CN101581706A - Analytical method of phenolic compounds in coal direct liquefaction oil - Google Patents

Analytical method of phenolic compounds in coal direct liquefaction oil Download PDF

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CN101581706A
CN101581706A CNA2009100861599A CN200910086159A CN101581706A CN 101581706 A CN101581706 A CN 101581706A CN A2009100861599 A CNA2009100861599 A CN A2009100861599A CN 200910086159 A CN200910086159 A CN 200910086159A CN 101581706 A CN101581706 A CN 101581706A
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coal
phenolic compound
enrichment
phenolic compounds
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CN101581706B (en
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毛学锋
李文博
朱晓苏
史士东
杜淑凤
高振楠
张晓静
胡发亭
朱肖曼
刘敏
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China Coal Research Institute CCRI
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Abstract

The invention relates to an analytical method of phenolic compounds in coal direct liquefaction oil, which is characterized by using 10 mass % of NaOH to extract enriched phenolic compounds, then using derivatization reagent BTSFA or DPPC and active agent pyridine to carry out quantitative derivatization reaction to obtain silicone ether derivative solution, and adopting chromatography-mass spectrometry to qualitatively analyze silicone ether derivatives of each free phenol and adopting gas phase chromatography to qualitatively analyze each free phenol. The method has wide detection range, simple and convenient operation and high sensitivity. The invention can qualitatively analyze 54 types of monomer phenolic compounds and 27 types of monomer phenolic compounds, and can be widely used for enrichment and analysis of phenolic compounds in coal direct liquefaction oil.

Description

The analytical approach of phenolic compound in the coal direct liquefaction oil
Technical field
The present invention relates to the coal direct liquefaction field, particularly relate to the analytical approach of phenolic compound in the coal direct liquefaction oil.
Background technology
Coal direct liquefaction (hereinafter to be referred as " coal liquefaction ") is a kind ofly can effectively alleviate the China's oil shortage, improve the primary energy utilization ratio, reduce coal and directly utilize one of with serious pollution novel coal chemical technology that brings.
Content of phenolic compounds is up to 20% in the once thick oil that coal liquefaction obtains, these phenolic compounds are in the follow-up upgrading process of liquefied coal coil, not only can increase the hydrogen consumption of process, improve the cost of liquefied coal coil, and the water that its reaction generates will have a negative impact the severity of increase follow-up hydrogenation reaction to catalyst activity and life-span.Simultaneously, the existence of phenols also can produce certain influence to the stability of liquefaction oil product, and the phenolic compound significant feature is to promote the formation of sediment and deepening of color.The researcher thinks to have only in the liquefied coal coil the senior phenols of part that the coal liquefaction reaction is had positive role, and most rudimentary phenols not only can not promote the coal liquefaction reaction, even some rudimentary phenolic compound hinders the coal liquefaction process because of polycondensation at high temperature takes place.In addition, phenolic compound is the valuable raw material of a plurality of fine chemistry industry industries such as agricultural chemicals, medicine, printing and dyeing, spices and important fine-chemical intermediate, and its price is several times even tens times of finished product fuel oil, has very high economic value added.High added value phenols technology is extracted in exploitation from the coal liquefaction oil product, vast market demand prospect and huge economic benefit are arranged, to further promote the economy of coal liquefaction technology, widen the comprehensive Utilization Ways of liquefied coal coil, strengthen the competitive edge of coal liquefaction self.
System, accurately, qualitative and quantitative analysis detects the type and the content of phenolic compound in the liquefied coal coil, is high efficiency extraction and the basis that rationally utilizes phenolic compound.The researcher starts from the seventies in last century to the analysis of aldehydes matter in the coal liquefaction product both at home and abroad, generally adopts methods such as nuclear magnetic resonance method, infra-red sepectrometry.Uses such as Sylvla 13C NMR has analyzed the aldehydes matter in the brown coal liquefaction oil, identify altogether phenol, neighbour// 6 kinds of compounds such as p-methyl phenol, xylenol and indenols, and adopt the area percentage method to determine content separately.After people such as Verkade and Wroblewski uses optimization 31P NMR analytic approach is applied in the coal mild pyrolysis product aldehydes matter when analyzing, and a qualitative identification goes out 19 kinds of individual phenolic compounds.People such as Winschel and Robbins uses Fourier infrared spectrum FTIR to analyze to take from the aldehydes matter in coal liquefaction pilot-plant coal liquefaction intermediate product and the final products, can only 21 kinds of monomer phenols of qualitative identification.This several method all produces than large deviation the analyzing and testing of the isomers that extensively is present in higher phenols, polyhydric phenol and One's name is legion in the liquefied coal coil.Chromatogram/mass spectrometry method is present the most widely used Separation of Organic Compounds authentication method, also is to the maximum method of liquefied coal coil phenolic compound research.People such as Curt obtain the methyl alcohol/CO of enrichment aldehydes matter by different solvents order extracting liquefied coal coil 2Solution is removed solvent methanol/CO by evaporation 2After, utilize the application of gas chromatorgraphy/mass analysis, with the contrast of reference material retention time and two kinds of methods of mass spectrometry, identify 22 kinds of monomer phenols altogether, adopt simple area percentage method to determine content separately.People such as Shi Quan are at mass spectrum journal (V0120, NO.2), when disclosing in the analysis catalytic cracking diesel oil phenolic compound, wherein phenolic compound only accounts for 0.2% of diesel oil gross mass, use N, two (TMS)-2 of O-, 2,2-trifluoroacetamide (BTSFA) is as silicon etherification reaction reagent, qualitative analysis comprise monomer phenol in the catalytic diesel oil, two rings, tricyclic antidepressants is totally 44 kinds of phenolic compounds, monomer phenols wherein do not carried out accurate quantitative analysis, and this kind method is for three ring higher phenols time-likes in addition, exist its chromatographic peak overlapping serious, problem such as can't effectively separate.
Because that liquefied coal coil is formed is complicated, of a great variety, phenols content height, polarity is strong, volatility is low, the isomers physicochemical property of One's name is legion is very similar in the liquefied coal coil in addition, use when having the methods analyst phenolic compound now, if direct injected, a great deal of phenols homolog overlap of peaks is serious, the double end peak occurs, can't effectively separate; After using derivatization reagent, though can significantly improve the separating effect of part phenols isomers, but big for molecular weight, volatility is low, the above senior phenols separating effect of three rings is not good, in addition, existing method just adopts the area percentage method to carry out simple quantitative test aspect quantitative test.Therefore no matter, use existing method, be on qualitative analysis monomer phenols species number amount, still all needing to be further improved aspect the accuracy of quantitative test monomer phenols content.
Summary of the invention
The objective of the invention is to is problem at the existence of above-mentioned prior art, be engaged in the development research and the long-term practice of DCL/Direct coal liquefaction for many years through the inventor, propose a kind of by adding activating agent, carry out silicon ether or phosphoryl chloride phosphorus oxychloride class derivative reaction, and then come the analytical approach of phenolic compound in the accurate qualitative, quantitative coal direct liquefaction oil.
Phenolic compound analytical approach in a kind of coal direct liquefaction oil provided by the invention is characterized in that comprising the following steps:
1. the enrichment of phenolic compound
In separating funnel, add coal liquefaction oil in succession, preferably＜420 the NaOH solution of ℃ coal liquefaction oil and 10 quality % fully shook 3-10 minute, wherein liquefied coal coil and NaOH mass ratio are 1: 0.25-1: 0.75, tell lower floor's water and upper organic phase behind the standing demix, upper organic phase extracts three times repeatedly with 10 quality %NaOH solution, the used NaOH amount of each extraction is 1 for the mass ratio of former liquefied coal coil and NaOH: 0.25-1: 0.75, obtain extracting lower floor's water respectively, merge whole four extraction lower floor waters, in separating funnel, use 10MH 2SO 4In and lower floor's water (for aqueous slkali) and regulate PH=1, shake 3-10 minute, preferred 5 minutes, after leave standstill to thorough layering (for example 10 to 20 minutes), the collection upper organic phase is used Na 2SO 4Dewater, organic phase solution enrichment in 40 ℃ of water-baths obtains the enrichment phenolic compound.
2. phenols derivatization treatment
With the 1. resulting enrichment phenolic compound of step, with derivatization reagent N, two (TMS)-2 of O-, 2,2, trifluoroacetamide (BTSFA) or diphenyl phosphoryl chloride (DPPC) and activating agent pyridine carry out quantitative derivative reaction, are that solvent obtains corresponding silicon ether derivant solution with the methylene chloride.For example the reaction equation of BTSFA and phenolic compound is:
Figure A20091008615900061
The phenols general formula
This solution was at room temperature placed 10-15 hour, wherein the enrichment phenolic compounds: derivatization reagent: the mass ratio of activating agent pyridine is 1: 3: 3 to 1: 10: 10.
3. the qualitative and quantitative analysis of phenolic compound
The silicon ether derivant of the 2. resultant solution employing of step chromatogram/mass spectrometry method to various free phenols carried out qualitative analysis and adopt gas chromatography that various monomer phenols are carried out corresponding quantitative test.For example described gas chromatograph is a U.S. Agilent 6890GC type gas chromatograph;
GC conditions: adopt Agilent 6890GC type gas chromatograph, chromatographic column DB-Perto, 100m * 0.25mm * 0.25 μ m, injector temperature: 300 ℃; Detector temperature: 300 ℃; Carrier gas is N 2, flow velocity is 1.5ml/min; Split sampling mode (split ratio 1: 150), the column temperature program: 70 ℃ of initial temperature, rise to 200 ℃ with 4 ℃/min heating rate, behind the constant temperature 3min again with 250 ℃ of 2 ℃/min heating rates, constant temperature;
Described chromatograph-mas spectrometer is Tianjin, island GC17A/QP5050 type gas chromatograph-mass spectrometer (GCMS), adopts DB-Perto post (Hewlett-Packard's production): 100m * 0.25mm * 0.25 μ m.
The gas chromatography mass spectrometry condition: chromatogram/GC-MS is Tianjin, island GC17A/QP5050, the EI ion gun, and ionization voltage 70eV, sweep limit is 50～500m/z, 230 ℃ of interface temperature, standard retrieval spectrum storehouse is NIST 98; GC conditions adopts Agilent 6890GC type gas chromatograph, chromatographic column DB-Perto, 100m * 0.25mm * 0.25 μ m, injector temperature: 300 ℃; Detector temperature: 300 ℃; Carrier gas is N 2, flow velocity is 1.5ml/min; Split sampling mode (split ratio 1: 150), the column temperature program: 70 ℃ of initial temperature, rise to 200 ℃ with 4 ℃/min heating rate, behind the constant temperature 3min again with 250 ℃ of 2 ℃/min heating rates, constant temperature.
In the coal direct liquefaction oil provided by the invention in the analytical approach of phenolic compound, described coal direct liquefaction oil is meant the coal liquefaction oil that various coals obtain at the whole bag of tricks, preferred＜420 ℃ liquefaction oil, for example among the CN438294A＜420 ℃ liquefaction oil.
The present invention adopts N, two (TMS)-2 of O-, 2,2, trifluoroacetamide (BTSFA) or DPPC are derivatization reagent, by silicon ether derivative reaction, various free phenols in (separating from coal liquefaction oil) phenols sample are converted into corresponding ether compound, when the phenols sample is carried out derivatization treatment, the adding pyridine promotes the complete silicon etherification reaction of the middle-and-high-ranking phenol of sample, thereby improved the accuracy of higher phenols compounds quantitative analysis results, owing to adopt N, two (TMS)-2 of O-, 2,2, trifluoroacetamide (BTSFA) or DPPC are derivatization reagent, and the phenols sample is carried out after silicon ether derivative reaction handles, higher phenols class homolog silicon etherate volatility height, thereby enlarged sensing range to phenolic compound, and easy and simple to handle, can significantly improve the separating effect that isomers is seen.
In the analytical approach provided by the invention, can adopt any gas chromatograph and chromatograph mass spectrometer, preferably adopt U.S. Agilent6890 type gas chromatograph; Used chromaticness-GC-MS is Tianjin, island GC17A/QP5050 type gas chromatograph-mass spectrometer (GCMS), adopts DB-Perto chromatographic column (Hewlett-Packard's production), 100m * 0.25mm * 0.25 μ m.
GC conditions: adopt Agilent 6890GC type gas chromatograph, chromatographic column DB-Perto, 100m * 0.25mm * 0.25 μ m, injector temperature: 300 ℃; Detector temperature: 300 ℃; Carrier gas is N 2, flow velocity is 1.5ml/min; Split sampling mode (split ratio 1: 150), the column temperature program: 70 ℃ of initial temperature, rise to 200 ℃ with 4 ℃/min heating rate, behind the constant temperature 3min again with 250 ℃ of 2 ℃/min heating rates, constant temperature.
The gas chromatography mass spectrometry condition: chromatogram/GC-MS is Tianjin, island GC17A/QP5050, the EI ion gun, and ionization voltage 70eV, sweep limit is 50～500m/z.230 ℃ of interface temperature.Standard retrieval spectrum storehouse is NIST98, and the gas chromatography part is identical with above-mentioned GC conditions.
Method of the present invention is carried out following checking: be example with phenol, it is good in 0.98～1.841 μ g/5 μ l scope internal linear, and related coefficient is 0.9998; Precision is 0.325%, and relative average debiation is 1.57%, and above digital proof this method is accurately and sensitivity.
Method provided by the invention has following advantage:
1. method provided by the invention is a kind of phenolic compound in the coal direct liquefaction oil to be carried out accurate qualitative and quantitative analysis method, and sensing range is wide, easy and simple to handle, highly sensitive.
2. this method is by when carrying out derivative reaction to phenolic compound, by adding an amount of activating agent (pyridine), not only effectively improve monomer phenol, the complete derivative reaction of two ring phenolic compounds, more can promote senior phenols and derivatization reagent complete reactions such as three rings, enlarge sensing range, significantly improved the separating effect between the phenols isomers, especially to the separating effect of senior phenols.
3. this method qualitative and quantitative analysis extractible high added value phenolic compound type and content in the liquefied coal coil, reasonable utilization and extraction for the high added value phenolic compound in the liquefied coal coil, strong experimental data is provided, widen the scope of utilizing of liquefaction oil simultaneously, strengthened the liquefied coal coil competitive power.
Description of drawings
Fig. 1 carries out the preceding chromatogram of silicon ether derivatization for enrichment phenolic compound in the coal direct liquefaction oil
Fig. 2 carries out chromatogram after the silicon ether derivatization treatment for enrichment phenolic compound in the coal direct liquefaction oil
Embodiment
The present invention further specifies with the following example and accompanying drawing, but protection scope of the present invention is not limited to the following example.
Embodiment 1
Take by weighing 27 kinds of standard free phenol compounds samples (seeing following table 1 for details) 2mg respectively, be dissolved in the methylene chloride, corresponding simultaneously every kind of standard free phenol adds 12ul N, two (TMS)-2 of O-, 2,2-trifluoroacetamide (BTSFA) silicon etherifying reagent and 20ul pyridine, it is quantitative to carry out hybrid standard phenol 25ml volumetric flask after the complete reaction, places behind the 12h standby under the room temperature.Get the mixed phenol standard specimen and carry out chromatograph-mass spectrometer coupling and gas chromatographic analysis, determine the standard retention time of various monomer phenols, get 5ml, 10ml, 15ml, 20ml standard phenol solution simultaneously respectively, set up the level Four table of corrections and use external standard number percent method carrying out quantitative test.Table 1 is depicted as by order successively and goes out the retention time of monomer phenols at peak and the retention time by derivant after the silicon etherificate.
Table 1
Figure A20091008615900081
Figure A20091008615900091
Embodiment 2
Be same as the chromatographic condition of embodiment 1
Take by weighing the 100g liquefied coal coil, add 25ml NaOH (10%) solution, abundant vibration 5min in separating funnel tells lower floor's water behind the standing demix, and the upper strata organic layer extracts three times repeatedly with NaOH (10%) solution, merge four lower floor's waters after, use H 2SO 4(10M) in the solution and lower floor's aqueous slkali and regulate PH=1, vibration 5min leaves standstill the 10min layering in separating funnel, collect the upper strata organic layer and add Na again 2SO 4Dewater, but solution under 40 ℃ of water bath condition just enrichment obtain phenolic compound in the liquefied coal coil.Get the phenolic compound 1.0mg of enrichment, add 6.0ulBTSFA, and add the 6ul pyridine, be solvent with the methylene chloride, in the 5ml volumetric flask, be mixed with 5ml solution, placed 12 hours under the room temperature, carry out gas chromatography-mass spectrometry analysis, gas chromatogram is seen Fig. 3, The qualitative analysis sees Table 2, and quantitative analysis results sees Table 3.
Table 2
Figure A20091008615900092
Figure A20091008615900101
Table 3
Figure A20091008615900102
As seen adopt the inventive method that phenolic compound in the liquefied coal coil is analyzed, not only can qualitative analysis wherein the kind of free phenol reach 54 kinds, and accurately quantitative test goes out wherein 27 kinds of free phenol kind compound contents, comprising part tricyclic antidepressants higher phenols, this is that existing at present method institute is inaccessiable.
Embodiment 3
When selecting diphenyl phosphoryl chloride (DPPC) for use as derivatization reagent, select N for use in other condition, two (TMS)-2,2 of O-, the condition of 2-trifluoroacetamide (BTSFA) during as derivatization reagent still can obtain the result identical with example 2.

Claims (2)

  1. The analytical approach of phenolic compound is characterized in that comprising the following steps: in 1 one kinds of coal direct liquefaction oils
    1. the enrichment of phenolic compound
    In separating funnel, the NaOH solution that adds coal liquefaction oil and 10 quality % respectively fully shook 3-10 minute, wherein liquefied coal coil and NaOH mass ratio are 1: 0.25-1: 0.75, tell lower floor's water and upper organic phase behind the standing demix, upper organic phase extracts three times repeatedly with 10 quality %NaOH solution, the used NaOH amount of each extraction is 1 for the mass ratio of former liquefied coal coil and NaOH: 0.25-1: 0.75, obtain extracting lower floor's water respectively, merge whole four extraction lower floor waters, in separating funnel, use 10M H 2SO 4In and lower floor's water and regulate PH=1, shake 3-10 minute, after leave standstill to thorough layering, the collection upper organic phase is used Na 2SO 4Dewater, organic phase solution enrichment in 40 ℃ of water-baths obtains the enrichment phenolic compound;
    2. phenols derivatization treatment
    With the 1. resulting enrichment phenolic compound of step, with derivatization reagent N, two (TMS)-2 of O-, 2,2, trifluoroacetamide or diphenyl phosphoryl chloride and activating agent pyridine carry out quantitative derivative reaction, are that solvent obtains corresponding silicon ether derivant solution with the methylene chloride, after solution was at room temperature placed 10-15 hour, enrichment phenolic compounds wherein: derivatization reagent: the mass ratio of activating agent pyridine was 1: 3: 3 to 1: 10: 10;
    3. the qualitative and quantitative analysis of phenolic compound
    The silicon ether derivant of the 2. resultant silicon ether derivant of step solution employing chromatogram/mass spectrometry method to various free phenols carried out qualitative analysis and adopt gas chromatography that various monomer phenols are carried out corresponding quantitative test.
  2. 2. according to the analytical approach of claim 1, it is characterized in that
    Described coal liquefaction oil is＜420 ℃ of coal liquefaction oil;
    Described form and aspect chromatograph is a U.S. Agilent 6890GC type gas chromatograph;
    GC conditions: chromatographic column DB-Perto, 100m * 0.25mm * 0.25 μ m, injector temperature: 300 ℃; Detector temperature: 300 ℃; Carrier gas is N 2, flow velocity is 1.5ml/min; Split ratio 1: 150, the column temperature program: 70 ℃ of initial temperature, rise to 200 ℃ with 4 ℃/min heating rate, behind the constant temperature 3min again with 250 ℃ of 2 ℃/min heating rates, constant temperature;
    Described chromatograph-mas spectrometer is Tianjin, island GC17A/QP5050 type gas chromatograph-mass spectrometer (GCMS), adopts the DB-Perto post: 100m * 0.25mm * 0.25 μ m,
    The application of gas chromatorgraphy/mass condition: chromatogram/GC-MS is Tianjin, island GC17A/QP5050, the EI ion gun, and ionization voltage 70eV, sweep limit is 50～500m/z, 230 ℃ of interface temperature, standard retrieval spectrum storehouse is NIST 98;
    GC conditions: chromatographic column DB-Perto, 100m * 0.25mm * 0.25 μ m, injector temperature: 300 ℃; Detector temperature: 300 ℃; Carrier gas is N 2, flow velocity is 1.5ml/min; Split ratio 1: 150, the column temperature program: 70 ℃ of initial temperature, rise to 200 ℃ with 4 ℃/min heating rate, behind the constant temperature 3min again with 250 ℃ of 2 ℃/min heating rates, constant temperature.
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RU2669266C1 (en) * 2017-07-03 2018-10-09 Российская Федерация, от имени которой выступает Федеральное агентство по техническому регулированию и метрологии (Росстандарт) Method of identification of impurity of investigated substance, related to its main component
CN109557215A (en) * 2019-01-16 2019-04-02 黑龙江八农垦大学 The method that PDMS micro-pipe extracts phenolic substances in root exudates after derivative

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US4508886A (en) * 1984-03-30 1985-04-02 The United States Of America As Represented By The United States Department Of Energy Method for making adhesive from biomass
CN101314716B (en) * 2008-05-17 2011-11-02 中国矿业大学 Dehydration and alcohol depolymerization process for low-disintegration coal in mild condition

Cited By (2)

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Publication number Priority date Publication date Assignee Title
RU2669266C1 (en) * 2017-07-03 2018-10-09 Российская Федерация, от имени которой выступает Федеральное агентство по техническому регулированию и метрологии (Росстандарт) Method of identification of impurity of investigated substance, related to its main component
CN109557215A (en) * 2019-01-16 2019-04-02 黑龙江八农垦大学 The method that PDMS micro-pipe extracts phenolic substances in root exudates after derivative

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