CN209182272U - In-situ chemical reaction device and its and the combined system with nuclear magnetic resonance - Google Patents
In-situ chemical reaction device and its and the combined system with nuclear magnetic resonance Download PDFInfo
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- CN209182272U CN209182272U CN201820929667.3U CN201820929667U CN209182272U CN 209182272 U CN209182272 U CN 209182272U CN 201820929667 U CN201820929667 U CN 201820929667U CN 209182272 U CN209182272 U CN 209182272U
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Abstract
The utility model relates to in-situ chemical reaction device and its and combined system with nuclear magnetic resonance, the in-situ chemical reaction device be sealing straight tubular reactor, including air inlet pipeline, outlet pipe, and the inner and outer tubes being nested；Outer tube bottom end closure, open top；Inner tube open bottom end, open top；It is furnished with removable sealing element in the top of inner tube and outer tube；There is gap between inner tube bottom end and outer tube bottom end；There is gap between inner pipe wall and outer tube wall；Air inlet pipeline is connected to inner tube；Outlet pipe is connected to outer tube；The material of the in-situ chemical reaction device is non-magnetic material.The device is suitable for the fields such as chemical, Material Field nuclear magnetic resonance research, the hyperpolarization nuclear magnetic resonance imaging that can also be used for medical domain and nuclear magnetic resonance spectroscopy test.
Description
Technical field
The utility model relates to a kind of in-situ chemical reaction device and its and combined system with nuclear magnetic resonance, be suitable for changing
It learns, the nuclear magnetic resonance research of Material Field, the hyperpolarization nuclear magnetic resonance imaging that can also be used for medical domain and nuclear magnetic resonance spectroscopy
The fields such as test.
Background technique
The on-spot study of the structure of matter is that most chemists seek assiduously under chemical reaction process and chemical reaction condition
Analysis means.Scientists attempt on-spot study chemical reaction process on a variety of chemical analysis instruments, to open chemistry
The secret of reaction process, but since chemical reaction process majority is extremely complex, and the office of chemical analysis instrument itself
It is sex-limited, it can only obtain chemical reaction process little information details.Nuclear magnetic resonance technique can mutually be surveyed by the body to measured matter
It tries and provides its structural information, in being very suitable to catalyst structure variation in research such as catalytic reaction process and reacting
Between species detection and cause the great interest of people.But the intrinsic muting sensitivity feature of nuclear magnetic resonance technique limits people
The on-spot study structure of matter and chemical reaction process practice.
The muting sensitivity of nuclear magnetic resonance technique is based on its physical principle, i.e. NMR signal intensity depends on external magnetic field
After the energy level splitting that middle atomic nucleus generates between different energy levels i on population difference.Its different energy level cloth inning meets Boltzmann point
Cloth, under thermal equilibrium condition, the difference very little of the i on population between nuclear difference energy level.In the two energy level systems that Zeeman is split point
In system, polarizability is defined as the difference of two ionic fractional abundances divided by the sum of i on population.At room temperature usually1H nuclear polarization can only reach
To 10-5Magnitude.To improve magnetic resonance detection sensitivity, usually there are two types of methods.A kind of method is improved in thermal balance item
Nuclear spin polarization degree under part, so major instrument manufacturer facility quotient constantly improves external magnetic field strength at present, to improve polarizability,
To improve detection sensitivity.But the raising of external magnetic field strength means the rapid increase of instrumentation cost, and theoretically
The mr techniques of higher resonant frequency are not supported yet.And another thinking is that nuclear spin polarization degree is improved by polarization transfer
To being more than thermal equilibrium condition, and detection sensitivity is greatlyd improve.Polarizability can be improved there are many effective method at present
Several orders of magnitude, such as spin-exchange optical pumping, dynamical nuclear polarization (DNP).Hyperpolarization is obtained by spin-exchange optical pumping129For the method for Xe in field of biomedicine, material structure research field has certain applications.
The access approaches of the rare inert gas of hyperpolarization are usually to utilize optical pumping spin-exchange method.It illustrates such as
Under, alkali metal is mixed with rare inert gas and is placed under the magnetic field of some strength, is shone using the circularly polarized light of specific wavelength
The mixture being located in magnetic field is penetrated, can be obtained the rare inert gas of hyperpolarization.Its principle is that alkali metal atom is made in magnetic field
It is split point with lower energy level, spin high degree of polarization under circularly polarized light effect, because alkali metal atom and rare inert gas are sufficiently mixed
It closes, its spin angular momentaum is passed to by rare inert gas by approach alkali metal such as collisions, therefore obtains the rare lazy of hyperpolarization
Property gas.Bouchiat etc. is studied [1] to spin-exchange metastasis, it is believed that the rare inert gas of alkali metal atom-
The Van der Waals molecule of formation plays an important role to the electronic polarization relaxation of alkali metal atom, in downfield in situation certainly
Rotation exchange process occur mainly between the Van der Waals molecule of the rare inert gas of alkali metal atom-, when use tesla
When the high-intensity magnetic field of magnitude, Van der Waals molecule, the spin between alkali metal atom and rare Inert gas molecule not will form
Exchanging mechanism can be explained by two body collision theory.Grover research discovery [2], in downfield, alkali metal atom and Xe are former
Spin-exchange between son has very high efficiency.The polarizability of rare inert gas can be made to mention using spin-exchange technology
It is high by about 103~105Magnitude.
The acquisition of hyperpolarized gas detects chemical reaction process using it for people and structure of matter knowledge provides greatly
Convenience.Last century the eighties, Fraissard [3] and Ripmeester [4] first will129Xe is introduced into as probe atom
The nuclear magnetic resonance research field of the catalysis materials such as molecular sieve.Xenon (Xe) is a kind of inertia monoatomic gas, hardly with it is other
Substance chemically reacts.129The nuclear-spin quantum number of Xe isotope is 1/2, natural abundance 26.4%.The spherical shape of xenon atom
Electron cloud is very big and is easily influenced by ambient enviroment.Due to not chemically reacted with other substances, so when contact material, pole
The surfaces externally and internally of substance easily is acted on, to influence129The cloud density of Xe, and then influence the magnetic screen of Xe core and influence it
Chemical shift.One peacekeeping two dimension129Xe NMR technology is widely used in studying pore structure, the object particle of inorganic and organic materials
Distribution, position and binding molecule coking on catalyst be in the diffusion process on surface etc..Its ambient enviroment of Xe atom pair
Sensibility has made129Xe NMR becomes one of the important means of catalyst structure research.The hyperpolarization of induced with laser129Xe isotope
Probe technique, by using inert Xe atom and substance interaction and with product in chemical reaction process and intermediary
Kind etc. interaction, can structure change to substance in chemical reaction process and the state of reaction intermediates kind etc. have
The research of effect.
The in situ NMR research of chemical reaction process has had vicennial history.Nineteen ninety-five, Hunger are carried out
The magnetic resonance detection of heterogeneous catalytic reaction (J.Chem.Soc.Chem.Commun.1995,1423-1424) in situ, to methanol
Catalytic conversion process system research is being carried out close under true reaction condition, it was found that be catalyzed in catalytic conversion process
Agent surface forms the evidence of reaction intermediates.Hyperpolarization nuclear magnetic resonance technique is used for material hole knot by Liu et al. [5~8]
In the research of structure and achieve many significant results.
[1]Bouchiat C C,Bouch iat M A,Porrier L C.Phys.Rev.1969,181:144
[2]Grover B C.Ph ys.Rev.Let t.1978,40:391
[3]Ito T,Fraissard J.J Chem Phys,1982,76(11):5225
[4]Ripmeester J A.J Am Chem Soc,1982,104(1):289
[5]Liu S B,Lin T S,Yang T C,Chen T H,Hong E C,Ryoo R.J Phys Chem,
1995,99(20):8277
[6] Sakthivel A, Huang S J, Chen W H, Lan Z H, Chen K, H, Kim T W, Ryoo R,
Chiang AS T,Liu S B.ChemMater,2004,16(16):3168
[7]Huang S J,Huang C H,Chen W H,Sun X P,Zeng X Z,Lee H K,Ripmeester J
A,Mou C Y,Liu S B.J PhysChem B,2005,109(2):681
[8]Huang S J,Huh S,Lo P S,Liu S H,Lin V S Y,Liu SB.Phys Chem Chem
Phys,2005,7(16): 3080
Utility model content
The utility model is intended to develop adaptability, and widely on-line NMR in situ detects and is combined other analysis hands
The chemical reaction equipment of section, other analysis means can be the analysis instruments such as mass spectrograph, chromatograph and spectrometer, by rare
Chemical reaction process is studied in the interaction of inert gas probe and chemical reaction system, furthermore is established the rare of hyperpolarization
Inert gas probe is controllable and effectively introduces the device of above-mentioned reactor, so that can cooperate between the two, to reach
Study the purpose of chemical reaction process.
To reach the target for applying the rare inert gas probe of hyperpolarization to study chemical reaction process, establishes and be suitable for nuclear-magnetism
The online chemical reactor and its control system for the in situ detection that resonates, the one aspect of the utility model, providing one kind can
The chemical reaction equipment to work under the conditions of nuclear magnetic resonance in situ, in-situ chemical reaction device, the in-situ chemical reaction device are close
Seal straight tubular reactor, including air inlet pipeline, outlet pipe, and the inner and outer tubes being nested；Outer tube bottom end closure, top are spacious
It opens；Inner tube open bottom end, open top；It is furnished with removable sealing element in the top of inner tube and outer tube；Inner tube bottom end and outer tube bottom
There is gap between end；There is gap between inner pipe wall and outer tube wall；Air inlet pipeline is connected to inner tube；Outlet pipe and outer
Pipe connection；The material of the in-situ chemical reaction device is non-magnetic material；The non-magnetic material is preferably glass, ceramics or has
Machine polymer.
Further, when reactant is solid phase, solid-phase reactant is filled in inner tube；When reactant is liquid phase, liquid phase
Reactant is filled in outer tube.
Further, when reactant is solid phase, solid-phase reactant is filled in bottom of inner tube；When reactant is liquid phase,
The bottom end of inner tube protrudes into the bottom of liquid phase reactor object close to the liquid level or inner tube of liquid phase reactor object.
Further, the in-situ chemical reaction device further includes gas control system, and the gas control system is equipped with two
A or more than two reaction gas intake lines, the reaction gas intake line set gradually pressure regulator valve, water oxygen along gas flow
Filter, mass flow controller, check valve.
The another aspect of the utility model provides in-situ chemical reaction device and nuclear magnetic resonance combined system, the combination system
System includes above-mentioned in-situ chemical reaction device；The in-situ chemical reaction device extend into the detection coil position of nmr probe
It sets；Reaction gas needed for in-situ chemical reaction is connected to through air inlet pipeline with inner tube.
Using the method for the in-situ chemical reaction and the detection chemical reaction of nuclear magnetic resonance combined system, including following step
Suddenly, solid-phase reactant is filled in inner tube or liquid phase reactor object is filled in outer tube by (1)；(2) in-situ chemical reaction device is stretched
Enter the detection coil position to nmr probe；(3) chemical reaction gas is passed through to inner tube through air inlet pipeline.
It is total to combine above-mentioned in-situ chemical reaction device application nuclear-magnetism using hyperpolarized gas as probe for the utility model another further aspect
Vibration technical research chemical reaction process and structure of matter feature.It is anti-to provide a rare inert gas probe generator, in-situ chemical
Device, nuclear magnetic resonance combined system are answered, the combined system includes above-mentioned in-situ chemical reaction device；The in-situ chemical reaction device is stretched
Enter the detection coil position to nmr probe；Reaction gas needed for in-situ chemical reaction is connected to through air inlet pipeline with inner tube；
The rare inert gas that rare inert gas probe generator generates is passed through inner tube through air inlet pipeline as detection gas.
Using above-mentioned rare inert gas probe generator, in-situ chemical reaction device and nuclear magnetic resonance combined system detectionization
Learn reaction method, use the rare inert gas of hyperpolarization as probe application nuclear magnetic resonance technique detecting material structural information with
And the device of chemical reaction process, include the following steps, solid-phase reactant is filled in inner tube or fills out liquid phase reactor object by (1)
It fills in outer tube；(2) in-situ chemical reaction device is extend into the detection coil position of nmr probe；(3) through air inlet pipeline to
Inner tube is passed through the rare inert gas of hyperpolarization and/or chemical reaction gas.
The another aspect of the utility model also provides rare inert gas probe generator, in-situ chemical reaction device, nuclear-magnetism
Resonance, gas analysis instrument combined system, the combined system include the in-situ chemical reaction device；In-situ chemical reaction device
It extend into the detection coil position of nmr probe；Outlet pipe is connected to the gas analysis instrument；The gas analyzer
Device is preferably quadrupole mass spectrometer or gas chromatograph.
Any of the above-described combined system can be applied to test in microporous catalyst material cellular structure.
In-situ chemical reaction device described in the utility model is made of special material.Since reactor is placed in high-intensity magnetic field
The heart, magnetic field strength can achieve 14 teslas or more, and special material requirement cannot include ferromagnetic material, because ferromagnetic
Property substance can influence nuclear magnetic resonance spectrometer magnetic field's regularity, to influence nuclear magnetic resonance under the action of high-intensity magnetic field strongly
Detection.The material also can not the material containing metal material or containing strong absorption of electromagnetic radiation.The principle of nuclear magnetic resonance
Show the electromagnetic radiation for emitting several hectowatts or even upper kw of power when magnetic resonance detection, above-mentioned material can largely absorb electromagnetism
Radiation, substantially reduces the efficiency of nuclear magnetic resonance, moreover it is possible to emit secondary radiation, and bring spurious signal in nmr spectrum；
Undesirable sample heating can be caused by having again, to influence the stabilization of detection and chemical reaction system.It is described in the utility model
Material can be material with above-mentioned requirements non-contravention, include the materials such as glass, ceramics, organic polymer.
In-situ chemical reaction device described in the utility model is not limited by nuclear magnetic resonance spectrometer magnetic field strength.Reactor
Pattern is only associated with the probe form of nuclear magnetic resonance spectrometer used, and realizes and be suitble to a variety of nuclear magnetic resonance spectrometer probe shapes
The reactor of formula.
The utility model relates to the device of on-spot study chemical reaction process, which is suitable for high temperature, low
It operates under the conditions of temperature, believes with the nuclear magnetic resonance that can provide chemical reaction process and the structure of matter with nuclear magnetic resonance technique combination
Breath, can also provide the reaction products information such as quadrupole mass spectrometry, and 50 milliseconds of time-resolved reaction dynamics also may be implemented and grind
Study carefully.The hyperpolarization nuclear magnetic resonance that the device is suitable for chemical, Material Field nuclear magnetic resonance research, can also be used for medical domain
The fields such as imaging and nuclear magnetic resonance spectroscopy test.
Detailed description of the invention
Fig. 1 gas control system, in-situ chemical reaction device and flow chart is combined with nuclear magnetic resonance spectrometer and mass spectrograph；
Fig. 2 coupled instrument system block diagram；
Fig. 3 A liquid probe reactor (gas-solid phase) structural schematic diagram
Fig. 3 B liquid probe reactor (gas-solid phase) decomposition diagram
Fig. 4 in-situ chemical reaction device and nuclear magnetic resonance apparatus, which are placed, schemes；
Fig. 5 A, 5B are liquid probe reactor (liquid phase) structural schematic diagram
The MFI structure hyperpolarization of Fig. 6 different disposal condition129Xe NMR spectra
Fig. 7 MFI structure sample 2# hyperpolarization129Xe NMR spectra
In Fig. 1,501,502 gas sources, 511,512 pressure regulator valves, 521,522 water oxygen filters, 531,532 mass flowmenters,
541,542 check valves, 551,552 ball valves, 594,596 shut-off valves, 561 pressure gauges, 597 hyperpolarized gas entrances, 592 nuclear-magnetisms
Resonance spectrometer, 593 reactors, 591 quadrupole mass spectrometer, 595 needle-valves；
In Fig. 2,811 reaction gas control systems, 812NMR spectrometer, 813 hyperpolarization generators, 814NMR control system,
815 quadrupole mass spectrometer；
In Fig. 3 B, 601 reactor outer tubes, 602 reactor inner tubes, 611 sealing bar fixing bolts, 612 sealing bars, 613 rubbers
Glue seals O circle, 621 inlet seal caps, 622 outlet seal caps, 623 air inlet pipe, 624 escape pipes, 631 solid reactants；
In Fig. 4,702 reactors, 711 nuclear magnetic resonance spectrometer superconducting coils 711, nmr probe 712, nuclear magnetic resoance spectrum
Instrument transmitting coil 713.
Specific embodiment
One specific implementation principle and operating method of the utility model are described below in conjunction with diagram.
Fig. 1 is gas control system, in-situ chemical reaction device and nuclear magnetic resonance spectrometer and other analysis instrument (such as mass spectrums
Instrument) synchronize the combination flow chart detected.Using magnetic nuclear resonance method, chemical reaction process is studied by hyperpolarization probe molecule
With structure of matter feature, this needs the in-situ chemical reaction system that uses of a nuclear magnetic resonance apparatus, including situ reactor and
Control of chemical reaction system.Control of chemical reaction system includes gas source type control facility, gas flow control facility, gas
Pressure controls facility, temperature of reactor control facility (being not drawn into figure).
The utility model gas control system can realize the concentration of rare inert gas and any adjusting control of flow.It is super
Probe of the rare inert gas as chemical reaction that polarize is adjustable as and reacts when coping with different chemical reaction demands
Chemical reaction system requires to be adapted in device.
Preferably, gas control system design there are two or more than two reaction gas air inlet pipelines, the reaction gas into
Air pipe sets gradually pressure regulator valve, water oxygen filter, mass flow controller, check valve along gas flow.Gas is by decompression
To after the pressure of setting, oxygen molecule and hydrone in gas are further filtered out by water oxygen filter, by quality stream
Amount controller control is to reactor 593 is entered after the gas flow of needs, and in chemical reaction process, hyperpolarized gas probe is through entering
Enter reactor after mouth 597, shut-off valve 596, the detection through nuclear magnetic resonance spectrometer 592 provides reaction process and structure of matter variation
Information, simultaneous reactions product can the analysis Jing Guo quadrupole mass spectrometer 591 provide reaction carry out degree information.Needle-valve 595 can
To adjust the reaction pressure of reactor.Reactor is carried out in broader Reaction conditions range.
Two or more air inlet pipelines converge before entering the reactor, and before converging, and are respectively set unidirectional
Valve.It can prevent other road gases from reversely oppressing the flowmeter on the road when a few road gas mixings and flow backwards.
The utility model is connected to per the mass flow controller on gas passage all the way by control to which dynamic controls
Per the output quantity of gas all the way, achieve the purpose that any control reaction gas and detection gas concentration.
The utility model relates to the channels flowed through to hyperpolarized gas probe, and certain material to be selected to be made, these materials can be with
It is brass, the inner wall of glass, polyethylene, polytetrafluoroethylene (PTFE) etc., the molding equipment of material described above is required to by functionalization
Processing.Functionalization, which refers to, herein covers surface using nonpolar solvent, removes the polar group on surface.Because of table
The polar group in face has very strong unpolarizing for the rare inert gas of hyperpolarization, therefore overrides interior table to greatest extent
The holding of the polar group in face inert gas polarizability rare for hyperpolarization is vital.Nonpolarity described herein is molten
Agent is often referred to silylating reagent, such as chlorosiloxane chlorosilane, it can be with the inner surface of the above-mentioned material to be covered
Firm connection, and effectively cover the polar group of its inner surface.
Fig. 2 is entire chemical reaction analysis coupled instrument system flow diagram.Nuclear magnetic resonance spectrometer 812 is the pass of system
Key instrument, it is in-situ chemical reaction described in the utility model and the rare inert gas probe NMR detection of hyperpolarization
Key equipment, situ reactor are placed in the detection coil of nuclear magnetic resonance spectrometer 812, usually it be commodity nuclear magnetic resoance spectrum
Instrument, NMR control system 814 provide radio-frequency pulse transmitting, NMR signal detection, situ reactor to nuclear magnetic resonance spectrometer
Temperature control etc..The gas that in-situ chemical reaction device needs is provided by reaction gas control system 811, the rare inert gas of hyperpolarization
Probe is provided by hyperpolarization generator 813, is examined after reaction product outflow reactor through quadrupole mass spectrometer 815 in situ reactor
Survey can provide reaction and carry out degree information.Next key aspect component is described, and to the control unrelated with utility model
System part is not described in detail.
The utility model in-situ chemical reaction device is sealed straight tubular reactor, closed at one end, the other end of reactor
Open, open one end can be dismounted equipped with sealed connection facility, can load and unload test sample, be tightly connected on facility and assembled
There is the turnover pipeline of gas.The reactor is inner tube and outer tube nested structure, and inner tube is nested in outer tube, and inner tube can be taken off.
The utility model relates to the device of on-spot study chemical reaction process, which is suitable for high temperature, low
It operates under the conditions of temperature, believes with the nuclear magnetic resonance that can provide chemical reaction process and the structure of matter with nuclear magnetic resonance technique combination
Breath, can also provide the reaction products information such as quadrupole mass spectrometry, the time-resolved reaction dynamic studies of millisecond also may be implemented.
The device be suitable for chemistry, Material Field nuclear magnetic resonance research, can also be used for the hyperpolarization nuclear magnetic resonance of medical domain at
The fields such as picture and nuclear magnetic resonance spectroscopy test.
Embodiment 1
A kind of way of realization of the utility model in-situ chemical reaction device is as shown in Figure 3A and Figure 3B, and Fig. 3 A is gas-solid phase reaction
The structure chart of device (reactor A), Fig. 3 B are that gas-solid phase reactor (reactor A) forms exploded view.
Reactor is closed straight pipe type, and the bottom end closure of the outer tube 601 of reactor, open top end, there are screw thread, top in top
By 612 sealed outer pipe 601 of sealing bar, 613 are enclosed equipped with rubber seal O in sealing bar 612, sealing bar 612 is solid by sealing bar
Determine bolt 611 to be sealed with outer tube 601.The turnover pipeline of gas is equipped in sealing bar 612.The reactor be inner tube with
Outer tube nested structure, gas is entered by inner tube reaches sample top, flows out after flowing through sample from bottom, through outer tube and inner tubal wall
Gap is exited.Reactor inner tube 602 can be taken off.Solid reactant is placed in bottom of inner tube, and bottom of inner tube is close to reactor outer tube
Bottom.When carrying out in situ NMR research, reactor A bottom extend into the detection coil position of nmr probe.
The position is at the center of nuclear magnetic resonance spectrometer superconducting coil, is intended to sample and is completely disposed within the scope of detection coil.Referring to attached
Fig. 4.Reactor is connect by pipeline with gas control equipment, and reaction gas is provided by gas control equipment, pressure, flow, instead
Should gas type etc. by its regulation.
The making material of chemical reactor selects non-magnetic material.Reaction tube is made of heatproof glass, and sealing bar has
PEEK material is made.The pressure that reactor can be resistant to can achieve 1MPa, and the temperature that can be resistant to is -100 DEG C to 400 DEG C.
Reactor can substitute the sample cell of nuclear magnetic resonance.
The working principle of reactor A is done described below:
Reactor A bottom extend into the detection coil position of nmr probe.The position is super in nuclear magnetic resonance spectrometer
At the center of loop, it is intended to sample and is completely disposed within the scope of detection coil.Reactor is connected by pipeline and gas control equipment
It connects, reaction gas is provided by gas control equipment, and pressure, flow, reaction gas type etc. are by its regulation.Reactor can be resistant to
Pressure can achieve 1MPa, the temperature that can be resistant to be -100 DEG C to 400 DEG C.Heterogeneous chemical reaction is in operating condition appropriate
Lower progress；The rare inert gas of hyperpolarization is passed through reactor by parallel pipeline, is surpassed while to realize reactor work
Polarize the magnetic resonance detection of rare inert gas probe.React the reacted device exit passageway outflow of the tail gas completed and through one
Controllable valve emptying, is connected with gas analysis instrument on flow pass, and analysis instrument can be quadrupole mass spectrometer either gas
Chromatography, the degree carried out to reaction product and reaction test and analyze.To realize magnetic resonance detection and other points
Instrument crosslinking is analysed in real time to analyze and research to reaction system.
There are two types of the working conditions of reactor A, difference be the operating position of reactor heating method difference and reactor not
Together.The first is online in situ NMR spectrometer working condition, and reactor is placed in inside nuclear magnetic resonance spectrometer when working, instead
The temperature control mode of device is answered to provide for the probe of nuclear magnetic resonance spectrometer itself, its usual temperature controlling range is smaller, but can
Really to realize in situ detection, chemical reaction can carry out the nuclear magnetic resonance of the rare inert gas probe of hyperpolarization while progress
Detection；Second is the quasi- home state of on-line NMR, positioned at the outside of nuclear magnetic resonance spectrometer, reactor when reactor works
Temperature control implemented by additional temperature control unit, its advantage is that reaction temperature is not limited by the temperature of nuclear magnetic resonance spectrometer
System, can achieve required any temperature, and reaction proceeds to a certain moment, can be transferred to core online for reactor is cracking
Inside magnetic spectrograph, magnetic resonance detection is carried out.This reaction utensil has following feature, collection chemical reaction, rare inert gas probe
Magnetic resonance detection is.It is gas that the reactor, which is suitable for research mobile phase, and stationary phase is the reactant of solid powdery
System.This reactor is suitable for the common liquid probe of nuclear magnetic resonance spectrometer.
When heterogeneous chemical reaction carries out under operating condition appropriate, the rare inert gas of hyperpolarization is passed through reactor, from
And realize the magnetic resonance detection that hyperpolarization rare inert gas probe is carried out while reactor work.React the tail gas completed
Reacted device exit passageway outflow is simultaneously vented through a controllable valve, and gas analysis instrument is connected on flow pass, is analyzed
The degree that instrument can carry out reaction product and reaction tests and analyzes.To realize magnetic resonance detection and other analyzers
Device combination in real time analyzes and researches to reaction system.
Embodiment 2
Another way of realization of above-mentioned chemical reactor, gas-liquid chemical reactor (reactor B), liquid reactants filling
In outer tube, basic structure is similar to reactor A, and difference is that the length of sample cell inner tube or shape are different, the reactor
Suitable for studying the heterogeneous chemical reaction system of liquids and gases.
Attached drawing 5A and 5B are respectively the structural schematic diagram of two kinds of different gas-liquid reactors: reactor shown in attached drawing 5A, interior
Pipe is 30~40mm shorter than the inner tube of reactor A, and when loading liquid reactants, inner tube bottom end (i.e. gas vent) is close to liquid in outer tube
The liquid level of precursor reactant object but liquid level is not contacted, so that the gas of flowing influences liquid smaller, liquid will not be by for such design
Gas, which is blown, to seethe and is bubbled, and does not have an impact substantially to the detection of nuclear magnetic resonance in this way.Reactor shown in attached drawing 5B, inner tube
Length is identical as reactor A inner tube, and inner tube (preferably its base diameter is smaller) reaches always the liquid of liquid reactants in outer tube
Bottom, entering the gas in liquid by inner tube can come into full contact with liquid, increase the contact area between gas-liquid, to increase
The solubility of gas in a liquid.The rare inert gas of hyperpolarization can be dissolved into liquid, and carrying out magnetic resonance detection can be with
Study the process of chemical reaction.
The reactor can not only carry out the nuclear magnetic resonance research of the rare inert gas of hyperpolarization, can also be anti-by acquiring
Other NMR signals of system are answered, such as1H spectrum,13The process of the further research chemical reaction such as C spectrum.The reactor is used
With learning gas and liquid multi-phase reaction system, it is applicable in nuclear-magnetism instrument range and is same as above a kind of reactor.
Embodiment 3
The present embodiment utilizes hyperpolarization129Xe probe studies the pore structure variation in the porous material of MFI structure.
Reactor described in Application Example 1, measured matter record the MFI structure material of each different structure at different temperature
's129Xe NMR spectra.
1. experimental method
1 reactor of Application Example, using hyperpolarization129Xe probe atom, research system are different preparations and processing method
The molecular sieve of obtained MFI structure, the molecular sieve system are 3 H-ZSM-5 (MFI structure) contrast samples, and sample 1 is original powder
H-ZSM-5 sample, that is, the H-ZSM-5 sample synthesized is not specially treated, about 40~60 mesh of sample particle (40~10 microns)；
Sample 2 is the binder of addition 40% on the basis of sample 1, and binder is the dusty material gamma oxidation aluminium powder of pore-free, is passed through
Extrusion forming is the graininess of 2~3 mm dias after mechanical mixture；Sample 3 is that the direct extrusion forming of sample 1 is 2~3 millimeters
The graininess of diameter.3 tested samples through 420 DEG C vacuum dehydration 20 hours, vacuum degree maintains 10-4Pa is horizontal.Carry out super
Change129The test of Xe nuclear magnetic resonance, test temperature is at -80 DEG C to 35 DEG C.129Xe resonant frequency is 110MHz, and pulse protocol is simple venation
Stroke sequence.
2. experimental result
H-ZSM-5 is the common microporous catalyst material of petrochemical industry, and wherein its pore properties is to influence industrial process
One of vital factor.Common hole analysis instrument such as physical adsorption appearance can provide the specific surface area and pore size distribution of material
Information, but it is helpless for the fine difference in duct.And xenon gas atoms are highly prone to week due to its electron outside nucleus cloud
The influence in collarette border, it is particularly sensitive to the variation of duct size.Fig. 6 is the hyperpolarization of above-mentioned 3 samples129Xe NMR spectra, from
In figure it can be found that under 273K, the H-ZSM-5 sample 1# without forming processes, chemical shift is~109ppm；Through being squeezed into
Its chemical shift of H-ZSM-5 sample 3# of type is~104ppm, and spectral peak slightly broadens；And the physical mixed H- of binder
There is the two peak structure with acromion within the scope of 104~109ppm in ZSM-5 sample 2#, and different treatment conditions occur bright
Aobvious difference.3 samples are carried out the study found that sample 1# and sample 3# is in all temperature models within the scope of -80 DEG C to 35 DEG C
It encloses and interior shows as a single peak, it is meant that its cellular structure is single, but the duct between them embodies
Difference.Fig. 7 gives spectral peak of the sample 2# within the scope of -30 DEG C to 35 DEG C, hence it is evident that finds out it with two peak structure.From spectral peak
Chemical shift analysis, the two peaks are microcellular structure, and aluminium oxide is usually not in microcellular structure, it is meant that this two kinds
Duct is all from the micropore of H-ZSM-5, and it is understood that the molecular sieve only has single micropore, and two peaks occur means have
Two kinds of different ducts occur, and two kinds of ducts are separation.This experimental result has the preparation of catalyst extremely important
Meaning.
Claims (9)
1. in-situ chemical reaction device, which is characterized in that
The in-situ chemical reaction device is sealing straight tubular reactor, including air inlet pipeline, outlet pipe, and the inner tube being nested
And outer tube；
Outer tube bottom end closure, open top；
Inner tube open bottom end, open top；
It is furnished with removable sealing element in the top of inner tube and outer tube；
There is gap between inner tube bottom end and outer tube bottom end；
There is gap between inner pipe wall and outer tube wall；
Air inlet pipeline is connected to inner tube；
Outlet pipe is connected to outer tube；
The material of the in-situ chemical reaction device is non-magnetic material.
2. in-situ chemical reaction device according to claim 1, which is characterized in that the non-magnetic material is glass, ceramics
Or organic polymer.
3. in-situ chemical reaction device according to claim 1 or 2, which is characterized in that
When reactant is solid phase, solid-phase reactant is filled in inner tube；
When reactant is liquid phase, liquid phase reactor object is filled in outer tube.
4. in-situ chemical reaction device according to claim 3, which is characterized in that
When reactant is solid phase, solid-phase reactant is filled in bottom of inner tube；
When reactant is liquid phase, the bottom end of inner tube protrudes into the bottom of liquid phase reactor object close to the liquid level or inner tube of liquid phase reactor object
Portion.
5. in-situ chemical reaction device according to claim 1, which is characterized in that the in-situ chemical reaction device further includes gas
Body control system, the gas control system are equipped with two or more reaction gas intake lines, the reaction gas input
Pipeline sets gradually pressure regulator valve, water oxygen filter, mass flow controller, check valve along gas flow.
6. the combined system of in-situ chemical reaction device and nuclear magnetic resonance, which is characterized in that
The combined system includes in-situ chemical reaction device described in claim 1-5 any one；
The in-situ chemical reaction device extend into the detection coil position of nmr probe；
Reaction gas needed for in-situ chemical reaction is connected to through air inlet pipeline with inner tube.
7. the combined system of in-situ chemical reaction device and nuclear magnetic resonance, which is characterized in that the combined system is rare indifferent gas
Body probe generator, in-situ chemical reaction device, nuclear magnetic resonance combined system；
The combined system includes in-situ chemical reaction device described in claim 1-5 any one；
The in-situ chemical reaction device extend into the detection coil position of nmr probe；
Reaction gas needed for in-situ chemical reaction is connected to through air inlet pipeline with inner tube；
The rare inert gas that rare inert gas probe generator generates is passed through inner tube through air inlet pipeline as detection gas.
8. the combined system of in-situ chemical reaction device and nuclear magnetic resonance, which is characterized in that the combined system is rare indifferent gas
Body probe generator, in-situ chemical reaction device, nuclear magnetic resonance, gas analysis instrument combined system；The combined system includes
In-situ chemical reaction device described in claim 1-5 any one；In-situ chemical reaction device extend into the inspection of nmr probe
Test coil position；Outlet pipe is connected to the gas analysis instrument.
9. the combined system of in-situ chemical reaction device and nuclear magnetic resonance according to claim 8, which is characterized in that the gas
Body analysis instrument is preferably quadrupole mass spectrometer or gas chromatograph.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110609053A (en) * | 2018-06-15 | 2019-12-24 | 中国科学院大连化学物理研究所 | In-situ chemical reactor and system for combining in-situ chemical reactor with nuclear magnetic resonance |
| CN111537540A (en) * | 2020-05-18 | 2020-08-14 | 中国科学院精密测量科学与技术创新研究院 | Para-hydrogen induced polarization device and method used in low magnetic field |
| CN116223554A (en) * | 2023-05-09 | 2023-06-06 | 中国科学院精密测量科学与技术创新研究院 | Device and method for detecting dDNP (digital dna pathway) probe molecule multichannel metabolic tracking |
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2018
- 2018-06-15 CN CN201820929667.3U patent/CN209182272U/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110609053A (en) * | 2018-06-15 | 2019-12-24 | 中国科学院大连化学物理研究所 | In-situ chemical reactor and system for combining in-situ chemical reactor with nuclear magnetic resonance |
| CN111537540A (en) * | 2020-05-18 | 2020-08-14 | 中国科学院精密测量科学与技术创新研究院 | Para-hydrogen induced polarization device and method used in low magnetic field |
| CN116223554A (en) * | 2023-05-09 | 2023-06-06 | 中国科学院精密测量科学与技术创新研究院 | Device and method for detecting dDNP (digital dna pathway) probe molecule multichannel metabolic tracking |
| CN116223554B (en) * | 2023-05-09 | 2023-08-04 | 中国科学院精密测量科学与技术创新研究院 | Device and method for detecting dDNP probe molecule multichannel metabolic tracking |
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