CN110044944A - A kind of magnetic resonance detection method for F- T synthesis waste water component analysis - Google Patents
A kind of magnetic resonance detection method for F- T synthesis waste water component analysis Download PDFInfo
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Abstract
The invention belongs to the analytical chemistry fields of F- T synthesis waste water component detection, more particularly to a kind of magnetic resonance detection method for F- T synthesis waste water component analysis, mainly solve application range existing for the analysis methods such as red, orange, green, blue, yellow (ROGBY) used by existing F- T synthesis waste water component detects and conventional magnetic nuclear resonance method it is limited, it is time-consuming long, the technical problems such as operating process is cumbersome and inhibit same core coupling effect, as a result provide very pure no coupling and split point one-dimensional hydrogen and compose.According to solutes different in F- T synthesis waste water1H‑1The relevant coupled signal of H same core chemical shift successively carries out ownership to the signal peak with characteristic chemical shifts occurred in one-dimensional spectrogram and points out, and realization tests and analyzes F- T synthesis waste water each component extremely classification.Measurement result of the invention, which eliminates conventional one-dimensional hydrogen, composes occurred coupling and splits point and peak overlap, and detection resolution is high, and easy to operate, time-consuming is shorter, can quickly and easily realize the component analysis to F- T synthesis waste water.
Description
Technical field
The invention belongs to the analytical chemistry fields of F- T synthesis waste water component detection, and in particular to one kind is used for F- T synthesis
The magnetic resonance detection method of waste water component analysis is to be given up based on One-Dimensional Pure chemical shift magnetic nuclear resonance method according to F- T synthesis
The coupled signal of the 1H-1H same core chemical shift correlated spectroscopy figure of different solutes in water has feature to what is occurred in one-dimensional spectrogram
The signal peak of chemical shift successively carries out the detection method that ownership is pointed out.
Background technique
Fischer-Tropsch synthesis is initially the German by entitled Franz Fischer and Hans Tropsch 1920
Year discovery a catalytic chemistry reaction, the process be Modern Coal-based Chemical production clean fuel liquid important process, it can will
Synthesis gas (carbon monoxide and hydrogen) is converted into liquid hydrocarbon fuel and its chemicals based on paraffin hydrocarbon, however is obtaining liquid
While fluid fuel, can discharge a greater amount of reaction generate water i.e. F- T synthesis waste water wherein the aldehyde containing short carbon chain, ketone, acid,
Tens kinds of small organic molecules such as ester.Not only pollute that small molecule is many kinds of but also complicated component discharge amount in F- T synthesis waste water
Greatly, aqueous solution is in acid, COD (COD) is high, has the characteristics that strong corrosive, processing difficulty are big.With Modern Coal-based Chemical
The fast development of industry, the production capacity status to accompany of advancing by leaps and bounds is: waste water (mainly reaction generates water) discharge amount is same
Step increases, and water treatment problems are increasingly severe, restricts the operation and sustainable development of Modern Coal-based Chemical technology and relevant enterprise at last.
If fast and effective analysis processing can be carried out to it, industrial production capacity will be greatly improved and realize green friendly waste water row
It puts.
The analysis means of F- T synthesis waste water are depended on chromatography (gas-chromatography and liquid chromatogram), however due to
F- T synthesis waste component is complicated, and pollution small organic molecule is all extremely either on molecular structure or in chemical characteristic
Similar, red, orange, green, blue, yellow (ROGBY) is all limited in these areas, and in most cases chromatography is required to chromatography
Column and analysis object are pre-processed, therefore also bring certain difficulty to mixture analysis.
Summary of the invention
Red, orange, green, blue, yellow (ROGBY) used by detecting the present invention be directed to existing F- T synthesis waste water component and conventional nuclear-magnetism are total
The analysis methods such as method of slight, application range is limited, time-consuming is long, operating process is cumbersome, provides a kind of purifying of F- T synthesis waste water
Displacement study nuclear magnetic resonance spectroscopy detection method.
In order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
Magnetic resonance detection method for F- T synthesis waste water component analysis is composed based on One-Dimensional Pure chemical shift, the party
Method is to change dimension after selecting corresponding pulses sequence in one-dimensional hydrogen spectrum and corresponding shaped pulse is arranged, continuous trimmer choosing ladder
It spends intensity and carries out pseudo- two dimension experiment sampling, spliced again using AU program and obtain new FID value, use Brooker Topspin 3.1
FID data are converted to obtain One-Dimensional Pure chemical shift hydrogen and compose and optimize spectrogram as a result, being according to different molecular in waste water by software
Existing chemical displacement value difference carries out ownership to its component and points out.Piece, which is continued to optimize, before carrying out two dimension experiment test selects gradient
It is to find out a suitable and lesser gradient value to carry out pseudo- two dimension sampling, can be good at point of control experiment in this way
Balance between resolution and sensitivity, gradient value is excessive, and the sensitivity that can seriously affect experiment makes test result lose meaning
Justice, and gradient value is too small, can not obtain the nuclear magnetic signal of all solutes in test specimen；And the data directly measured are one
A two dimension experimental data, it is therefore desirable to which one can just be obtained by carrying out processing data by the related software and its application program of Brooker
Dimension decoupling hydrogen spectrum.
Further, the One-Dimensional Pure chemical shift spectrum is sampled based on three kinds of pulse trains.In three kinds of pulses
It is all using compacting J coupling effect on the mechanism of action of sequence, realization multiplet collapse is unimodal signal.
Further, the magnetic resonance detection method for the component analysis of F- T synthesis waste water is based on one-dimensional purifying
Displacement study spectrum, this method are to change dimension after selecting corresponding pulses sequence in one-dimensional hydrogen spectrum and corresponding shaped pulse is arranged,
It is continuously increased gradient intensity and carries out pseudo- two dimension experiment sampling, specific step is as follows for test:
The first step, it is accurate to measure 50~700 μ l of F- T synthesis wastewater sample, the deuterated reagent of itself and 700~50 μ l are mixed
It closes, 400~750 μ l of mixed liquor is taken to be put into Liquid NMR spectrometer in sample cell；
Second step, test before debugging nuclear magnetic resonance chemical analyser temperature be 273K~323K, setting airflow rate be 200~
800lph, constant sample 10~40 minutes at the temperature of setting and air-flow；It chooses pulse train zg, zg30 or zgpr test should
The common one-dimensional hydrogen spectrum of sample；
Third step, the one-dimensional hydrogen spectrum that duplication second step is tested, setting spectrum width determine centre frequency；Changing pulse train is
After " push1dzs_Gset ", simultaneously constantly trimmer selects gradient intensity GPZ2 value to setting shaped pulse, so that in F- T synthesis waste water
Constituent signals all appear in spectrogram；
4th step recalls Two-dimensional Pulsed sequence in the case where suitable piece selects gradient intensity GPZ2, be arranged 180 ° of shaped pulses and
GPZ1 value continuouslys optimize correlated sampling parameter after being 80%, obtains a pseudo- two-dimentional experimental data；
5th step, using the AU program of purifying displacement study to obtained by the 4th step on 3.1 software of Brooker Topspin
Puppet two dimension experiment handled, data sampling complete.Constant experimental temperature and constant gas during the test, and by sample
The static stabilization for both contributing to sample of product；Every test is successively carried out according to the experimental procedure to be provided with conducive to experiment survey is carried out
Examination.
Further, the spectrometer that the magnetic resonance detection method uses is 300~800MHz liquid core with gradient fields
Resonance spectrometer.Pure one-dimensional nuclear magnetic resonance hydrogen spectrum can be obtained very well in above-mentioned field strength, if in higher degree field strength
Nmr spectrometer can provide more highly sensitive one-dimensional hydrogen spectrum, can be certain in combination with One-Dimensional Pure chemical shift nuclear magnetic resonance
The resolution ratio of spectrogram is improved in degree.
Further, deuterated reagent is heavy water, deuterated methanol, deuterated acetone or deuterated-N, N- diformazan in the first step
Base formamide.The deuterated reagent as suggested in the present invention used can be mixed effectively with F- T synthesis waste water to be measured, uniformly mix expense
Synthetic wastewater sample is ask to provide convenience to test.
Further, the piece in the third and four steps selects gradient intensity GPZ2 value, and adjusting range is 0.2%~20%
Between, in the case where selecting gradient intensity for ever-increasing, obtain a series of free induction decay FID value.Piece selects gradient
Value determines the clean level of spectrogram, adjusts its desired value within the above range, can not only reduce workload but also can obtain
FID value converted after can then provide ideal One-Dimensional Pure chemical shift spectrum.
Further, the shaped pulse classification is Gauss, Reburp or Rsnob, and specific pulsewidth and its right is arranged
The duration answered is respectively 10KHz and 30ms.Three of the above shaped pulse be determined by the sample sequence of the experiment must
The selective exitation pulse wanted, the pulsewidth for F- T synthesis wastewater sample strobe pulse are to be set as 10KHz and duration
30ms is sampled, and more accurate fitting can be carried out to two-dimentional FID.
Further, the pulse train that the 4th step is recalled be " push1dz ", " psyche.mf " or
"psycetse.mf".Three kinds of pulse protocols belong to the sampling pulse sequence of One-Dimensional Pure chemical shift nuclear magnetic resonance, can reach
To experiment purpose, however they still have any different in sensitivity, therefore are had in test sample more using different pulse train
Selection, while experimental results can be compared, selection wherein more excellent result.
Further, the 4th step continues to optimize correlated sampling parameter, and as follows, sampling number TD value is arranged in sampling parameter
For 8k~64k, directly dimension spectrum width is the integral multiple of indirect dimension spectrum width and indirect dimension value takes 30~150Hz, and CNST20 value is
10~25Hz.The sampling number provided in the present invention, the resolution ratio spectrum that the value tieed up indirectly can have been obtained in two dimension sampling
Figure as a result, wherein sampling number increase can take on a new look spectrogram signal-to-noise ratio, while reducing directly to tie up and can shorten survey with the ratio tieed up indirectly
Try the time.
Further, the utilization AU program is spliced again obtains new FID value, uses 3.1 software of Brooker Topspin
It converts to obtain One-Dimensional Pure chemical shift hydrogen for FID data to compose and optimize spectrogram as a result, its concrete operations are as follows: first by new FID
Value is converted into two-dimensional map, then transfers macros " pshift ", obtains One-Dimensional Pure chemical shift hydrogen spectrum after executing the order,
Processing is advanced optimized to spectrogram afterwards；Described to advanced optimize processing to spectrogram, specific optimal conditions are adjustment linewidth factor
LB is -5~5Hz, and carries out Fourier transformation, phase adjustment, baseline correction, then obtains related pure chemistry displacement hydrogen nuclear magnetic resonance
Spectrum.Processing is optimized to obtained one-dimensional spectrogram according to above-mentioned post processing mode and the suitable LB value of adjustment can not only be eliminated
It part vestigial sideband and can be improved spectrogram rate respectively, spectrogram be presented in a better way.
Compared to red, orange, green, blue, yellow (ROGBY), nmr analysis has its advantage, such as analysis without deriving to sample
Sample composition will not be destroyed simultaneously by changing processing, and can be directly observed mixture aldehyde material hair from nmr analysis spectrogram
Raw hydration reaction.Nmr analysis used in the present invention not only has the advantages that conventional hydrogen spectrum, but also solves
A point situation is split in the same core coupling of intramolecular, so that each signal is unimodal in one-dimensional spectrogram only corresponds to chemical environment
Hydrogen, enormously simplify analysis difficulty, rapidly and efficiently Fischer-Tropsch waste water component can be carried out pointing out analysis.
A kind of magnetic resonance detection method for F- T synthesis waste water component analysis of the invention is based on one-dimensional purifying
Displacement study nuclear magnetic resonance spectroscopy obtains point of each component hydrogen shift in mixture by the sampling configuration using pseudo- two dimension experiment
Cloth data further use macros " pshift " for gained 2-D data progress conversion process and then obtain an one-dimensional spectrogram,
According to the coupled signal of the 1H-1H same core chemical shift correlated spectroscopy figure of solutes different in F- T synthesis waste water, in one-dimensional spectrogram
The signal peak with characteristic chemical shifts occurred successively carries out ownership and points out, and realizes to F- T synthesis waste water each component extremely class
It carry out not analysis detection.The present invention is based on One-Dimensional Pure chemical shift nuclear magnetic resonance spectroscopies to detect in Fischer-Tropsch synthetic wastewater respectively at grouping
At magnetic nuclear resonance method.In entire test process, required sample size is few, will not destroy sample and be not necessarily to before carrying out to sample
Processing can carry out nuclear-magnetism detection, and this method test acquired results are concise, One-Dimensional Pure chemical shift nuclear magnetic resonance spectroscopy, base
The distribution number of each component hydrogen shift in mixture is obtained in its test philosophy is the sampling configuration by testing using pseudo- two dimension
According to further using macros " pshift " for gained 2-D data and carry out conversion process, while also solving intramolecular hydrogen
A point situation is split in same core coupling, so that the unimodal hydrogen for only corresponding to a chemical environment of each signal in one-dimensional spectrogram, significantly
Analysis difficulty is simplified, rapidly and efficiently Fischer-Tropsch waste water component can be carried out pointing out analysis.
Detailed description of the invention
Fig. 1 is that pulse is that " push1dz " test one pure chemistry of gained is displaced hydrogen nuclear magnetic resonance in the embodiment of the present invention 1
Spectrum；
Fig. 2 is that pulse is that " psyche.mf " tests gained One-Dimensional Pure chemical shift hydrogen nuclear magnetic resonance in the embodiment of the present invention 2
Spectrum；
It is that " psycetse.mf " tests gained One-Dimensional Pure chemical shift core that Fig. 3, which is that pulse is pulse in the embodiment of the present invention 3,
Magnetic resonance hydrogen spectrum；
Fig. 4 is one-dimensional routine hydrogen spectrum measured by the embodiment of the present invention 4；
Fig. 5 is that pulse is that " psyche.mf " tests gained One-Dimensional Pure chemical shift hydrogen nuclear magnetic resonance in the embodiment of the present invention 4
Spectrum；
Fig. 6 is that pulse is that " psycetse.mf " tests gained One-Dimensional Pure chemical shift nuclear magnetic resonance in the embodiment of the present invention 5
Hydrogen spectrum is composed with conventional hydrogen；A) conventional one-dimensional hydrogen spectrum b) compose by the one-dimensional hydrogen of purifying displacement study；
Fig. 7 is two-dimensional diffusion sequence spectrum (DOSY) measured in ratio example.
Specific embodiment
Embodiment 1:
The magnetic resonance detection method for the component analysis of F- T synthesis waste water in the present embodiment is based on one-dimensional purifying
Displacement study spectrum, this method are to change dimension after selecting corresponding pulses sequence in one-dimensional hydrogen spectrum and corresponding shaped pulse is arranged,
Continuous trimmer selects gradient intensity to carry out pseudo- two dimension experiment sampling, is spliced again using AU program and obtains new FID value, uses cloth Shandong
FID data are converted to obtain One-Dimensional Pure chemical shift hydrogen and compose and optimize spectrogram as a result, according in waste water by gram 3.1 software of Topspin
The chemical displacement value difference that different molecular is presented carries out ownership to its component and points out.Include the following steps:
Firstly, selection corresponding pulses sequence " push1dz " changes dimension afterwards and corresponding shape is arranged in one-dimensional hydrogen spectrum
Pulse Gauss；
Then, continuous trimmer selects gradient intensity to carry out pseudo- two dimension experiment sampling, the specific steps are as follows:
The first step, the accurate 50 μ l of F- T synthesis waste water (I) sample that measures are mixed with the 700 deuterated water of μ l, are taken after uniformly mixed
400 μ l of liquid is closed to be put into 300MHz Liquid NMR spectrometer in sample cell.
Second step, debugging nuclear magnetic resonance chemical analyser temperature is 273K before testing, and sets air-flow as 200lph, when keeping test
Sample to be tested is static, and at the temperature of setting and air-flow after constant sample 10min, chooses pulse train zg and tests a routine
Hydrogen spectrum.
Third step, the one-dimensional hydrogen spectrum that duplication second step is tested, setting spectrum width determine centre frequency；Changing pulse train is
After " push1dzs_Gset ", setting shaped pulse and constantly trimmer select gradient intensity GPZ2 value to be followed successively by 0.2%, 0.4%,
0.6%, 0.8%, 1.0%, 1.2%, until all appearing in the constituent signals in surveyed F- T synthesis waste water in spectrogram.
4th step, the one-dimensional spectrogram that duplication third step is tested recall two dimension in the case where suitable piece selects gradient intensity GPZ2
Pulse train is " push1dz " and will be sampled as dimension is set as two-dimentional sampling configuration simultaneously；Setting sampling number TD value be 8K,
It is respectively 80%, 0.2% that the indirect dimension of spectrum width, which is 30Hz, CNST20 10Hz, GPZ1 and GPZ2,；And 180 ° of shaped pulses are set
It is sampled after Gauss and obtains a pseudo- two dimension FID data.
5th step, using the AU program of purifying displacement study to obtained by the 4th step on 3.1 software of Brooker Topspin
Puppet two dimension experiment handled, data sampling complete.
New FID value is obtained finally, splicing again using AU program, using 3.1 software of Brooker Topspin by FID data
Transformation obtains One-Dimensional Pure chemical shift hydrogen and composes and optimize spectrogram as a result, the chemical displacement value presented according to different molecular in waste water
Difference carries out ownership to its component and points out.Specifically: two-dimensional map is converted by new FID value first, then transfers macros
" pshift " is executed and is obtained One-Dimensional Pure chemical shift hydrogen spectrum after the order, after processing is advanced optimized to spectrogram；Described pair of spectrum
Figure advanced optimizes processing, and specific optimal conditions are that adjustment linewidth factor LB is -5Hz, and carries out Fourier transformation, phase tune
It is as shown in Figure 1 then to obtain One-Dimensional Pure chemical shift nuclear magnetic resonance spectroscopy of the present invention for whole, baseline correction.This method is obvious
It eliminates coupling to split point and signal overlap, is conducive to the identification of signaling molecule.
Embodiment 2:
The magnetic resonance detection method for the component analysis of F- T synthesis waste water in the present embodiment is based on one-dimensional purifying
Displacement study spectrum, this method are to change dimension after selecting corresponding pulses sequence in one-dimensional hydrogen spectrum and corresponding shaped pulse is arranged,
Continuous trimmer selects gradient intensity to carry out pseudo- two dimension experiment sampling, is spliced again using AU program and obtains new FID value, uses cloth Shandong
FID data are converted to obtain One-Dimensional Pure chemical shift hydrogen and compose and optimize spectrogram as a result, according in waste water by gram 3.1 software of Topspin
The chemical displacement value difference that different molecular is presented carries out ownership to its component and points out.Include the following steps:
Firstly, selection corresponding pulses sequence " psyche.mf " changes dimension afterwards and corresponding shape is arranged in one-dimensional hydrogen spectrum
Shape pulse Reburp；
Then, continuous trimmer selects gradient intensity to carry out pseudo- two dimension experiment sampling, the specific steps are as follows:
The first step, the accurate 350 μ l of F- T synthesis waste water (II) sample that measures are mixed with the 400 deuterated water of μ l, are taken after uniformly
500 μ l of mixed liquor is put into 600MHz Liquid NMR spectrometer in sample cell.
Second step, debugging nuclear magnetic resonance chemical analyser temperature is 293K before testing, and sets air-flow as 500lph, when keeping test
Sample to be tested is static, and at the temperature of setting and air-flow after constant sample 20min, chooses pulse train zg30 and tests one often
Advise hydrogen spectrum.
Third step, the one-dimensional hydrogen spectrum that duplication second step is tested, setting spectrum width determine centre frequency；Changing pulse train is
After " push1dzs_Gset ", setting shaped pulse and constantly trimmer select gradient intensity GPZ2 value to be followed successively by 0.2%, 0.4%,
0.6%, 0.8%, 1.0%, 1.2%, until all appearing in the constituent signals in surveyed F- T synthesis waste water in spectrogram.
4th step, the one-dimensional spectrogram that duplication third step is tested recall two dimension in the case where suitable piece selects gradient intensity GPZ2
Pulse train is " psyche.mf " and will be sampled as dimension is set as two-dimentional sampling configuration simultaneously；Sampling number TD value, which is arranged, is
32K, spectrum width it is indirect dimension be 80Hz, CNST20 15Hz, GPZ1 and GPZ2 be respectively 80%, 10%；And 180 ° of shapes are set
It is sampled after pulse Reburp and obtains a pseudo- two dimension FID data.
5th step, using the AU program of purifying displacement study to obtained by the 4th step on 3.1 software of Brooker Topspin
Puppet two dimension experiment handled, data sampling complete.
New FID value is obtained finally, splicing again using AU program, using 3.1 software of Brooker Topspin by FID data
Transformation obtains One-Dimensional Pure chemical shift hydrogen and composes and optimize spectrogram as a result, the chemical displacement value presented according to different molecular in waste water
Difference carries out ownership to its component and points out.Specifically: two-dimensional map is converted by new FID value first, then transfers macros
" pshift " is executed and is obtained One-Dimensional Pure chemical shift hydrogen spectrum after the order, after processing is advanced optimized to spectrogram；Described pair of spectrum
Figure advanced optimizes processing, and specific optimal conditions are that adjustment linewidth factor LB is 0Hz, and carries out Fourier transformation, phase tune
It is as shown in Figure 2 then to obtain One-Dimensional Pure chemical shift nuclear magnetic resonance spectroscopy of the present invention for whole, baseline correction.Fig. 2 is the present invention
2 one pure chemistry of gained of embodiment is displaced nuclear magnetic resonance spectroscopy, can clearly find from figure, be not present in hydrogen spectrum
Coupling is split point, it is corresponding it is each be displaced the hydrogen that peak is a kind of chemical environment in a compound, it is clear and legible to point out component.
Embodiment 3:
The magnetic resonance detection method for the component analysis of F- T synthesis waste water in the present embodiment is based on one-dimensional purifying
Displacement study spectrum, this method are to change dimension after selecting corresponding pulses sequence in one-dimensional hydrogen spectrum and corresponding shaped pulse is arranged,
Continuous trimmer selects gradient intensity to carry out pseudo- two dimension experiment sampling, is spliced again using AU program and obtains new FID value, uses cloth Shandong
FID data are converted to obtain One-Dimensional Pure chemical shift hydrogen and compose and optimize spectrogram as a result, according in waste water by gram 3.1 software of Topspin
The chemical displacement value difference that different molecular is presented carries out ownership to its component and points out.Include the following steps:
Firstly, selection corresponding pulses sequence " psycetse.mf " is changed dimension afterwards and is arranged corresponding in one-dimensional hydrogen spectrum
Shaped pulse Rsnob；
Then, continuous trimmer selects gradient intensity to carry out pseudo- two dimension experiment sampling, the specific steps are as follows:
The first step, the accurate 700 μ l of F- T synthesis waste water (III) sample that measures are mixed with the 50 deuterated water of μ l, are taken after uniformly mixed
750 μ l of liquid is closed to be put into 800MHz Liquid NMR spectrometer in sample cell.
Second step, debugging nuclear magnetic resonance chemical analyser temperature is 323K before testing, and sets air-flow as 800lph, when keeping test
Sample to be tested is static, and at the temperature of setting and air-flow after constant sample 40min, chooses pulse train zgpr and tests one often
Advise hydrogen spectrum.
Third step, the one-dimensional hydrogen spectrum that duplication second step is tested, setting spectrum width determine centre frequency；Changing pulse train is
After " push1dzs_Gset ", setting shaped pulse and constantly trimmer select gradient intensity GPZ2 value to be followed successively by 0.2%, 0.4%,
0.6%, 0.8%, 1.0%, 1.2%, until all appearing in the constituent signals in surveyed F- T synthesis waste water in spectrogram.
4th step, the one-dimensional spectrogram that duplication third step is tested recall two dimension in the case where suitable piece selects gradient intensity GPZ2
Pulse train is " psycetse.mf " and will be sampled as dimension is set as two-dimentional sampling configuration simultaneously；Sampling number TD value is set
It is respectively 80%, 20% that indirect dimension for 64K, spectrum width, which is 150Hz, CNST20 25Hz, GPZ1 and GPZ2,；And 180 ° of shapes are set
It is sampled after shape pulse Rsnob and obtains a pseudo- two dimension FID data.
5th step, using the AU program of purifying displacement study to obtained by the 4th step on 3.1 software of Brooker Topspin
Puppet two dimension experiment handled, data sampling complete.
New FID value is obtained finally, splicing again using AU program, using 3.1 software of Brooker Topspin by FID data
Transformation obtains One-Dimensional Pure chemical shift hydrogen and composes and optimize spectrogram as a result, the chemical displacement value presented according to different molecular in waste water
Difference carries out ownership to its component and points out.Specifically: two-dimensional map is converted by new FID value first, then transfers macros
" pshift " is executed and is obtained One-Dimensional Pure chemical shift hydrogen spectrum after the order, after processing is advanced optimized to spectrogram；Described pair of spectrum
Figure advanced optimizes processing, and specific optimal conditions are that adjustment linewidth factor LB is 5Hz, and carries out Fourier transformation, phase tune
It is as shown in Figure 3 then to obtain One-Dimensional Pure chemical shift nuclear magnetic resonance spectroscopy of the present invention for whole, baseline correction.It can be with from figure
Clearly discovery be not present coupling in hydrogen spectrum and has split point, and corresponding each peak that is displaced is one kind in a compound
The hydrogen of chemical environment, it is clear and legible to point out component.
Embodiment 4:
The magnetic resonance detection method for the component analysis of F- T synthesis waste water in the present embodiment is based on one-dimensional purifying
Displacement study spectrum, this method are to change dimension after selecting corresponding pulses sequence in one-dimensional hydrogen spectrum and corresponding shaped pulse is arranged,
Continuous trimmer selects gradient intensity to carry out pseudo- two dimension experiment sampling, is spliced again using AU program and obtains new FID value, uses cloth Shandong
FID data are converted to obtain One-Dimensional Pure chemical shift hydrogen and compose and optimize spectrogram as a result, according in waste water by gram 3.1 software of Topspin
The chemical displacement value difference that different molecular is presented carries out ownership to its component and points out.Include the following steps:
Firstly, selection corresponding pulses sequence " psyche.mf " changes dimension afterwards and corresponding shape is arranged in one-dimensional hydrogen spectrum
Shape pulse Gauss；
Then, continuous trimmer selects gradient intensity to carry out pseudo- two dimension experiment sampling, the specific steps are as follows:
The first step, the accurate 400 μ l of F- T synthesis waste water (IV) sample that measures are mixed with the 350 deuterated water of μ l, are taken after uniformly
400 μ l of mixed liquor is put into 400MHz Liquid NMR spectrometer in sample cell.
Second step, debugging nuclear magnetic resonance chemical analyser temperature is 293K before testing, and sets air-flow as 200lph, when keeping test
Sample to be tested is static, and at the temperature of setting and air-flow after constant sample 15min, chooses pulse train zg and tests a routine
Hydrogen spectrum.
Third step, the one-dimensional hydrogen spectrum that duplication second step is tested, setting spectrum width determine centre frequency；Changing pulse train is
After " push1dzs_Gset ", setting shaped pulse and constantly trimmer select gradient intensity GPZ2 value to be followed successively by 0.2%, 0.4%,
0.6%, 0.8%, 1.0%, 1.2%, until all appearing in the constituent signals in surveyed F- T synthesis waste water in spectrogram.
4th step, the one-dimensional spectrogram that duplication third step is tested recall two dimension in the case where suitable piece selects gradient intensity GPZ2
Pulse train is " psyche.mf " and will be sampled as dimension is set as two-dimentional sampling configuration simultaneously；Sampling number TD value, which is arranged, is
8K, spectrum width it is indirect dimension be 50Hz, CNST20 15Hz, GPZ1 and GPZ2 be respectively 80%, 1.5%；And 180 ° of shapes are set
It is sampled after pulse Gauss and obtains a pseudo- two dimension FID data.
5th step, using the AU program of purifying displacement study to obtained by the 4th step on 3.1 software of Brooker Topspin
Puppet two dimension experiment handled, data sampling complete.
New FID value is obtained finally, splicing again using AU program, using 3.1 software of Brooker Topspin by FID data
Transformation obtains One-Dimensional Pure chemical shift hydrogen and composes and optimize spectrogram as a result, the chemical displacement value presented according to different molecular in waste water
Difference carries out ownership to its component and points out.Specifically: two-dimensional map is converted by new FID value first, then transfers macros
" pshift " is executed and is obtained One-Dimensional Pure chemical shift hydrogen spectrum after the order, after processing is advanced optimized to spectrogram；Described pair of spectrum
Figure advanced optimizes processing, and specific optimal conditions are that adjustment linewidth factor LB is 3Hz, and carries out Fourier transformation, phase tune
Whole, baseline correction, then obtaining One-Dimensional Pure chemical shift nuclear magnetic resonance spectroscopy of the present invention such as Fig. 4 is the embodiment of the present invention 4
Measured one-dimensional conventional hydrogen spectrum；Fig. 5 is that pulse is " psycetse.mf " test one purifying of gained in the embodiment of the present invention 4
Displacement study nuclear magnetic resonance spectroscopy.It can clearly be found from Fig. 5, compared with conventional hydrogen spectrum 4, One-Dimensional Pure chemical shift hydrogen spectrum
In coupling be not present split point, it is corresponding it is each be displaced the hydrogen that peak is a kind of chemical environment in a compound, wait refer to
The component spectral peak recognized is clear and legible.
Embodiment 5:
The magnetic resonance detection method for the component analysis of F- T synthesis waste water in the present embodiment is based on one-dimensional purifying
Displacement study spectrum, this method are to change dimension after selecting corresponding pulses sequence in one-dimensional hydrogen spectrum and corresponding shaped pulse is arranged,
Continuous trimmer selects gradient intensity to carry out pseudo- two dimension experiment sampling, is spliced again using AU program and obtains new FID value, uses cloth Shandong
FID data are converted to obtain One-Dimensional Pure chemical shift hydrogen and compose and optimize spectrogram as a result, according in waste water by gram 3.1 software of Topspin
The chemical displacement value difference that different molecular is presented carries out ownership to its component and points out.Include the following steps:
Firstly, selection corresponding pulses sequence " psycetse.mf " is changed dimension afterwards and is arranged corresponding in one-dimensional hydrogen spectrum
Shaped pulse Gauss；
Then, continuous trimmer selects gradient intensity to carry out pseudo- two dimension experiment sampling, the specific steps are as follows:
The first step, the accurate 50 μ l of F- T synthesis waste water (I) sample that measures are mixed with the 700 deuterated water of μ l, are taken after uniformly mixed
400 μ l of liquid is closed to be put into 300MHz Liquid NMR spectrometer in sample cell.
Second step, debugging nuclear magnetic resonance chemical analyser temperature is 273K before testing, and sets air-flow as 200lph, when keeping test
Sample to be tested is static, and at the temperature of setting and air-flow after constant sample 10min, chooses pulse train zg and tests a routine
Hydrogen spectrum.
Third step, the one-dimensional hydrogen spectrum that duplication second step is tested, setting spectrum width determine centre frequency；Changing pulse train is
After " push1dzs_Gset ", setting shaped pulse and constantly trimmer select gradient intensity GPZ2 value to be followed successively by 0.2%, 0.4%,
0.6%, 0.8%, 1.0%, 1.2%, until all appearing in the constituent signals in surveyed F- T synthesis waste water in spectrogram.
4th step, the one-dimensional spectrogram that duplication third step is tested recall two dimension in the case where suitable piece selects gradient intensity GPZ2
Pulse train is " psycetse.mf " and will be sampled as dimension is set as two-dimentional sampling configuration simultaneously；Sampling number TD value is set
It is respectively 80%, 1.2% that indirect dimension for 8K, spectrum width, which is 50Hz, CNST20 15Hz, GPZ1 and GPZ2,；And 180 ° of shapes are set
It is sampled after shape pulse Gauss and obtains a pseudo- two dimension FID data.
5th step, using the AU program of purifying displacement study to obtained by the 4th step on 3.1 software of Brooker Topspin
Puppet two dimension experiment handled, data sampling complete.
New FID value is obtained finally, splicing again using AU program, using 3.1 software of Brooker Topspin by FID data
Transformation obtains One-Dimensional Pure chemical shift hydrogen and composes and optimize spectrogram as a result, the chemical displacement value presented according to different molecular in waste water
Difference carries out ownership to its component and points out.Specifically: two-dimensional map is converted by new FID value first, then transfers macros
" pshift " is executed and is obtained One-Dimensional Pure chemical shift hydrogen spectrum after the order, after processing is advanced optimized to spectrogram；Described pair of spectrum
Figure advanced optimizes processing, and specific optimal conditions are that adjustment linewidth factor LB is 3Hz, and carries out Fourier transformation, phase tune
Whole, baseline correction then obtains One-Dimensional Pure chemical shift nuclear magnetic resonance spectroscopy measured by the embodiment of the present invention 5 and one-dimensional conventional hydrogen
Spectrum is as shown in Figure 6；
Comparative example:
To show that a pure chemistry is displaced nuclear magnetic resonance detection method compared to other conventional nuclear magnetic resonance (expansions in the present invention
Dissipate sequence spectrum) method superiority, using two-dimensional diffusion sort spectrum (DOSY) magnetic nuclear resonance method to F- T synthesis waste water component
Analyzed, as a result see Fig. 7, from the implementation process and result figure of this method it is found that this method not only the testing time it is longer and
And test result traffic congestion stacks seriously compared to Fig. 6, separating effect is unobvious, is unable to reach one-dimensional pure chemistry in the present invention
It is displaced accurate analysis of the magnetic nuclear resonance method to F- T synthesis waste water component.
Claims (10)
1. a kind of magnetic resonance detection method for F- T synthesis waste water component analysis, it is characterised in that: described is used to take
The magnetic resonance detection method of support synthetic wastewater component analysis is composed based on One-Dimensional Pure chemical shift, and this method is composed in one-dimensional hydrogen
Dimension is changed after upper selection corresponding pulses sequence and corresponding shaped pulse is set, and continuous trimmer selects gradient intensity to carry out puppet two
Dimension experiment sampling, is spliced again using AU program and obtains new FID value, become FID data using 3.1 software of Brooker Topspin
Get in return One-Dimensional Pure chemical shift hydrogen compose and optimize spectrogram as a result, the chemical displacement value presented according to different molecular in waste water not
It is pointed out with ownership is carried out to its component.
2. a kind of magnetic resonance detection method for F- T synthesis waste water component analysis according to claim 1, special
Sign is: the One-Dimensional Pure chemical shift spectrum is sampled based on three kinds of pulse trains.
3. a kind of magnetic resonance detection method for F- T synthesis waste water component analysis according to claim 2, special
Sign is: the magnetic resonance detection method for the component analysis of F- T synthesis waste water is composed based on One-Dimensional Pure chemical shift,
This method is to change dimension after selecting corresponding pulses sequence in one-dimensional hydrogen spectrum and corresponding shaped pulse is arranged, and is continuously increased ladder
It spends intensity and carries out pseudo- two dimension experiment sampling, specific step is as follows for test:
The first step, it is accurate to measure 50~700 μ l of F- T synthesis wastewater sample, it is mixed with the deuterated reagent of 700~50 μ l, is taken
400~750 μ l of mixed liquor is put into Liquid NMR spectrometer in sample cell；
Second step, test before debugging nuclear magnetic resonance chemical analyser temperature be 273K~323K, setting airflow rate be 200~
800lph, constant sample 10~40 minutes at the temperature of setting and air-flow；It chooses pulse train zg, zg30 or zgpr test should
The common one-dimensional hydrogen spectrum of sample；
Third step, the one-dimensional hydrogen spectrum that duplication second step is tested, setting spectrum width determine centre frequency；Changing pulse train is
After " push1dzs_Gset ", simultaneously constantly trimmer selects gradient intensity GPZ2 value to setting shaped pulse, so that in F- T synthesis waste water
Constituent signals all appear in spectrogram；
4th step recalls Two-dimensional Pulsed sequence in the case where suitable piece selects gradient intensity GPZ2, and 180 ° of shaped pulses and GPZ1 is arranged
Value continuouslys optimize correlated sampling parameter after being 80%, obtains a pseudo- two-dimentional experimental data；
5th step, using the AU program of purifying displacement study to the 4th obtained puppet of step on 3.1 software of Brooker Topspin
Two dimension experiment is handled, and data sampling is completed.
4. a kind of magnetic resonance detection method for F- T synthesis waste water component analysis according to claim 3, special
Sign is: the spectrometer that the magnetic resonance detection method uses is 300~800MHz Liquid NMR wave spectrum with gradient fields
Instrument.
5. a kind of magnetic resonance detection method for F- T synthesis waste water component analysis according to claim 4, special
Sign is: deuterated reagent is heavy water, deuterated methanol, deuterated acetone or deuterated-N,N-dimethylformamide in the first step.
6. a kind of magnetic resonance detection method for F- T synthesis waste water component analysis according to claim 5, special
Sign is: the piece in the third and four steps selects gradient intensity GPZ2 value, and adjusting range is between 0.2%~20%, not
Break increased in the case where selecting gradient intensity, obtains a series of free induction decay FID value.
7. a kind of magnetic resonance detection method for F- T synthesis waste water component analysis according to claim 6, special
Sign is: the shaped pulse classification be Gauss, Reburp or Rsnob, and be arranged specific pulsewidth and its it is corresponding continue when
Between be respectively 10KHz and 30ms.
8. a kind of magnetic resonance detection method for F- T synthesis waste water component analysis according to claim 7, special
Sign is: the pulse train that the 4th step is recalled is " push1dz ", " psyche.mf " or " psycetse.mf ".
9. a kind of magnetic resonance detection method for F- T synthesis waste water component analysis according to claim 8, special
Sign is: the 4th step continues to optimize correlated sampling parameter, and sampling parameter setting is as follows, and sampling number TD value is 8k~64k,
Directly dimension spectrum width is the integral multiple of indirect dimension spectrum width and indirect dimension value takes 30~150Hz, and CNST20 value is 10~25Hz.
10. -9 described in any item a kind of magnetic resonance detections for F- T synthesis waste water component analysis according to claim 1
Method, it is characterised in that: the utilization AU program is spliced again obtains new FID value, will using 3.1 software of Brooker Topspin
FID data, which convert to obtain One-Dimensional Pure chemical shift hydrogen, composes and optimizes spectrogram as a result, its concrete operations are as follows: first by new FID value
It is converted into two-dimensional map, then transfers macros " pshift ", obtains One-Dimensional Pure chemical shift hydrogen spectrum after executing the order, after
Processing is advanced optimized to spectrogram；Described to advanced optimize processing to spectrogram, specific optimal conditions are adjustment linewidth factor LB
For -5~5Hz, and Fourier transformation, phase adjustment, baseline correction are carried out, then obtains related pure chemistry displacement hydrogen nuclear magnetic resonance
Spectrum.
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