CN109991258A - A kind of magnetic resonance detection method of F- T synthesis water constituent - Google Patents
A kind of magnetic resonance detection method of F- T synthesis water constituent Download PDFInfo
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Abstract
The invention belongs to the analytical chemistry fields of F- T synthesis water constituent detection, and in particular to a kind of magnetic resonance detection method of F- T synthesis water constituent is based on three-dimensional NMR diffusion sequence spectrum-1H‑1H same core chemical shift correlated spectroscopy, it is different with the difference of coupled signal using the diffusion rate of each ingredient in a solvent in F- T synthesis water, diffusion rate obtained and coupled signal data are showed in the form of three-dimensional map, the transverse and longitudinal coordinate of map is chemical shift, ordinate is diffusion coefficient, according to the difference of each component diffusion coefficient in F- T synthesis water, the chemical shift plane with different diffusion coefficients is obtained on ordinate, then basis1H‑1The coupled signal of H same core chemical shift correlated spectroscopy figure, successively identification has the compound of same diffusion coefficient value, realizes the detection to each ingredient in F- T synthesis water.The resulting analysis visual result of this method is illustrated, and detection resolution is high, easy to operate, and as a result accurately, accuracy is high, can qualitative and quantitative detection F- T synthesis water sample composition, and be suitable for the qualitative detection of a variety of low-carbon small molecule compound ingredients.
Description
Technical field
The invention belongs to the analytical chemistry fields of F- T synthesis water constituent detection, and in particular to a kind of F- T synthesis water constituent
Magnetic resonance detection method, the present invention is a kind of based on three-dimensional NMR diffusion sequence spectrum-1H-1H same core chemical potential phase shift
The nuclear magnetic spectrum for closing spectrum, the Difference test using the diffusion rate in a solvent of each ingredient in F- T synthesis water and coupled signal take
Hold in the palm the magnetic nuclear resonance method of the composition of each ingredient in synthetic water.
Background technique
F- T synthesis is the key technology during ICL for Indirect Coal Liquefaction, is using synthesis gas as raw material, in catalyst and suitably
Reaction condition under liquid hydrocarbon fuel and its chemicals of the synthesis based on paraffin hydrocarbon technical process, product includes various alkane
Hydrocarbon, alkene, oxygen-containing organic compound and by-product CO2And H2O.With the continuous development of China's coal liquefaction industry, especially ten thousand
The extensive use of tonne syrup state bed Fischer Tropsch synthetic technology, while obtaining liquid fuel, the water phase that can also obtain 10,000 tons is produced
Object.If these water-phase products are precisely analyzed and efficiently used, it can get tens kinds of organic oxygen-containings such as a large amount of alcohol, aldehyde, ketone, acid
Compound, as good chemical products and large Chemical Manufacture raw material has broad application prospects and commercial value.
However, the main component in F- T synthesis water is that structure is similar, small molecule compound similar in molecular weight makes score
Analysis identification is very difficult.Further, since each compositional polarity is similar, thermal stability is poor, also that the analysis for increasing reaction mixture is difficult
Degree.The conventionals method of analysis such as gas chromatography and high performance liquid chromatography, application range is limited, operating process is complicated.For example, gas
It often needs to carry out particular procedure to chromatographic column during GC headspace analysis analysis F- T synthesis water, tests needs to adapt to it.
Cover entitled " the gas chromatography measurement Fischer-Tropsch synthesized water phase product being published on the 1st phase " chromatography " of volume 33 in 2014 such as blue and green
In low-carbon alcohols, aldehyde, ketone compound " method, pass through and temperature programming is carried out to polarity chromatographic column realize separation to each ingredient.
Liquid chromatogram in most cases can avoid complicated derivatization operation, but also usually need by the polarity of modulation mobile phase
Structure is completed using the more expensive analytical standard product auxiliary of price to point out.
Conventional nuclear magnetic resonance map, such as1H and13C spectrum, it is very convenient when analyzing pure substance, but the detection to mixture
With following limitation:1In H nuclear magnetic resonance map, each twocomponent signal peak of mixture is crowded in narrow map range (about 20
Ppm in), it is easy to cause signal overlap, greatly increases spectrum analysis difficulty.13Although C nuclear magnetic resoance spectrum has biggish spectrum width
(about 200 ppm), but13C spectrum can lose many important nuclear-magnetism information, such as coupling information, split a point situation, spectral peak integral, this is right
It will also result in very big difficulty in substance parsing.It usually requires by X-Y scheme, such as1H-1H correlation (COSY, TOCSY) and1H-13C
Related (HSQC, HMBC) etc. carries out complicated spectrum unscrambling ownership.
Summary of the invention
Gas chromatography used by being detected the present invention be directed to existing F- T synthesis water constituent and high performance liquid chromatography
The conventionals method of analysis such as method, application range is limited, operating process is complicated.The method of offer can overcome conventional nuclear magnetic resonance technique
With gas phase, the limitation of liquid chromatography technology, the magnetic resonance detection method of a F- T synthesis water constituent is provided.
In order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
A kind of magnetic resonance detection method of F- T synthesis water constituent of the invention is based on based on three-dimensional NMR diffusion row
Sequence spectrum-1H-1H same core chemical shift correlated spectroscopy is believed using the diffusion rate of each ingredient in a solvent in F- T synthesis water and coupling
Number difference it is different, diffusion rate obtained and coupled signal data are showed in the form of three-dimensional map, the transverse and longitudinal of map is sat
It is designated as chemical shift, ordinate is diffusion coefficient, according to the difference of each component diffusion coefficient in F- T synthesis water, on ordinate
The chemical shift plane with different diffusion coefficients is obtained, then basis1H-1The coupling of H same core chemical shift correlated spectroscopy figure is believed
Number, successively identification has the compound of same diffusion coefficient value, realizes the detection to each ingredient in F- T synthesis water.Base of the present invention
Sequence spectrum-is spread in three-dimensional NMR1H-1H same core chemical shift correlated spectroscopy nuclear magnetic spectrum detection Fischer-Tropsch synthetic water in respectively at
The magnetic nuclear resonance method of the composition divided.In entire test process, required sample size is few and will not destroy sample, without pair
Sample carries out the diffusion rate directly measured in the case where pre-treatment each ingredient in a solvent and coupled signal, to close to Fischer-Tropsch
The each component of Cheng Shuizhong is detected.This method provides a kind of easy to operate, and detection speed is fast, the F- T synthesis water of high sensitivity
The magnetic resonance detection method of ingredient.
Further, the three-dimensional NMR diffusion sequence spectrum-1H-1The testing procedure of H same core chemical shift correlated spectroscopy are as follows:
1) 50 ~ 450 μ l of F- T synthesis water sample is taken, deuterated reagent 450-50 μ l is dissolved in, which is transferred to nuclear magnetic resonance
In sample cell, above-mentioned sample cell is put into Liquid NMR spectrometer；2) adjustment nuclear magnetic resonance chemical analyser temperature is 273 K
To 323 K, air-flow is 100 ~ 1000 lph, at the temperature of setting and air-flow, sample constant 10 ~ 60 minutes；3) in minimum
Gradient fields and greatest gradient measure the one-dimensional hydrogen nuclear magnetic spectrogram of the mixture respectively off field；4) selection diffusion sequence spectrum with1H-1H is same
The assembled pulse sequence of coring displacement study Correlated Spectroscopy optimizes correlated sampling parameter, acquires three-dimensional map；5) the three-dimensional nuclear-magnetism obtained
Resonance diffusion sequence spectrum-1H-1The nuclear magnetic spectrum of H same core chemical shift correlated spectroscopy, and optimize relevant processing ginseng on this basis
Number obtains in longitudinal dimension has specific diffusion coefficient value1H-1H same core chemical shift correlated spectroscopy closes Fischer-Tropsch to realize
The detection of each ingredient of Cheng Shuizhong.Sample is dissolved in deuterated reagent, it is ensured that sample normally locks field test in magnetic field；
273 K to 323 K, air-flow are that 100 ~ 1000 lph sample constant 5 ~ 60 minutes, can at the temperature of setting and air-flow
Utmostly to reduce the sample influence of temperature gradient and air-flow gradient to test result during the test；Sample is in setting
Constant 10 ~ 60 minutes at temperature and air-flow, sample temperature can be made to keep constant during the test, reduced because of temperature shakiness
Sample interior solution convection current caused by fixed；The one-dimensional proton of the mixture is measured respectively off field in minimal gradient field and greatest gradient
Magnetic spectrum figure, diffusion sequence spectrum with1H-1The data acquisition of H same core chemical shift correlated spectroscopy needs to change pulsed field gradient, in minimum
Guarantee the accuracy of acquisition data off field with greatest gradient；Selection diffusion sequence spectrum with1H-1The group of H same core chemical shift correlated spectroscopy
Pulse train is closed, correlated sampling parameter is optimized, acquires three-dimensional map；Optimize the three-dimensional NMR that relevant processing parameter obtains
Diffusion sequence spectrum-1H-1The nuclear magnetic spectrum of H same core chemical shift correlated spectroscopy, and obtain have in longitudinal dimension on this basis
Specific diffusion coefficient value1H-1H same core chemical shift correlated spectroscopy, to realize the detection to each ingredient in F- T synthesis water.Number
It needs to optimize sampling parameter and processing parameter according to acquisition and data handling procedure, so that the result obtained is more accurate.
Further, deuterated reagent includes: deuterated water, deuterated methanol, deuterated acetone, deuterated dimethyl in the first step
Sulfoxide or deuterated-N,N-dimethylformamide.Correct selection deuterated reagent, is conducive to dissolve Fischer-Tropsch water sample, obtain uniform
Sample mixture is conducive to nuclear-magnetism test.
Further, the nuclear-magnetism spectrum resonance spectrometer in the first step is 200 ~ 800 MHz liquid with gradient fields
Nuclear magnetic resonance chemical analyser.The diffusion coefficient of molecule is to obtain a series of different spectrums by the way that pulsed gradient field intensity is altered in steps
Figure, is fitted to signal.
Further, the one-dimensional proton of the mixture is measured in the third step respectively under greatest gradient and minimal gradient
Magnetic spectrum figure, selected one-dimensional pulse sequence are ledbpgp2s1d, and pre-optimized sampling parameter, diffusion time (Δ), which is arranged, is
50 ~ 200ms, gradient application time (δ/2) are 600 ~ 2500 μ s, the gradient field strength range used for 2% ~ 98%,
The one-dimensional hydrogen spectrum matching similarity range that minimal gradient field and greatest gradient obtain off field is 2% ~ 10%.In this similarity dimensions
It is interior, it can preferable analog signal.
Further, the 4th step selection diffusion sequence spectrum with1H-1The assembled pulse sequence of H same core chemical shift correlated spectroscopy
Column selection ledbpgpco2s3d.This pulse is on the basis of nuclear magnetic resonance measuring molecule self-diffusion coefficient classics test method
It develops, the eddy current effect occurred in shielding probe in experiment can be greatly reduced, obtained accurately with the above pulse
Data.
Further, the three-dimensional NMR diffusion sequence spectrum-1H-1H same core chemical shift correlated spectroscopy, test parameter are set
Fixed GPZ6 value is 100%, and diffusion time is 50 ~ 250 ms, and pulse field gradient pwm value is 600 ~ 2500 μ s, and pulse is swept
The multiple that number is 8 is retouched, sky sweeps the multiple that number is 8, and three-dimensional map sampling number is 8 ~ 128 times, the sampling of every spectrogram
Points are 16k ~ 128k.The diffusion rate and coupling information of the molecule more accurately obtained after optimization sampling parameter, test parameter
Without optimization, obtained test result will be by very big error.
Further, the three-dimensional NMR diffusion sequence spectrum-1H-1The three-dimensional map of H same core chemical shift correlated spectroscopy
It is handled and is obtained by Brooker Topspin software.Brooker Topspin is the professional treatment software of diffusion rate and coupling information.
Can within the scope of minimal error accurate simulation sample diffusion coefficient.
Further, the three-dimensional map is handled by Brooker Topspin software, sets three-dimensional map processing parameter strong point
It is 32 ~ 512, the data point of every spectrogram is 218 ~ 1024.Obtained number is presented in good mode after optimization processing parameter
According to.
Detailed description of the invention
Fig. 1 is the three-dimensional NMR diffusion sequence spectrum-of the embodiment of the present invention 11H-1H same core chemical shift correlated spectroscopy;
Fig. 2 is the embodiment of the present invention 21H-1H same core chemical shift correlated spectroscopy figure;
Fig. 3 is the embodiment of the present invention 31H-1H same core chemical shift correlated spectroscopy figure;
Fig. 4 be the embodiment of the present invention 4 one-dimensional hydrogen (1H) spectrogram;
Fig. 5 is the embodiment of the present invention 41H-1H same core chemical shift correlated spectroscopy figure.
Specific embodiment
Embodiment 1:
A kind of magnetic resonance detection method of F- T synthesis water constituent of the invention is based on based on three-dimensional NMR diffusion row
Sequence spectrum-1H-1H same core chemical shift correlated spectroscopy is believed using the diffusion rate of each ingredient in a solvent in F- T synthesis water and coupling
Number difference it is different, diffusion rate obtained and coupled signal data are showed in the form of three-dimensional map, the transverse and longitudinal of map is sat
It is designated as chemical shift, ordinate is diffusion coefficient, according to the difference of each component diffusion coefficient in F- T synthesis water, on ordinate
The chemical shift plane with different diffusion coefficients is obtained, then basis1H-1The coupling of H same core chemical shift correlated spectroscopy figure is believed
Number, successively identification has the compound of same diffusion coefficient value, realizes the detection to each ingredient in F- T synthesis water.It specifically includes
Following steps:
Three-dimensional NMR diffusion sequence spectrum-1H-1The test of H same core chemical shift correlated spectroscopy, specifically:
Step 1: taking 50 μ L of Fischer-Tropsch water (I) sample that 450 μ L of deuterated dimethyl sulfoxide solvent is added, and after all dissolutions, is added
Into nuclear magnetic tube, to further analyze.Blend sample is put into 200M Liquid NMR spectrometer, spectrometer temperature is set
Degree be 273K, air-flow be 100 lph, constant temperature 10 minutes；
Step 2: selection diffusion sequence spectrum ledbpgp2s1d pulse train, setting diffusion time (Δ) is 50 ms, and gradient applies
Time (δ/2) is 1000 μ s, and gradient intensity (GPZ) is the 2% of greatest gradient intensity, the one-dimensional hydrogen spectrum of acquisition first；Setting is expanded
Dissipating time (Δ) is 50 ms, and gradient application time (δ/2) is 600 μ s, and gradient intensity (GPZ) is the 98% of greatest gradient intensity,
Second hydrogen spectrum is acquired with this condition；Obtain two maps are matched, keep the intensity of two spectrograms consistent, match ratio
Example (scale) value is 10%；
Step 3: selection diffusion sequence spectrum with1H-1The ledbpgpco2s3d assembled pulse sequence of H same core chemical shift correlated spectroscopy
Column, setting sampling parameter GPZ6 value are 100%, and gradient application time (δ/2) is 600 μ s, and used pulse scanning times are
8；It is 8 that used sky, which sweeps number,；Used three-dimensional map sampling number 8 times, the sampling number of every spectrogram are 16k,
Three-dimensional spectrum data are acquired under this condition
Step 4: carrying out data processing with software Topspin 3.1, the three-dimensional diffusion that can be obtained sequence spectral technology with1H-1H
Same core chemical shift correlated spectroscopy spectrogram, so that each ingredient is tentatively distinguished in three-dimensional space in mixture.Expand according in three-dimensional map
Dissipate sequence spectrum with1H-1The twocomponent signal position that H same core chemical shift correlated spectroscopy is shown sets three-dimensional map processing parameter strong point
It is 32, the data point of every spectrogram is 218, and interception has different diffusion coefficients on ordinate1H-1H same core chemical shift
Related two-dimensional surface extracts the map of compound and carries out analysis and refer to according to the proton coupling information in same Spin System
Recognize, is accurately pointed out according to main component of the proton coupled signal to F- T synthesis water.Fig. 1 is the spatial nuclei of the embodiment of the present invention 1
Magnetic resonance diffusion sequence spectrum-1H-1H same core chemical shift correlated spectroscopy.
Embodiment 2:
A kind of magnetic resonance detection method of F- T synthesis water constituent of the invention is based on three-dimensional NMR diffusion sequence spectrum
-1H-1H same core chemical shift correlated spectroscopy utilizes the diffusion rate in a solvent of each ingredient in F- T synthesis water and coupled signal
Difference is different, diffusion rate obtained and coupled signal data is showed in the form of three-dimensional map, the transverse and longitudinal coordinate of map is
Chemical shift, ordinate are diffusion coefficient, according to the difference of each component diffusion coefficient in F- T synthesis water, are obtained on ordinate
Chemical shift plane with different diffusion coefficients, then basis1H-1The coupled signal of H same core chemical shift correlated spectroscopy figure, according to
Secondary identification has the compound of same diffusion coefficient value, realizes the detection to each ingredient in F- T synthesis water.It specifically includes following
Step:
Three-dimensional NMR diffusion sequence spectrum-1H-1The test of H same core chemical shift correlated spectroscopy, specifically:
Step 1: taking 100 μ L of Fischer-Tropsch water (II) sample that 400 μ L of deuterated dimethyl sulfoxide solvent is added, and after all dissolutions, is added
Into nuclear magnetic tube, to further analyze.Blend sample is put into 400M Liquid NMR spectrometer, spectrometer temperature is set
Degree be 293K, air-flow be 400 lph, constant temperature 25 minutes；
Step 2: selection diffusion sequence spectrum ledbpgp2s1d pulse train, setting diffusion time (Δ) is 100ms, and gradient applies
Time (δ/2) is 1000 μ s, and gradient intensity (GPZ) is the 2% of greatest gradient intensity, the one-dimensional hydrogen spectrum of acquisition first；Setting is expanded
Dissipating time (Δ) is 100 ms, and gradient application time (δ/2) is 1000 μ s, and gradient intensity (GPZ) is greatest gradient intensity
98%, second hydrogen spectrum is acquired with this condition；Obtain two maps are matched, keep the intensity of two spectrograms consistent,
It is 5% with ratio (scale) value；
Step 3: selection diffusion sequence spectrum with1H-1The ledbpgpco2s3d assembled pulse sequence of H same core chemical shift correlated spectroscopy
Column, setting sampling parameter GPZ6 value are 100%, and gradient application time (δ/2) is 1000 μ s, and used pulse scanning times are
16；It is 16 that used sky, which sweeps number,；Used three-dimensional map sampling number 32 times, the sampling number of every spectrogram are
32k acquires three-dimensional spectrum data under this condition
Step 4: carrying out data processing with software Topspin 3.2, can be obtained three-dimensional diffusion sequence spectral technology with1H-1H is same
Coring displacement study Correlated Spectroscopy spectrogram, so that each ingredient is tentatively distinguished in three-dimensional space in mixture.It is spread according in three-dimensional map
Sequence spectrum with1H-1The twocomponent signal position that H same core chemical shift correlated spectroscopy is shown, set three-dimensional map processing parameter strong point as
64, the data point of every spectrogram is 218, and interception has different diffusion coefficients on ordinate1H-1The phase of H same core chemical shift
Two-dimensional surface is closed, according to the proton coupling information in same Spin System, the map of compound is extracted and carries out analysis and point out,
It is accurately pointed out according to main component of the proton coupled signal to F- T synthesis water.Fig. 2 is the embodiment of the present invention 11H-1The same coring of H
Displacement study correlation spectrogram.
Embodiment 3:
A kind of magnetic resonance detection method of F- T synthesis water constituent of the invention is based on based on three-dimensional NMR diffusion row
Sequence spectrum-1H-1H same core chemical shift correlated spectroscopy is believed using the diffusion rate of each ingredient in a solvent in F- T synthesis water and coupling
Number difference it is different, diffusion rate obtained and coupled signal data are showed in the form of three-dimensional map, the transverse and longitudinal of map is sat
It is designated as chemical shift, ordinate is diffusion coefficient, according to the difference of each component diffusion coefficient in F- T synthesis water, on ordinate
The chemical shift plane with different diffusion coefficients is obtained, then basis1H-1The coupling of H same core chemical shift correlated spectroscopy figure is believed
Number, successively identification has the compound of same diffusion coefficient value, realizes the detection to each ingredient in F- T synthesis water.It specifically includes
Following steps:
Three-dimensional NMR diffusion sequence spectrum-1H-1The test of H same core chemical shift correlated spectroscopy, specifically:
Step 1: taking 250 μ L of Fischer-Tropsch water (III) sample that 250 μ L of deuterated dimethyl sulfoxide solvent is added, and after all dissolutions, is added
Into nuclear magnetic tube, to further analyze.Blend sample is put into 600M Liquid NMR spectrometer, spectrometer temperature is set
Degree be 303K, air-flow be 600 lph, constant temperature 45 minutes；
Step 2: selection diffusion sequence spectrum ledbpgp2s1d pulse train, setting diffusion time (Δ) is 150ms, and gradient applies
Time (δ/2) is 1000 μ s, and gradient intensity (GPZ) is the 2% of greatest gradient intensity, the one-dimensional hydrogen spectrum of acquisition first；Setting is expanded
Dissipating time (Δ) is 150 ms, and gradient application time (δ/2) is 1500 μ s, and gradient intensity (GPZ) is greatest gradient intensity
98%, second hydrogen spectrum is acquired with this condition；Obtain two maps are matched, keep the intensity of two spectrograms consistent,
It is 4% with ratio (scale) value；
Step 3: selection diffusion sequence spectrum with1H-1The ledbpgpco2s3d assembled pulse sequence of H same core chemical shift correlated spectroscopy
Column, setting sampling parameter GPZ6 value are 100%, and gradient application time (δ/2) is 1500 μ s, and used pulse scanning times are
16；It is 16 that used sky, which sweeps number,；Used three-dimensional map sampling number 64 times, the sampling number of every spectrogram are 64k,
Three-dimensional spectrum data are acquired under this condition
Step 4: carrying out data processing with software Topspin 3.5, can be obtained three-dimensional diffusion sequence spectral technology with1H-1H is same
Coring displacement study Correlated Spectroscopy spectrogram, so that each ingredient is tentatively distinguished in three-dimensional space in mixture.It is spread according in three-dimensional map
Sequence spectrum with1H-1The twocomponent signal position that H same core chemical shift correlated spectroscopy is shown, set three-dimensional map processing parameter strong point as
128, the data point of every spectrogram is 218, and interception has different diffusion coefficients on ordinate1H-1H same core chemical shift
Related two-dimensional surface extracts the map of compound and carries out analysis and refer to according to the proton coupling information in same Spin System
Recognize, is accurately pointed out according to main component of the proton coupled signal to F- T synthesis water.Fig. 3 is the embodiment of the present invention 31H-1H is same
Coring displacement study Correlated Spectroscopy figure.
Embodiment 4:
A kind of magnetic resonance detection method of F- T synthesis water constituent of the invention is based on based on three-dimensional NMR diffusion row
Sequence spectrum-1H-1H same core chemical shift correlated spectroscopy is believed using the diffusion rate of each ingredient in a solvent in F- T synthesis water and coupling
Number difference it is different, diffusion rate obtained and coupled signal data are showed in the form of three-dimensional map, the transverse and longitudinal of map is sat
It is designated as chemical shift, ordinate is diffusion coefficient, according to the difference of each component diffusion coefficient in F- T synthesis water, on ordinate
The chemical shift plane with different diffusion coefficients is obtained, then basis1H-1The coupling of H same core chemical shift correlated spectroscopy figure is believed
Number, successively identification has the compound of same diffusion coefficient value, realizes the detection to each ingredient in F- T synthesis water.It specifically includes
Following steps:
Three-dimensional NMR diffusion sequence spectrum-1H-1The test of H same core chemical shift correlated spectroscopy, specifically:
Step 1: taking 450 μ L of Fischer-Tropsch water (IV) sample that 50 μ L of deuterated dimethyl sulfoxide solvent is added, and after all dissolutions, is added
Into nuclear magnetic tube, to further analyze.Blend sample is put into 800M Liquid NMR spectrometer, spectrometer temperature is set
Degree be 323K, air-flow be 1000 lph, constant temperature 60 minutes；
Step 2: selection diffusion sequence spectrum ledbpgp2s1d pulse train, setting diffusion time (Δ) is 200ms, and gradient applies
Time (δ/2) is 1000 μ s, and gradient intensity (GPZ) is the 2% of greatest gradient intensity, the one-dimensional hydrogen spectrum of acquisition first；Setting is expanded
Dissipating time (Δ) is 200 ms, and gradient application time (δ/2) is 2500 μ s, and gradient intensity (GPZ) is greatest gradient intensity
98%, second hydrogen spectrum is acquired with this condition；Obtain two maps are matched, keep the intensity of two spectrograms consistent,
It is 2% with ratio (scale) value；
Step 3: selection diffusion sequence spectrum with1H-1The ledbpgpco2s3d assembled pulse sequence of H same core chemical shift correlated spectroscopy
Column, setting sampling parameter GPZ6 value are 100%, and gradient application time (δ/2) is 2500 μ s, and used pulse scanning times are
32；It is 32 that used sky, which sweeps number,；Used three-dimensional map sampling number 128 times, the sampling number of every spectrogram are
128k acquires three-dimensional spectrum data under this condition
Step 4: carrying out data processing with software Topspin 4.0, can be obtained three-dimensional diffusion sequence spectral technology with1H-1H is same
Coring displacement study Correlated Spectroscopy spectrogram, so that each ingredient is tentatively distinguished in three-dimensional space in mixture.It is spread according in three-dimensional map
Sequence spectrum with1H-1The twocomponent signal position that H same core chemical shift correlated spectroscopy is shown, set three-dimensional map processing parameter strong point as
512, the data point of every spectrogram is 1024, and interception has different diffusion coefficients on ordinate1H-1H same core chemical shift
Related two-dimensional surface extracts the map of compound and carries out analysis and refer to according to the proton coupling information in same Spin System
Recognize, is accurately pointed out according to main component of the proton coupled signal to F- T synthesis water.Fig. 4 is the one-dimensional hydrogen of the embodiment of the present invention 4
(1H) spectrogram.Fig. 5 is the embodiment of the present invention 41H-1H same core chemical shift correlated spectroscopy figure.
The result shows that nuclear magnetic resonance chemical analyser is very sensitive to hydrogen nuclei detection, it is capable of detecting when the lower object of content
Faint signal is accurately pointed out in matter, realization.For same wastewater sample, chromatographic process and nuclear-magnetism is used to quantify skill
Art is detected.It is analysis result below:
A: the nuclear-magnetism method detection in the present invention；B: gas chromatography detection
By comparison, it was found that: magnetic nuclear resonance method, which detects small molecule compound, has superiority than gas chromatography detection, quasi-
Exactness accuracy is high, it was demonstrated that the test method is accurate and reliable, can be used for the identification of complex mixture.
Claims (10)
1. a kind of magnetic resonance detection method of F- T synthesis water constituent, it is characterised in that: the core of the F- T synthesis water constituent
Magnetic resonance detection method is based on three-dimensional NMR diffusion sequence spectrum-1H-1H same core chemical shift correlated spectroscopy, is closed using Fischer-Tropsch
The composition of each ingredient in the Difference test F- T synthesis water of each ingredient of Cheng Shuizhong diffusion rate in a solvent and coupled signal.
2. the magnetic resonance detection method of F- T synthesis water constituent according to claim 1, it is characterised in that: described three
Tie up nuclear magnetic resonance diffusion sequence spectrum-1H-1H same core chemical shift correlated spectroscopy diffusion rate obtained and coupled signal data are with three
Dimension map form shows, and the transverse and longitudinal coordinate of map is chemical shift, and ordinate is diffusion coefficient, according in F- T synthesis water respectively at
The difference for dividing diffusion coefficient obtains the chemical shift plane with different diffusion coefficients, then basis on ordinate1H-1H is same
The coupled signal of coring displacement study Correlated Spectroscopy figure, successively identification has the compound of same diffusion coefficient value, realizes and closes to Fischer-Tropsch
The detection of each ingredient of Cheng Shuizhong.
3. the magnetic resonance detection method of F- T synthesis water constituent according to claim 2, it is characterised in that: the three-dimensional
Nuclear magnetic resonance diffusion sequence spectrum-1H-1The testing procedure of H same core chemical shift correlated spectroscopy are as follows:
The first step takes 50 ~ 450 μ l of F- T synthesis water sample, is dissolved in deuterated reagent 450-50 μ l, which is shifted
Into nuclear magnetic resonance sample pipe, above-mentioned sample cell is put into Liquid NMR spectrometer；
Second step, adjustment nuclear magnetic resonance chemical analyser temperature are 273 K to 323 K, and air-flow is 100 ~ 1000 lph, are being set
Temperature and air-flow under, sample constant 10 ~ 60 minutes；
Third step measures the one-dimensional hydrogen nuclear magnetic spectrogram of the mixture in minimal gradient field and greatest gradient respectively off field；
4th step, selection diffusion sequence spectrum with1H-1The assembled pulse sequence of H same core chemical shift correlated spectroscopy optimizes correlated sampling
Parameter acquires three-dimensional map；
5th step, the three-dimensional NMR diffusion sequence spectrum-of acquisition1H-1The nuclear magnetic spectrum of H same core chemical shift correlated spectroscopy, and
Optimize relevant processing parameter on the basis of this to be obtained in longitudinal dimension with specific diffusion coefficient value1H-1H same core chemical potential
Correlated Spectroscopy is moved, to realize the detection to each ingredient in F- T synthesis water.
4. the magnetic resonance detection method of F- T synthesis water constituent according to claim 3, it is characterised in that: described first
Deuterated reagent includes: deuterated water, deuterated methanol, deuterated acetone, deuterated dimethyl sulfoxide or deuterated-N, N- dimethyl formyl in step
Amine.
5. the magnetic resonance detection method of F- T synthesis water constituent according to claim 4, it is characterised in that: described first
Nuclear-magnetism spectrum resonance spectrometer in step is 200 ~ 800 MHz Liquid NMR spectrometers with gradient fields.
6. the magnetic resonance detection method of F- T synthesis water constituent according to claim 5, it is characterised in that: the third
Measure the one-dimensional hydrogen nuclear magnetic spectrogram of the mixture, selected one-dimensional pulse sequence in step respectively under greatest gradient and minimal gradient
It is classified as ledbpgp2s1d, pre-optimized sampling parameter, setting diffusion time (Δ) is 50 ~ 200ms, gradient application time (δ/
It 2) is 600 ~ 2500 μ s, the gradient field strength range used is obtained in minimal gradient field and greatest gradient off field for 2% ~ 98%
The one-dimensional hydrogen spectrum matching similarity range obtained is 2% ~ 10%.
7. the magnetic resonance detection method of F- T synthesis water constituent according to claim 6, it is characterised in that: the described 4th
Step selection diffusion sequence spectrum with1H-1The assembled pulse sequence selection ledbpgpco2s3d of H same core chemical shift correlated spectroscopy.
8. the magnetic resonance detection method of F- T synthesis water constituent according to claim 7, it is characterised in that: the three-dimensional
Nuclear magnetic resonance diffusion sequence spectrum-1H-1H same core chemical shift correlated spectroscopy, the GPZ6 value that test parameter is set is 100%, diffusion time
For 50 ~ 250 ms, pulse field gradient pwm value is 600 ~ 2500 μ s, the multiple that pulse scanning times are 8, and sky sweeps number
For 8 multiple, three-dimensional map sampling number is 8 ~ 128 times, and the sampling number of every spectrogram is 16k ~ 128k.
9. the magnetic resonance detection method of F- T synthesis water constituent according to claim 8, it is characterised in that: the three-dimensional
Nuclear magnetic resonance diffusion sequence spectrum-1H-1The three-dimensional map of H same core chemical shift correlated spectroscopy is handled by Brooker Topspin software and is obtained
?.
10. the magnetic resonance detection method of F- T synthesis water constituent according to claim 9, it is characterised in that: described three
It ties up map to be handled by Brooker Topspin software, set three-dimensional map processing parameter strong point as 32 ~ 512, the number of every spectrogram
Strong point is 218 ~ 1024.
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