CN108037194A - To the method for polycyclic aromatic hydrocarbon autoclave hydrogenation products qualitative, quantitative - Google Patents
To the method for polycyclic aromatic hydrocarbon autoclave hydrogenation products qualitative, quantitative Download PDFInfo
- Publication number
- CN108037194A CN108037194A CN201711060906.2A CN201711060906A CN108037194A CN 108037194 A CN108037194 A CN 108037194A CN 201711060906 A CN201711060906 A CN 201711060906A CN 108037194 A CN108037194 A CN 108037194A
- Authority
- CN
- China
- Prior art keywords
- sample
- aromatic hydrocarbon
- gas chromatograph
- quantitative
- polycyclic aromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/38—Flow patterns
- G01N30/46—Flow patterns using more than one column
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N30/68—Flame ionisation detectors
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a kind of method to polycyclic aromatic hydrocarbon autoclave hydrogenation products qualitative, quantitative.This method comprises the following steps：Sample to be tested is passed through into gas chromatograph split sampling mouth sample introduction, gas chromatograph split sampling mouth connects two identical chromatographic columns in parallel, two root chromatogram columns are connected respectively to mass spectrograph and flame ionic detector, qualitative analysis is carried out to sample using the data that mass spectrograph detects, the data that flame ionic detector detects carry out quantitative analysis to sample.Apply the technical scheme of the present invention, by the chromatographic column to polycyclic aromatic hydrocarbon autoclave hydrogenation products by gas chromatograph split sampling mouth sample introduction to two same models in parallel, respectively qualitative, quantitative is carried out on MS (mass spectrograph) and fid detector (flame ionic detector), it is greatly saved sample minute, reduce standard specimen purchase consumption, can efficiently, quickly react the autoclave hydrogenation situation of polycyclic aromatic hydrocarbon.
Description
Technical field
The present invention relates to technical field of coal chemical industry, and polycyclic aromatic hydrocarbon autoclave hydrogenation products are determined in particular to a kind of
The quantitative method of property.
Background technology
During the direct liquefaction of coal, numerous conditions influence the conversion ratio of DCL/Direct coal liquefaction, such as the property of feed coal
Matter, atmospheric condition, solvent, the species of catalyst and technological parameter of operation etc., wherein solvent are to influence DCL/Direct coal liquefaction conversion
The essential condition of rate.
The effect of solvent has heat of solution coal, dissolving hydrogen, hydrogen supply and transmits hydrogen and the reaction of direct and coal etc..Hydrogen supply performance is good
Solvent not only directly affect the conversion ratio and oil yield of coal, also help coal slurry prepare, conveying and the flowing in heating furnace
Property etc..Solvent hydrogen supply capacity and solvent composition are closely related, and DCL/Direct coal liquefaction solvent is mainly by alkane, saturated hydrocarbons, monocyclic virtue
Hydrocarbon, double ring arene and thrcylic aromatic hydrocarbon composition, most of hydrogen supply capacity come from the hydrogenation of aromatics of double ring arene and thrcylic aromatic hydrocarbon.By
In the complexity of structure, most of hydrogenation of aromatics can not commercially be bought, at present the main side using polycyclic aromatic hydrocarbon hydrogenation
Method obtains, and qualitative and quantitative analysis is carried out to the hydrogenation products of polycyclic aromatic hydrocarbon this requires a set of fast and accurately method.It is related
The qualitative and quantitative analysis of polycyclic aromatic hydrocarbon hydrogenation products, traditional method be using liquid chromatography-mass spectrography, gas chromatography-mass spectrum into
Simple qualitative of row, or qualitative, quantitative is carried out to the hydrogenation of aromatics easily bought using the method for establishing standard curve, these
The method solvent Buying Cycle is long, solvent-oil ratio is big, and the hydrogenation products to being difficult to buy standard specimen are difficult to quantitative analysis.
The content of the invention
The present invention is intended to provide a kind of method to polycyclic aromatic hydrocarbon autoclave hydrogenation products qualitative, quantitative, to solve existing skill
The big technical problem of solvent-oil ratio is used to polycyclic aromatic hydrocarbon autoclave hydrogenation products qualitative, quantitative in art.
To achieve these goals, according to an aspect of the invention, there is provided a kind of be hydrogenated with polycyclic aromatic hydrocarbon autoclave
The method of product qualitative, quantitative.This method comprises the following steps：By sample to be tested by gas chromatograph split sampling mouth sample introduction,
Gas chromatograph split sampling mouth connects two identical chromatographic columns in parallel, and two root chromatogram columns are connected respectively to mass spectrograph and fire
Flame ion detector, qualitative analysis is carried out using the data that mass spectrograph detects to sample, what flame ionic detector detected
Data carry out quantitative analysis to sample.
Further, the model HP-5MS chromatographic columns of chromatographic column.
Further, the specification of chromatographic column is 30m × 0.25 μm of 250 μ m.
Further, carrier gas used in gas chromatograph is nitrogen.
Further, gas chromatograph uses constant flow rate pattern.
Further, the sample size of sample to be tested is 0.2 μ L, split ratio 100:1, injector temperature is 290~310
DEG C, inlet pressure 12.537psi, chromatography column flow is 1mL/min, gas chromatograph internal detector temperature 310~330
℃。
Further, the hydrogen gas flow of flame ionic detector is 30~40mL/min, the flow of air-breathing gas
For 300~400mL/min.
Further, quantitative analysis uses area normalization method.
Further, the split sampling mouth of gas chromatograph is provided with a double aperture seal packing ring.
Apply the technical scheme of the present invention, gas chromatograph split sampling will be passed through to polycyclic aromatic hydrocarbon autoclave hydrogenation products
Mouth sample introduction is to the chromatographic column of two same models in parallel, and in MS (mass spectrograph) and fid detector, (flame ion detects respectively
Device) on carry out qualitative, quantitative, be greatly saved sample minute, reduce standard specimen purchase consumption, can efficiently, quickly instead
The autoclave of polycyclic aromatic hydrocarbon is answered to be hydrogenated with situation.
Brief description of the drawings
The accompanying drawings which form a part of this application are used for providing a further understanding of the present invention, and of the invention shows
Meaning property embodiment and its explanation are used to explain the present invention, do not form inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 shows the method to polycyclic aromatic hydrocarbon autoclave hydrogenation products qualitative, quantitative according to an embodiment of the present invention
Flow diagram；And
Fig. 2A and Fig. 2 B respectively illustrate anthracene autoclave hydrogenation products MS and FID the detection spectrogram of embodiment 1；
Fig. 3 A and Fig. 3 B respectively illustrate luxuriant and rich with fragrance autoclave hydrogenation products MS and FID the detection spectrogram of embodiment 2；And
Fig. 4 A and Fig. 4 B respectively illustrate the 1- methyl naphthalenes of embodiment 3, luxuriant and rich with fragrance autoclave hydrogenation products MS and FID detection spectrum
Figure.
Embodiment
It should be noted that in the case where there is no conflict, the feature in embodiment and embodiment in the application can phase
Mutually combination.Below with reference to the accompanying drawings and the present invention will be described in detail in conjunction with the embodiments.
The final purpose of the present invention mainly establishes a kind of accurate, quick, easy measure polycyclic aromatic hydrocarbon autoclave hydrogenation production
The method of thing.
A kind of typical embodiment according to the present invention, there is provided a kind of to polycyclic aromatic hydrocarbon autoclave hydrogenation products qualitative, quantitative
Method.This method comprises the following steps：As shown in Figure 1, by sample to be tested by the split sampling mouth of gas chromatograph 10 into
Sample, the double split flow injection port of gas chromatograph connect two identical chromatographic columns in parallel, and two root chromatogram columns are connected respectively to matter
Spectrometer 20 and flame ionic detector 30, sample is carried out qualitative analysis, flame ion inspection using the data that mass spectrograph detects
Survey the data that device detects and quantitative analysis is carried out to sample.
Apply the technical scheme of the present invention, gas chromatograph split sampling will be passed through to polycyclic aromatic hydrocarbon autoclave hydrogenation products
Mouth sample introduction is to the chromatographic column of two same models in parallel, and in MS (mass spectrograph) and fid detector, (flame ion detects respectively
Device) on carry out qualitative, quantitative, be greatly saved sample minute, reduce standard specimen purchase consumption, can efficiently, quickly instead
The autoclave of polycyclic aromatic hydrocarbon is answered to be hydrogenated with situation.
After sample introduction, there are two corresponding MS and FID test maps in analysis result, and the compound of two collection of illustrative plates is one a pair of
Answer, compound is quantified using FID detections data, MS detection data are qualitative to compound progress, due to polycyclic aromatic hydrocarbon
Hydrogenation products property is similar, and the error that correction factor produces can be neglected, and quantitative approach can directly use area normalization method.The party
Method is quick, easy, has higher repeatability and accuracy.
A kind of typical embodiment according to the present invention, the split sampling mouth of gas chromatograph are provided with a double aperture seal
Packing ring.Preferably, the model HP-5MS chromatographic columns of chromatographic column.Polycyclic aromatic hydrocarbon and its hydrogenation products are low pole and non-polarization
Compound, HP-5MS chromatographic columns fixer is (5% phenyl)-methyl polysiloxane, according to " similar compatibility " principle, using this model
Chromatographic column can preferably separate polycyclic aromatic hydrocarbon hydrogenation products.
Preferably, the specification of chromatographic column is 30m × 0.25 μm of 250 μ m.The composition letter of polycyclic aromatic hydrocarbon hydrogenation products compound
Single, more easily separated analysis, can separate component using 30m × 0.25 μm of 250 μ m, it is not necessary to the color of longer thinner specification
Column is composed, reduces analysis cost.
A kind of typical embodiment according to the present invention, carrier gas used in gas chromatograph are nitrogen.
Preferably, gas chromatograph uses constant flow rate pattern.Due to the temperature programming used during chromatographic
Pattern, constant flow rate pattern can be such that flow does not change with the rise of temperature, so that reproducibility of analysis results and precision
Higher.
Gas chromatograph is subjected to chromatographic condition optimization, finds the optimal separation bar of polycyclic aromatic hydrocarbon autoclave hydrogenation products
Part.Preferably, the sample size of sample to be tested is 2 μ L, split ratio 100:1, injector temperature is 290~310 DEG C, injection port pressure
Power is 12.537psi, and chromatography column flow is 1mL/min, 310~330 DEG C of gas chromatograph internal detector temperature.Wherein, 100:1
Split ratio, refer to liquor sample injection injector gasification and with carrier gas after mixing, 1/101 sample and carrier gas enter color
Column is composed, 100/101 sample and air emptying, are herein identical into the amount of flame detector and mass detector sample.
Preferably, the hydrogen gas flow of flame ionic detector is 30~40mL/min, and the flow of air-breathing gas is
300~400mL/min.
Beneficial effects of the present invention are further illustrated below in conjunction with embodiment.
Since hydrogenation products structure is similar, there is similar correction factor on same fid detector, correction can be neglected
The error that the different band of the factor is come, the testing result of the correction factor of part of standards compound on fid detector are shown in Table 1, table
Material on the basis of middle toluene, correction factor fmRepresent, the correction factor f of n-compoundiRepresent.
Table 1
Embodiment 1
The autoclave hydrogenation products 1.5mL of anthracene is taken in chromatogram bottle, sets chromatographic condition：Sample size is 0.2 μ L, chromatographic column
Flow is 1mL/min, chromatographic program Elevated Temperature Conditions 60 DEG C (2min), and 2 DEG C/min rises to 250 DEG C.The detection of detector MS and FID
Collection of illustrative plates such as Fig. 2A and Fig. 2 B, the hydrogenation products result such as table 2 below measured.
Table 2
Embodiment 2
The autoclave hydrogenation products 1.5mL of phenanthrene is taken to set chromatographic condition in chromatogram bottle：Sample size is 0.2 μ L, chromatographic column
Flow is 1mL/min, and chromatographic program Elevated Temperature Conditions rise to 250 DEG C for 60 DEG C of (5min) 2 DEG C/min.The inspection of detector MS and FID
Mapping spectrum such as Fig. 3 A and Fig. 3 B, the hydrogenation products result measured such as table 3.
Table 3
Embodiment 3
The autoclave hydrogenation products 1.5mL of 1- methyl naphthalenes and luxuriant and rich with fragrance mixture is taken to set chromatographic condition in chromatogram bottle：Sample introduction
It is 1mL/min to measure as 0.2 μ L, chromatography column flow, and chromatographic program Elevated Temperature Conditions rise to 250 DEG C for 50 DEG C of (2min) 1.5 DEG C/min.
The test map of detector MS and FID such as Fig. 4 A and Fig. 4 B, the hydrogenation products result measured such as table 4.
Table 4
It can be seen from the above description that the above embodiments of the present invention realize following technique effect：To polycyclic
During aromatic hydrogenation product qualitative, quantitative, hydrogenation is produced using the chromatograph equipped with split sampling mouth and same model chromatographic column in parallel
Thing carries out qualitative and quantitative analysis.This method is fast and convenient, using the proximity of polycyclic aromatic hydrocarbon hydrogenation products correction factor, reaches
Do not establishing any graticule, purpose of the single injected sampling to hydrogenation products qualitative, quantitative.Minute is short, solvent consumption is few, measure
It is efficient, be conducive to timely detect polycyclic aromatic hydrocarbon autoclave hydrogenation products.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the invention, for the skill of this area
For art personnel, the invention may be variously modified and varied.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should all be included in the protection scope of the present invention.
Claims (9)
- A kind of 1. method to polycyclic aromatic hydrocarbon autoclave hydrogenation products qualitative, quantitative, it is characterised in that comprise the following steps：It will treat Sample by the split sampling mouth sample introduction of gas chromatograph, the split sampling mouth of the gas chromatograph connect two it is in parallel Identical chromatographic column, two chromatographic columns are connected respectively to mass spectrograph and flame ionic detector, are examined using the mass spectrograph The data measured carry out the sample qualitative analysis, and the data that the flame ionic detector detects carry out the sample Quantitative analysis.
- 2. the according to the method described in claim 1, it is characterized in that, model HP-5MS chromatographic columns of the chromatographic column.
- 3. according to the method described in claim 2, it is characterized in that, the specification of the chromatographic column is 30m × 250 μ m, 0.25 μ m。
- 4. according to the method described in claim 1, it is characterised in that carrier gas used in the gas chromatograph is nitrogen.
- 5. according to the method described in claim 1, it is characterised in that the gas chromatograph uses constant flow rate pattern.
- 6. according to the method described in claim 5, it is characterised in that the sample size of the sample to be tested is 0.2 μ L, and split ratio is 100:1, injector temperature is 290~310 DEG C, inlet pressure 12.537psi, and chromatography column flow is 1mL/min, the gas 310~330 DEG C of chromatography internal detector temperature.
- 7. according to the method described in claim 1, it is characterized in that, the hydrogen gas flow of the flame ionic detector is 30 ~40mL/min, the flow of air-breathing gas is 300~400mL/min.
- 8. according to the method described in claim 1, it is characterized in that, the quantitative analysis uses area normalization method.
- 9. according to the method described in claim 1, it is characterized in that, the split sampling mouth of the gas chromatograph is provided with one Double aperture seal packing ring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711060906.2A CN108037194A (en) | 2017-11-01 | 2017-11-01 | To the method for polycyclic aromatic hydrocarbon autoclave hydrogenation products qualitative, quantitative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711060906.2A CN108037194A (en) | 2017-11-01 | 2017-11-01 | To the method for polycyclic aromatic hydrocarbon autoclave hydrogenation products qualitative, quantitative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108037194A true CN108037194A (en) | 2018-05-15 |
Family
ID=62093695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711060906.2A Pending CN108037194A (en) | 2017-11-01 | 2017-11-01 | To the method for polycyclic aromatic hydrocarbon autoclave hydrogenation products qualitative, quantitative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108037194A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110646556A (en) * | 2019-09-26 | 2020-01-03 | 中国神华煤制油化工有限公司 | Method for analyzing components of organic sample |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0825981B2 (en) * | 1987-05-27 | 1996-03-13 | 和光純薬工業株式会社 | Novel pyrene derivative and high performance liquid chromatography using the same as a labeling agent |
| CN104422748A (en) * | 2013-09-03 | 2015-03-18 | 中国石油化工股份有限公司 | Method for evaluating hydrogen donating ability of hydrogen donor for reaction matrix |
-
2017
- 2017-11-01 CN CN201711060906.2A patent/CN108037194A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0825981B2 (en) * | 1987-05-27 | 1996-03-13 | 和光純薬工業株式会社 | Novel pyrene derivative and high performance liquid chromatography using the same as a labeling agent |
| CN104422748A (en) * | 2013-09-03 | 2015-03-18 | 中国石油化工股份有限公司 | Method for evaluating hydrogen donating ability of hydrogen donor for reaction matrix |
Non-Patent Citations (7)
| Title |
|---|
| M. I. BAIKENOV ET AL: "Catalytic Hydrogenation of Anthracene in Ethanol", 《SOLID FUEL CHEMISTRY》 * |
| M. I. BAIKENOV ET AL: "Effect of New Catalytic Systems on the Process of Anthracene Hydrogenation", 《SOLID FUEL CHEMISTRY》 * |
| MICHAEL W. BEDELL: "Comparison of Hydrogen Transfer from Cyclic Olefins and Hydroaromatic Donors under Thermal and Catalytic Liquefaction Conditions", 《ENERGY & FUELS》 * |
| ROBERTO ROSAL ET AL: "Estimation of the concentration of hydroaromatic compounds in a hydrogenated anthracene oil", 《FUEL》 * |
| TAO YUAN ET AL: "Catalytic hydrogenation of polycyclic aromatic hydrocarbons over palladium/γ-Al2O3 under mild conditions", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| 蔡新恒 等: "催化裂化柴油中多环芳烃加氢转化的分子水平表征", 《石油化工（石油加工）》 * |
| 陈冬花: "工业萘加氢精制产品的气相色谱分析", 《色谱》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110646556A (en) * | 2019-09-26 | 2020-01-03 | 中国神华煤制油化工有限公司 | Method for analyzing components of organic sample |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101315353B (en) | Method for detecting perfuming homogeneity of cigarette production based on marker | |
| CN205426869U (en) | Adopt portable designing's non -methane total hydrocarbon analysis module | |
| CN103336070B (en) | The pick-up unit of sulfur-bearing failure gas component and method in a kind of quantitative detection sulfur hexafluoride electrical equipment | |
| CN106841442B (en) | Method for simultaneously determining vinyl acetate and six benzene series in water-based adhesive | |
| CN108717106A (en) | The device and its detection method of total sulfur content in a kind of detection natural gas | |
| CN104698115A (en) | Method for measuring content of n-alkanes in liquid paraffin | |
| CN103675080A (en) | Headspace sampler and ion mobility spectrometry combined system | |
| CN108037194A (en) | To the method for polycyclic aromatic hydrocarbon autoclave hydrogenation products qualitative, quantitative | |
| CN104330490B (en) | Utilize the external standard assay method of benzene and benzene homologues in the glyceryl triacetate of head space-gaseous mass spectrum | |
| CN106525998A (en) | Method of measuring content of benzene series ingredients in stationary pollution source waste gas | |
| CN205080119U (en) | Volatility organic gas on -line monitoring system | |
| CN104390926A (en) | Online rapid detection method of herba andrographis concentrated decolorization process | |
| CN105044263B (en) | A kind of gas chromatogram method of inspection of 4-ethyoxyl-2,3-difluorophenol | |
| CN203405450U (en) | Detection device for quantitatively detecting sulfur-containing fault gas components in sulphur hexafluoride electrical equipment | |
| CN110412191A (en) | A kind of non-first total hydrocarbon benzene homologues online gc of list detector list ten-way valve | |
| CN104614477A (en) | Method for determining trace methanol content of 1-butylene | |
| CN206818606U (en) | Electric automobile power battery system fire produces the qualitative and quantitative analysis device of gas | |
| CN109632989A (en) | A kind of four compound mensuration device and method of heavy oil of high throughput | |
| CN208255220U (en) | The device of total sulfur content in a kind of detection natural gas | |
| CN203672845U (en) | Trace sulfide chromatographic analyzer | |
| CN201716291U (en) | Analyzer for measuring gas | |
| CN101819192A (en) | Method for detecting naphthalene content in washing oil by gas chromatography | |
| CN108020484A (en) | A kind of method of quick measurement crude oil saturated vapor pressure | |
| CN104931641B (en) | Petroleum asphaltene component analysis method | |
| CN106596745A (en) | Method for analyzing products for removing alkene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180515 |