(660e) Determination of Anthracene, Phenanthrene and Carbazole in Crude Anthracene By Capillary GC | AIChE

(660e) Determination of Anthracene, Phenanthrene and Carbazole in Crude Anthracene By Capillary GC

Authors 

Hui-ping, L. - Presenter, Zhengzhou University
Wei, L., Zhengzhou University
Su-yu, J., Zhengzhou University
Zhang, D., Zhengzhou University

Determination of anthracene, phenanthrene and carbazole in crude anthracene by capillary GC

LIU Wei, JIANG Su-yu, Li Hui-ping*

School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001, China

* Corresponding author phone: (+86) 0371-67781807; fax: (+86) 0371-67781807

E-mail: huipingli@zzu.edu.cn

Abstract: A method was established for the determination of anthracene, phenanthrene and carbazole in crude anthracene by capillary GC. The qualitative analysis of main components in crude anthracene was analyzed by GC-MS, where N,N-dimethylformamide (DMF) was used as solvent and phenoxazine as internal standard substance. The results showed that the components of the crude anthracene could be separated well and twenty-two components were identified. The average contents of three main components were 39.59% for anthracene, 17.93% for phenanthrene, 15.48% for carbazole respectively. The relative standard deviations (RSDs) of the measurements for them are less than 2%. The recovery ratio is over 98%. The method is of high accuracy and precision, also, it is quick, sensitive, simple and suitable for industrial production analysis.

Key word: capillary column GC; anthracene; phenanthrene; carbazole

1. Introduction

Crude anthracene (CA), yellow-green crystal, is a distillation fraction from coal tar with the boiling point range of 300oC~360oC. The main components in CA such as anthracene (A), phenanthrene (P) and carbazole (C) are of highly value-added [1], and are not or cannot be economically obtained from the petroleum industry. It is significant to analyze the content of CA accurately, which is the basis for the separation and purification of A, P, C from CA. Therefore, it is very important to establish a method which can analyze the content of main components in CA accurately and quickly.

CA consists of many components, differing only slightly in properties [2], therefore, it is difficult to analyze and separate them. For example, Wang, J.G. [3] studied the content of A in CA using GC with internal standard method. Li, C. [4] obtained the contents of A and P in CA using GC with external standard method. Here, CA was analyzed by GC-MS qualitatively and the content of A, P and C were determined quantitatively by the standard curve method in this work,which can eliminate the influence of some operations, also, reduce the trouble of weighing and calculating, and is more accurate, reliable than external standard method.

2. Experiment Sections

2.1 Instruments and reagents

Shimadzu GC-MS QP2010, Tianmei GC-7900, Anthracene (A), phenanthrene (P), carbazole (C), and phenoxazine are GC grade reagents, DMF (A.R.). Crude anthracene (CA) was from Henan Baoshun Chemical Technology Co., Ltd.

2.2 Chromatographic conditions

GC: SE-54 capillary column (30 m×0.32 mm×0.5 μm) was selected. The temperature- programmed route as follows: staring from 140oC (0.1 μL injection volume) for 4 min, then increased by 20oC/min to 180oC, held for 5 min, and further increased by 20oC/min to 300oC, held for 5 min. The temperature of the vaporization chamber and FID detector: 300oC, the flow rate of H2: 40 mL/min, the pressure of air: 0.36 MPa, carrier gas N2 (purity>99.999%): 0.5 MPa.

GC-MS: SE-54 capillary column (30 m×0.32 mm×0.25 μm) was used, the temperature were: 300oC (inlet), 250oC (FID), 230oC (ion source) and 250oC (surface). The temperature-programmed rout was the same as the above GC (0.2 μL injection volume). And the components were qualitatively analyzed by NIST 08 library. The flow rate was 1.04 mL/min and the split ratio was 30: 1.

2.3 Method

A amount of CA was fully dissolved in DMF. The samples were analyzed by GC-MS qualitatively (Fig. 1) and quantitatively analyzed by GC with the internal standard curve method. The qualitative results of the main components are shown in Tab. 1.

Fig. 1 GC-MS spectra of CA

Tab. 1 Qualitative results of the components in CA

sequence

retention time/min

component

sequence

retention time/min

component

1

2.974

Naphthene

12

11.467

Anthracene

2

4.159

1-Methylnaphthalene

13

11.767

Naphtho[2,1-b]thiophene

3

5.135

Biphenyl

14

12.184

Carbazole

4

5.451

2-Ethylnaphthalene

15

13.150

2-Methylanthracene

5

5.826

2,3-Dimethylnaphthalene

16

13.300

9-Methylanthracene

6

6.315

Acenaphthene

17

13.567

3-Methylcarbazole

7

6.697

Dibenzofuran

18

14.592

Fluoranthene

8

7.558

Fluorene

19

15.017

Pyrene

9

7.951

4-Methylbiphenyl

20

15.649

1,2-Benzfluorene

10

10.590

Dibenzothiophene

21

15.767

2,3-Benzfluorene

11

11.234

Phenanthrene

22

17.040

Benz(a)anthracene

Fig. 1 and Tab. 1 showed that the composition of CA is complex, of which twenty-two components can be identified. However, the main components are A, P, C, fluorene and dibenzofuran.

3. Results and discussion

3.1 Selection of chromatographic column

SE-54 column was used to analyze CA, as shown in Fig. 2.

Fig. 2 Chromatogram of CA added with internal standard substance

It can be seen from Fig. 2 that the peaks of A (No. 2), P (No. 1), C (No. 3) and phenoxazine (No. 4) were well separated. Also, the peaks of A, P, C were close to each other, and the peak of P was earlier.

3.2 Standard curves of A, P and C

The standard curves of A, P and C were obtained by using mi/ms ~Ai/As (Fig. 3). The linear regression equations for the standard curves of A, P and C were shown in Fig.3, Where y is the ratio of peak area and x is the ratio of mass. The results showed that there was a good linear relationship between mi /ms and Ai/As.

Fig. 3 Standard curves for A, P and C

3.3 Precision test

The RSDs were calculated and shown in Tab. 2.

Tab. 2 Results of precision of CA (unit%)

Sample No.

Measurement result %

Average %

SD %

RSD %

1

A

41.13

40.18

40.23

40.00

40.11

41.25

40.48

0.553

1.366

P

19.70

19.33

19.28

19.30

19.28

19.32

19.37

0.162

0.836

C

14.61

14.54

14.84

15.26

14.90

14.68

14.64

0.262

1.766

2

A

36.76

37.20

37.35

37.62

37.24

37.80

37.33

0.363

0.971

P

16.99

17.28

17.49

17.27

17.35

17.76

17.36

0.257

1.482

C

14.32

14.40

14.73

14.80

14.54

14.94

14.59

0.241

1.650

3

A

38.39

38.18

37.63

37.23

37.88

37.31

37.77

0.465

1.232

P

16.94

16.74

17.08

16.72

17.07

16.67

16.87

0.184

1.088

C

14.66

14.88

14.80

14.39

14.51

14.55

14.63

0.261

1.803

4

A

42.46

42.66

42.25

41.41

41.08

41.46

41.89

0.651

1.554

P

18.63

18.81

18.64

18.49

18.18

18.48

18.54

0.212

1.142

C

17.28

17.03

17.13

16.69

16.73

17.31

17.03

0.266

1.563

Tab. 2 showed that the RSDs were as follows: A: 0.971%~1.554%; P: 0.836%~1.482%; C: 1.563%~1.803%, which are less than 2%.

3.4 Recovery test

The contents of A, P, C in CA were determined, respectively (see Tab. 3).

Tab. 3 Results of sample recovery

Sample No.

Object

Original value /g

Added amount /g

Total /g

Recovery %

1

A

0.0245

0.0098

0.0342

98.98

0.0132

0.0376

99.30

P

0.0115

0.0076

0.0191

99.57

0.0130

0.0244

98.85

C

0.0103

0.0067

0.0170

99.26

0.0133

0.0235

99.31

2

A

0.0332

0.0080

0.0412

99.54

0.0123

0.0456

100.85

P

0.0147

0.0070

0.0216

99.02

0.0130

0.0274

98.05

C

0.0134

0.0090

0.0222

98.81

0.0146

0.0279

99.50

3

A

0.0417

0.0071

0.0487

99.39

0.0120

0.0538

100.90

P

0.0181

0.0085

0.0265

98.29

0.0125

0.0305

99.08

C

0.0166

0.0082

0.0249

101.27

0.0145

0.0311

100.22

From Tab. 3, it can be seen that the relative error is within ± 2%, therefore, the method can be considered as being of high accuracy.

3.5 Determination of CA

The percentage (Xi %) of A, P, C was calculated according to the following formula:

Where ms/m0 is the ratio of the mass of the internal standard substance to CA, and mi/ms was calculated by the standard curve. The results were shown in Tab. 4.

Tab. 4 Measurement results of CA

Object

Measurement result %

Average %

A

42.91

41.67

40

37.8

36.76

38.39

39.59

P

18.47

18.11

19.3

17.76

16.99

16.94

17.93

C

17.29

16.58

15.26

14.94

14.12

14.66

15.48

4. Conclusions

Twenty-two components in crude anthracene were identified by GC-MS in this study, of which anthracene, phenanthrene, carbazole, fluorene and dibenzofuran were the main components. The average contents were 39.59% for anthracene, 17.93% for phenanthrene, 15.48% for carbazole respectively. The relative standard deviations (RSDs) of the measurements were 0.971%~1.544% for anthracene, 0.836%~1.482% for phenanthrene and 1.563%~1.803% for carbazole. The recovery ratios were 98.98%~100.9% for anthracene, 98.05%~99.57% for phenanthrene and 98.81%~101.27% for carbazole. The results revealved that the analysis method is of high accuracy and great significance to analyze and purify the main components from crude anthracene, also, it is helpful to make full use of resources and reduce environmental pollution.

5. References

[1] Pan, B.; Wang, B.; Wang, Y.; Xu, P.; Wang, L.; Chen, J.; Ma, D. A simple carbazole-N-benzimidazole bipolar host material for highly efficient blue and single layer white phosphorescent organic light-emitting diodes. J. Mater. Chem. C 2014, 2 (14), 2466-2469.

[2] Ye, C.P.; D, X.X.; Li, W.Y.; Wu, T.T.; Fan, M.M.; Feng, J. Highly efficient solvent screening for separating carbazole from crude anthracene. Energy Fuels 2016, 30, 3529-3534.

[3] Wang, J.G.; Liu, C.X. et al. Determination of anthracene in coal tar crude anthracene by capillary gas chromatography [J]. Journal of Wuhan University of Science and Technology, 2006, 29 (6): 567-568.

[4] Li, C.; Chen, G.P. et al., et al. Determination of anthracene and phenanthrene in crude anthracene by capillary gas chromatography [J]. Metallurgical Analysis 2015, 35 (1): 72-76.


 

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