydrate hole by the influence (claiming the hole occupation rate again) of guest molecule filling ratio, and the more big then hydrate structure of occupation rate is more stable.The size of guest molecule and gas phase fugacity are the principal elements that influences the hole occupation rate.The filling of guest molecule in the hydrate lattice is at random, has only when the hole of guest molecule occupation rate reaches certain value to form stable hydrate structure.The hole occupation rate of guest molecule also is subjected to condition effect such as guest molecule shape and hydrate accelerant simultaneously except being subjected to the temperature and pressure condition effect.Common host molecule under given conditions and guest molecule only form a kind of hydrate of structure, but the structure of hydrate also may change along with the change of hydrating condition, or makes hydrate structure change because of the interpolation of another kind of guest molecule.For example the trimethylene hydrate is when temperature change and the structure I that causes and the transformation between the II; CH
4Form the structure I hydrate during gas pure state, add tetrahydrofuran and then form structure I I type hydrate as hydrate formation agent.
The hydrate structure that causes because of condition in the experimentation changes and can't directly determine, must characterize concrete hydrate structure by structure analysis instruments such as XRD, NMR, Ramans.Be subjected to the influence of hydrate formation and decomposition condition, common hydrate reaction still is by maximum pressure-bearing and the hydrate forms desired seal condition of several groups of bolt to guarantee this reactor, yet this design has brought great inconvenience for the structure analysis sampling of hydrate.The change of the discharging of pressure and temperature all can cause the decomposition of hydrate in the sampling process, and this just requires XRD, NMR and Raman sampling to carry out under low temperature environment, and sampling finishes in a short period of time.Yet moving with the realization of low temperature sampling environment of heavy stainless steel cauldron is all very difficult, and sampling result is not satisfactory.Simultaneously, because traditional hydrate reaction still form adopts plexiglas more, in position in the Raman analysis process, resin closely structure influence laser to the focusing of hydrate sample, its strong Raman signal has been covered hydrate structures of samples signal, makes in-situ Raman analyze hydrate work and becomes very difficult.Therefore, a kind of convenient carrying, can realize the reactor of quick sampling, low temperature environment and in-situ Raman analysis, the analysis and research work of hydrate structure is had decisive influence.
Summary of the invention
The objective of the invention is to overcome the difficult problem of taking a sample when existing hydrate structure is analyzed, a kind of hydrate characterization apparatus of in-situ Raman analysis and the analytical approach of hydrate sample in-situ Raman are provided, both be applicable to hydrate thermodynamics and kinetics research, be applicable to again that the hydrate sampling carried out the research of branch bleed laminate structures such as XRD, NMR and in-situ Raman.
For realizing above purpose, the present invention has taked following technical scheme: the hydrate characterization apparatus that a kind of in-situ Raman is analyzed, comprise stable air supply unit, hydrate generation/resolving cell, temperature control unit, data acquisition and processing unit, stablize air supply unit and be used for providing test gas to hydrate generation/resolving cell; Hydrate generation/resolving cell by injecting gas in the reactor in it and test mixed solution, carries out hydrate and generates or decomposition run under predetermined condition; The temperature control unit is used for the temperature variation of control hydrate generation/resolving cell; Data acquisition and processing unit are used for gathering, preserving and analyze the data such as variation of temperature, pressure and the gas composition of hydrate generation/resolving cell, and pressure and the temperature control cell temperature of control reactor.
Stable air supply unit comprises gas cylinder, compressor, surge tank and PID operation valve, and described gas cylinder forms one with reactor and is connected branch road, and described gas cylinder, compressor, surge tank and one of PID operation valve formation are connected branch road and are connected with described reactor; When storage pressure was enough high, gas directly entered reactor by gas cylinder, or provided experiment required pressure via surge tank for reactor; When storage pressure is low, realize stable air-flow supply by compressor.
Hydrate generation/resolving cell comprises reactor, magnetic stirring apparatus, vacuum pump and gas chromatograph, and described magnetic stirring apparatus is arranged in the reactor, and vacuum pump is connected with reactor respectively with gas chromatograph.But the gas composition in the gas chromatograph on-line monitoring hydration generative process changes, and can change the volumetric molar concentration of each component gas in the decomposition of hydrate process simultaneously and analyze.
The temperature control unit comprises constant water bath box and is arranged on the outer dismountable low temperature liquid nitrogen chuck of reactor that described reactor and surge tank all are arranged in the warm water bath cabinet.Generate needs according to hydrate, these two kinds of refrigeration modes can be changed.Both can place water-bath to form hydrate reactor, and also reactor can be placed the liquid nitrogen cryogenics chuck form hydrate; The reactor that forms hydrate in water-bath can be placed the liquid nitrogen cryogenics chuck equally, be used for the scanning analysis of carrying, sampling and the in-situ Raman of reactor.
The data collection and analysis system comprises data collecting card, computing machine and each temperature/pressure sensor, it is used for gathering experimental data automatically every setting-up time, and the experimental pressure in the control reactor and temperature control unit, curves such as the temperature-time of acquisition, pressure-time, be used for the analysis to hydrate generation and decomposing state, described data collecting card is connected with reactor with surge tank, PID operation valve respectively, computing machine and described data acquisition card connection.
The reactor that wherein is used for the hydrate generation and decomposes is key component of the present invention.The formation of hydrate need be carried out in hyperbaric environment, and traditional reactor all is by the paired fixation reaction still of many groups bolt, ensures hyperbaric environment with this.Usually the bolt number that adopts must be more than 4, and 4 groups of (8) bolts are modal fixed form.To organize the reactor of bolt different more and with tradition, the hydrate reaction still that the present invention relates to adopts the mode of flat seal, only need one group of (3) outer bolt get final product, wherein the reactor top pressure that can bear is 8MPa, has and can realize sampling fast and convenient characteristics of carrying.3 bolt shapes triangular in shape among the present invention fix being connected of reaction kettle cover and kettle, and the processing of leaving a blank is done in the outside of kettle cover and bolt junction, and width is identical with the diameter of bolt.In the sample analysis process, as long as back out the single bolt of a side with spanner, two bolts of loosening opposite side, can take off the kettle cover translation, thereby realize fast hydrate sample in the still being taken out, be used for XRD and NMR and analyze, long by sample time and hydrate structure that cause is unstable or the problem of decomposing when avoiding XRD, NMR to analyze.Reactor device among the present invention is equally applicable to the thermodynamic study of hydrate phase balance, is applicable to that also hydrate generates the dynamics research of induction time, generating rate etc., is particularly useful for the analytical test of hydrate structure.
The described reactor outside is equipped with dismountable liquid nitrogen cryogenics chuck, the liquid nitrogen cryogenics chuck is made by copper sheet, two parts chuck that separates is by the splicing of chuck interface, hold liquid nitrogen or cold-producing medium or heating agent in the liquid nitrogen cryogenics chuck, the import of reactor both sides is connected the heat transfer that circulates of pump or condenser with outlet.Removing the liquid nitrogen cryogenics chuck can place constant water bath box to experimentize reactor; The liquid nitrogen cryogenics chuck is installed can directly experimentize under liquid nitrogen environment.Moving in the analytic process with the hydrate sample of reactor, the liquid nitrogen cryogenics chuck provides low temperature environment for the hydrate sample, guarantees the stability of hydrate structure in the sample analysis process.
The form that described reactor surface arranges is made of at the high-purity quartz glass more than 95% a pair of ultraviolet light transmittance.Laser directly penetrates quartz glass, and the hydrate sample of reactor inside is carried out the in-situ Raman analysis, obtains hydrate crystalline form and structural information accurately, is used for the variation that the laser raman original position is analyzed hydrate structure.This hydrate generation/resolving cell namely is applicable to the thermodynamic study of hydrate phase balance, is applicable to that also hydrate generates the dynamics research of induction time, generating rate etc., is particularly useful for the analytical test of hydrate structure.
The present invention compared with prior art has following advantage:
1, the convenient carrying of the reactor in this experimental provision and dismounting can be finished the sampling of hydrate in a short period of time;
2, the detachable liquid nitrogen cryogenics chuck of this experimental provision employing can not only guarantee the Stability Analysis of Structures of hydrate in the analytical sampling process, and directly provide low temperature environment for the generation of hydrate according to requirement of experiment;
3, the form ultraviolet-transmitting high-purity quartz glass that reactor adopts in this experimental provision, can not only be used for observation and shooting record that hydrate generation/decomposable process crystalline form changes, and be applicable to laser raman original position analysis hydrate sample, obtain hydrate structure information accurately;
4, adopt water bath with thermostatic control and liquid nitrogen cryogenics chuck in this experimental provision, can experimental requirement change.
Description of drawings
Fig. 1 is the structural representation of this EXPERIMENTAL EXAMPLE;
Fig. 2 is the reactor synoptic diagram of the band liquid nitrogen cryogenics chuck in this EXPERIMENTAL EXAMPLE;
Fig. 3 is the bolt distribution plan on the reactor kettle cover in this EXPERIMENTAL EXAMPLE.
Embodiment
Below in conjunction with the drawings and specific embodiments content of the present invention is described in further details.
Embodiment:
See also Fig. 1, the hydrate characterization apparatus that a kind of in-situ Raman is analyzed, comprise stable air supply unit, hydrate generation/resolving cell, temperature control unit, data acquisition and processing unit, stablize air supply unit and be used for providing test gas to hydrate generation/resolving cell; Hydrate generation/resolving cell by injecting gas in the reactor 6 in it and test mixed solution, carries out hydrate and generates or decomposition run under predetermined condition; The temperature control unit is used for the temperature variation of control hydrate generation/resolving cell; Data acquisition and processing unit are used for gathering, preserving and analyze the data such as variation of temperature, pressure and the gas composition of hydrate generation/resolving cell, and control reactor pressure and temperature control cell temperature.
See also Fig. 2, the hydrate reaction still 6 of band liquid nitrogen cryogenics chuck is the hydrate sample apparatus for placing of convenient resettlement.The liquid nitrogen cryogenics chuck provides low temperature environment for the structure analysis of hydrate, guarantees the stability of hydrate structure in resettlement, the sampling and analysing process.See also Fig. 3, three outer bolt, 18 shapes triangular in shape on the reactor 6 distribute, and are the key structures that the hydrate sample can be taken out fast.
Stable air supply unit comprises gas cylinder 1, compressor 2, surge tank 3 and PID operation valve 13, and gas cylinder 1 forms one with reactor 6 and is connected branch road, and gas cylinder 1, compressor 2, surge tank 3 and 13 one of the formation of PID operation valve are connected branch road and are connected with reactor 6.When storage pressure was higher, gas directly entered reactor 6 by gas cylinder 1, or provided experiment required pressure via surge tank 3 for reactor 6; When storage pressure is low, realize stable air-flow supply by compressor 2.By the control software on PID operation valve 13 and the computing machine 11, can carry out constant pressure experimentation.
Hydrate generates/decomposes unit and comprises reactor 6, magnetic stirring apparatus 5, vacuum pump 14 and gas chromatograph 10.Magnetic stirring apparatus 5 is arranged in the reactor 6, and vacuum pump 14 is connected with reactor 6 respectively with gas chromatograph 10.The temperature control unit comprises constant water bath box 4 and the dismountable low temperature liquid nitrogen chuck 17 that is arranged on outside the reactor 6, and hydrate reaction still 6 both can place constant water bath box 4, liquid nitrogen cryogenics chuck 17 can be installed again carry out the generation of hydrate and decompose experiment.Gas enters reactor by air intake opening 20 and participates in hydration reaction in the hydrate generative process.Gas compositions in the reactor 6 change, and vacuum pump 14 gas in the exhaust line of finding time forms certain vacuum tightness, opens exhausr port 22 valves fast, and the gas that takes a morsel enters pipeline, by gas chromatography 10 its gas composition is analyzed.
Temperature control unit among the present invention comprises two independent parts.Both can provide experiment temperature required by constant water bath box 4, also can accelerate the generation of hydrate by the heat that the mode that liquid nitrogen cryogenics chuck 17 is installed is taken away in the hydrate generative process, simultaneously can also provide low temperature environment for carrying and the sample analysis of hydrate sample, guarantee the hydrate stability of sample.
The data collection and analysis system comprises data collecting card 15, computing machine 11 and each temperature/pressure sensor, it is used for gathering experimental data automatically every setting-up time, and experimental pressure and temperature control unit in the control reactor 6, described data collecting card 15 is connected with surge tank 3, PID operation valve 13 and reactor 6 respectively, and computing machine 11 is connected with data collecting card 15.Data acquisition and processing unit are collected each temperature, pressure value by data collecting card 15, import in the computing machine 11 and record, analyze.
The specific embodiment of hydrate sample analysis is as follows:
1, the quick sampling of present embodiment hydrate sample and XRD scanning analysis method are as follows:
1), the washed with de-ionized water reactor, drying; Preparing experiment usefulness gas and solution allocation;
2), solution is added in the reactor, reactor is installed, is placed water bath to be cooled to the experimental temperature of setting;
3), treat temperature stabilization after, gas is used in logical experiment in the reactor, washes away 3 evacuation of air of reactor; Or adopt the mode that vacuumizes to drain air;
4), feed experiment usefulness gas to set pressure, open magnetic agitation, the beginning hydrate generates experiment, the record experimental data.
5), treat that hydrate generates after, close the hydrate air intake valve, reactor is taken out of from water bath, the liquid nitrogen cryogenics chuck of liquid nitrogen is housed in its outside, remove to the XRD analysis test cabinet, carry out sample analysis;
6), treat XRD low temperature scanning ambient stable after, open vent valve, back out the single bolt of a side, two bolts of loosening opposite side after the kettle cover translation taken out, take out hydrate sample in the still fast;
7), sample places on the XRD sample platform fast, by directional light analysis scan sample, avoids the analytical error that causes because sample surfaces is inhomogeneous;
8), finish specimen preparation, carry out the XRD analysis of hydrate structure.
2, the quick sampling of present embodiment hydrate sample and NMR scanning analysis method are as follows:
1) washed with de-ionized water reactor, drying; Preparing experiment usefulness gas and solution allocation;
2) solution is added in the reactor, reactor is installed, place water bath to be cooled to the experimental temperature of setting;
3) treat temperature stabilization after, gas is used in logical experiment in the reactor, washes away 3 evacuation of air of reactor; Or adopt the mode that vacuumizes to drain air;
4) feed experiment usefulness gas to set pressure, open magnetic agitation, the beginning hydrate generates experiment, the record experimental data.
5) treat that hydrate generates after, close the hydrate air intake valve, reactor is taken out of from water bath, the liquid nitrogen cryogenics chuck of liquid nitrogen is housed in its outside, remove to NMR analytical test chamber, carry out sample analysis;
6) treat the levelling of NMR condition and " V " peak position after, open vent valve, back out the single bolt of a side, two bolts of loosening opposite side after the kettle cover translation taken out, take out hydrate sample in the still fast;
7) sample places fast and is in the liquid nitrogen control box agate mortar, and the hydrate sample is ground to form powdery, is filled in the sample hose of 4mm, determines that sample builds, and sample hose is installed, and carries out NMR and analyzes;
3, present embodiment hydrate sample in-situ Raman analytical approach is as follows:
1) washed with de-ionized water reactor, drying; Preparing experiment usefulness gas and solution allocation;
2) solution is added in the reactor, reactor is installed, place water bath to be cooled to the experimental temperature of setting;
3) treat temperature stabilization after, gas is used in logical experiment in the reactor, washes away 3 evacuation of air of reactor; Or adopt the mode that vacuumizes to drain air;
4) feed experiment usefulness gas to set pressure, open magnetic agitation, the beginning hydrate generates experiment, the record experimental data.
5) treat that hydrate generates after, close the hydrate air intake valve, reactor is taken out of from water bath, the liquid nitrogen cryogenics chuck of liquid nitrogen is housed in its outside, remove to the Raman analysis test cabinet, carry out the in-situ Raman analysis;
6) reactor is put on adjustable sample platform, changes scanning lens and connect chamfering, adjust the reactor position and make chamfering just press close to the reactor form, focusing is carried out scanning analysis to the hydrate structure of reactor inside;
7) can be to the gas in the reactor by adjusting experiment table under the mountain, liquid is Gu three-phase carries out scanning analysis respectively; By adjusting focusing position, the hydrate structure of distance form different depth is analyzed, obtain comprehensive and concrete hydrate structure signal in the still.
Above-listed detailed description is at the specifying of possible embodiments of the present invention, and this embodiment is not in order to limiting claim of the present invention, and the equivalence that all the present invention of disengaging do is implemented or change, all should be contained in the claim of this case.
Claims (9)
1. the hydrate characterization apparatus analyzed of an in-situ Raman, it is characterized in that: comprise stable air supply unit, hydrate generation/resolving cell, temperature control unit, data acquisition and processing unit, stablize air supply unit and be used for providing test gas to hydrate generation/resolving cell; Hydrate generation/resolving cell by injecting gas in the reactor in it (6) and test mixed solution, carries out hydrate and generates or decomposition run under predetermined condition; The temperature control unit is used for the temperature variation of control hydrate generation/resolving cell; Data acquisition and processing unit are used for gathering, preserving and analyze the variation of temperature, pressure and the gas composition of hydrate generation/resolving cell, and pressure and the temperature control cell temperature of control reactor (6).
2. the hydrate characterization apparatus analyzed of in-situ Raman as claimed in claim 1, it is characterized in that: stable air supply unit comprises gas cylinder (1), compressor (2), surge tank (3) and PID operation valve (13), described gas cylinder (1) forms one with reactor (6) and is connected branch road, and described gas cylinder (1), compressor (2), surge tank (3) and one of PID operation valve (13) formation are connected branch road and are connected with described reactor (6); When storage pressure was higher than the required predetermined pressure of experiment, gas directly entered reactor (6) by gas cylinder (1), or provided experiment required pressure via surge tank (3) for reactor (6); When storage pressure is lower than the required predetermined pressure of experiment, realize stable air-flow supply by compressor (2).
3. the hydrate characterization apparatus analyzed of in-situ Raman as claimed in claim 1 or 2, it is characterized in that: hydrate generation/resolving cell comprises reactor (6), magnetic stirring apparatus (5), vacuum pump (14) and gas chromatograph (10), described magnetic stirring apparatus (5) is arranged in the reactor (6), and vacuum pump (14) is connected with reactor (6) respectively with gas chromatograph (10).
4. the hydrate characterization apparatus analyzed of in-situ Raman as claimed in claim 3, it is characterized in that: the temperature control unit comprises constant water bath box (4) and is arranged on the outer dismountable low temperature liquid nitrogen chuck (17) of reactor (6) that described reactor (6) and surge tank (3) all are arranged in the warm water bath cabinet (4).
5. data collection and analysis as claimed in claim 2 system, it is characterized in that: the data collection and analysis system comprises data collecting card (15), computing machine (11) and each temperature/pressure sensor, it is used for gathering experimental data automatically every setting-up time, and experimental pressure and temperature control unit in the control reactor (6), described data collecting card (15) is connected with surge tank (3), PID operation valve (13) and reactor (6) respectively, and computing machine (11) is connected with described data collecting card (15).
6. the hydrate characterization apparatus analyzed of in-situ Raman as claimed in claim 1, it is characterized in that: described reactor (6) adopts the form of flat seal, realize the pressurize sealing by three outer bolt (18), wherein bolt (18) distribution triangular in shape, the top pressure that reactor (6) can bear is 8MPa, is provided with handle (19) at kettle cover.
7. the hydrate characterization apparatus analyzed of in-situ Raman as claimed in claim 1, it is characterized in that: described reactor (6) outside is equipped with dismountable liquid nitrogen cryogenics chuck (17), liquid nitrogen cryogenics chuck (17) is made by copper sheet, two parts chuck that separates is by chuck interface (24) splicing, hold liquid nitrogen or cold-producing medium or heating agent in the liquid nitrogen cryogenics chuck (17), the import (16) of reactor (6) both sides is connected the heat transfer that circulates of pump or condenser with outlet (23).
8. the hydrate characterization apparatus analyzed of in-situ Raman as claimed in claim 1, it is characterized in that: the form (7) that described reactor (6) surface arranges is made of at the high-purity quartz glass more than 95% a pair of ultraviolet light transmittance.
9. an analytical approach that adopts the hydrate characterization apparatus to carry out hydrate sample in-situ Raman is characterized in that, comprises the steps:
1) washed with de-ionized water reactor, drying; Preparing experiment usefulness gas and solution allocation;
2) solution is added in the reactor, reactor is installed, place water bath to be cooled to the experimental temperature of setting;
3) treat temperature stabilization after, gas is used in logical experiment in the reactor, washes away three evacuation of air of reactor; Or adopt the mode that vacuumizes to drain air;
4) feed experiment usefulness gas to set pressure, open magnetic agitation, the beginning hydrate generates experiment, the record experimental data;
5) treat that hydrate generates after, close the hydrate air intake valve, reactor is taken out of from water bath, the liquid nitrogen cryogenics chuck of liquid nitrogen is housed in its outside, remove to the Raman analysis test cabinet, carry out the in-situ Raman analysis;
6) reactor is put on adjustable sample platform, changes scanning lens and connect chamfering, adjust the reactor position and make chamfering just press close to the reactor form, focusing is carried out scanning analysis to the hydrate structure of reactor inside;
7) can be to the gas in the reactor by adjusting experiment table under the mountain, liquid is Gu three-phase carries out scanning analysis respectively; By adjusting focusing position, the hydrate structure of distance form different depth is analyzed, obtain comprehensive and concrete hydrate structure signal in the still.
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