MINISTRY OF EDUCATION
AND TRAINING

VIETNAM ACADEMY
OF SCIENCE AND
TECHNOLOGY

GRADUATE UNIVERSITY SCIENCE AND TECHNOLOGY
------- *** -------

STUDY TO DETERMINE THE CONTENT OF SOME
CHLORBENZEN COMPOUNDS FROM UNINTENTIONAL
EMISSION SOURCES IN INDUSTRIAL ZONES IN THAI
NGUYEN PROVINCE

Major: Analyticalchemistry
Code: 9.44.01.18

SUMMARY OF DOCTORAL THESIS

Ha Noi, 2019

1


This thesis is completed at: Vietnam Academy of Science and
Technology

Scientific instructors:
Assoc. Dr. TU BINH MINH
Assoc. Dr. NGUYEN THI HUE

Vietnam. This is a topical issue in current conditions when health and
environment in Vietnam are at an alarming level. Therefore, I decided
to choose the topic "Study to determine the content of some
chlorbenzen compounds from unintentional emission sources in
industrial zones in Thai Nguyen province", contributing to the
protection and sustainable development of ecological environment in
Thai Nguyen province.
2. Research objectives of the thesis
- Study the process of simultaneous determination and evaluation of
the

method of

analyzing 7

chlorobenzene,
3

including 1,2-


dichlorobenzene (1,2-DCB); 1,3-dichlorobenzene (1,3-DCB); 1,2,4trichlorobenzene (1,2,4-TCB); 1,2,3,4-tetrachlorbenzene (1,2,3,4TeCB), 1,2,4,5-tetraclobenzene (1,2,4,5-TeCB); pentaclobenzene
(PeCB) and hexaclobenzene (HCB) in trace and superficial content in
flue gas samples and industrial waste (fly ash, bottom ash, input
materials).
- Adopting an optimal procedure to simultaneously identify
chlorobenzene in industrial samples including waste gas, ash,
materials of some industrial fields in industrial zones in Thai Nguyen
province.
- Preliminary assessment of the level and emission characteristics of

emissions and the risk of chlorobenzene on humans from a number of
industries in Thai Nguyen province.
4. New contributions of the thesis
1. Optimized conditions to simultaneously identify 7 clobezen
targets, in industrial samples (waste gas samples and waste solid
samples (Fly ash, bottom ash) in trace amounts and super stains using
GC-ECD and GC-MS.
2. Successfully developed the process of analyzing
chlorbenzen compounds in trace amounts and super stains.
3. The first step was to identify and determine the emission
level through the emission factor and the annual emission of 7
chlorbenzenes from industrial solid waste samples in Thai Nguyen
province.
This is the first published study in Vietnam on unintentional
emission levels of chlorbenzenes in some industries. Thereby
contributing to the control of emissions to limit and completely
eliminate hazardous POPs in the environment, meeting the
requirements of the Stockholm Convention, towards sustainable
development in Vietnam

5


CHAPTER 1: OVERVIEW OF RESEARCH PROBLEMS
1.1. OVERVIEW OF THE RESEARCH SUBJECT
1.1.1. Overview of Chlorobenzens
Derivatives of chlorbenzenes C6H (6-x) Clx form a stable and
colorless group with a pleasant odor. Chlorine can be substituted for
six hydrogen atoms on benzene rings to be able to form twelve
different chlorinate compounds including: Monoclobenzene (MCB);

a-Fe2O3 metal .....) to create copper lower chlorine CBs
1.2. DOMESTIC AND OVERSEAS STUDY SITUATION
1.2.1. Studies in the world
In recent years, a number of studies have also focused on
unintentional POPs emissions from the production of non-ferrous
metals and ferrous metals, iron ore production of iron and steel, coke
production and other secondary color metallurgy process. A research
in China in the industry of zinc and lead metals production in 2007
showed that the average emission factor of PCDD / Fs in gas samples
for lead and zinc manufacturing industry is 98.2 and 0.35, respectively.
ng TEQ / (Nm3); in fly ash samples is 5.64 ng TEQ / g with zinc
industry; 0.05 ng TEQ / g in lead manufacturing industry. Emission
factors of gas samples for PCBs from zinc and lead production are
respectively 2,786 and 0,002 ng TEQ / Nm3.The formation and
reduction of emissions of clobenzene, polychlorinated dibenzo-pdioxin and dibenzofurans polychlorinated (PCDD / Fs) have been
studied in a typical dry cement kiln in China. Emissions of PCDD / F
and CBz in emissions are 0.16 ng I-TEQ Nm-3 and 26 µg / Nm3
respectively. The concentration of 1,2-DCB ranges from 100 - 9424
ng / Nm3; 1.3 and 1.4 –DCBz are 223 - 6409 ng / Nm3 1,3,5 / 1,2,4 /
1,2,3- TCB in the range of 35 - 3542 ng / Nm3 (of which 1.2, 4
accounts for the largest amount); 1,2,3,5-TeCB & 1,2,4,5-TeCB range
between 2 - 491 ng / Nm3, while isomer 1,2,3,4-TeCB is 6 - 562 ng /
Nm3 ; Concentrations PeCB and HCB range from 1 to 335 ng / Nm3
and 1 to 128 ng / Nm3 respectively.
1.2.2. Domestic studies in Vietnam
Studies on POPs compounds such as dioxin / furan, DDT,
PCBs in Vietnam have been of interest since the end of the 20th
century because of their toxicity and changes in awareness in
7


g

Factor
y sign

Type of
productio
n

Capacit
y
(ton / h)

Emissio
n rate
(Nm3 /
h)

Averag
e
capacit
y / year

THÁI NGUYÊN
1

2

Viet Trung
black


7000

8


3

4

5

6

7

8

9

10

11

12

Duc Thinh
Mechanical
Company
Thai

Cooperativ
e
Dong Hy
General
Hospital
Incinerator
for
domestic
waste - DaPhu Luong
town
Household
waste

12/2017

NMLK
3

Cast Iron

2,5

-

2496

03/2017

NMLK
4


16500

6530

03/2017

NMVL
2

brick

5,0

-

8040

06/2014

NMVL
3

Cement

40

-

7920

1

Domestic
waste

0,45

-

2900

03/2017

LDSH
2

Domestic
waste

0,7

-

2900

9


13


2900

03/2017

LDSH
4

Domestic
waste

0,7

-

2900

2.2. RESEARCH METHODS
2.2.1. Objectives of the study
2.2.2. research content
2.2.3. Methods of document review
2.2.4. Survey method
2.2.5. Experimental method
2.2.5.1. Sampling, shipping and preservation methods
2.2.5.2. Sampling and actual sample information
2.2.5.3. Method of CBz analysis on GC-ECD equipment
2.2.5.4. Study the sample processing process and confirm the use
value of the method
2.2.5.5. Analysis of real samples
2.2.5.6. Evaluation of emission levels and assessment of the risk of
chlorbenzen compounds

further studies. After investigating the optimal conditions when
analyzing CBz with GC-ECD, the parameters are listed in Table 3.1.
Table 3.1. Excellent parameters when analyzing CBz on
GC-ECD 2010 device
Pump port temperature
220 ° C
Air flow mode
Pressure
Column head pressure
100 kPa
Volumetric
suction 1 µl
sample
Pump mode
Divide the line
Line split rate
1:10
Sample
pumping Pressure
program rate
Flow
through 1 ml / minute
column
Separation
column
SPB-608 (30 m × 0.25 mm × 0.25 µm)
Column oven temperature program
70 oC
Heating speed 10° C / min; hold 2
70 oC to 120oC

5
6
7
8
9

Name of substance
1.3 Diclobenzen
1.2 Diclobenzen
1.2.4 Triclobenzen
1.2.4.5 Tetraclobenzen
1.2.3.4 Tetraclobenzen
Pentaclobenzen
Hexaclobenzen
CB 209
Pentanitroclobenzen

Retention time (minute)
4.667
5.310
7.812
10.707
11.974
14.016
16.729
17.545
17.885

3.1.2. Results of evaluation of stability of CBz analytical signal on
GC-ECD device

solution 10 ng / g

( 1: 1,3-DCB; 2: 1,2- DCB; 3: 1,2,4 - TCB; 4: 1,2,4,5 - TeCB;5: 1,2,3,4 – TeCB;
6: PeCB; 7: HCB;8: PeCNB)
Figure 3. 1. Chromatogram of CBz on GC / MS device

14


Based on the analytical conditions on GC-MS, analyze and
inject some analytical samples with complex background as waste ash
onto GC-ECD and GC-MS to confirm the presence of Chlorbenzenes
in these samples
3.1.4.2. Detection limit (IDL) and quantitative limit (IQL) of CBz on
GC / MS equipment
LOD values of GC / MS chromatography equipment for CBz
range from 1.25 to 3.75 ppb and LOQ values from 4.16 to 12.5 ppb.
3.2. STUDYING CONDITIONS OF EXCLUSION AND
EXECUTION OF CBz
3.2.1. Investigate the optimal conditions for sample cleaning on
GC-ECD equipment
3.2.1.1. Liquid - solid extraction method
The results of the survey show that the recovery of CBz which
when extracting with different solvents varies widely from 66.7 to
96.1%. It can be seen that the recovery of all CBz is uniformly high
when extracted with DM1.1 (from 81.8 to 96.1%) and DM 2.3 (80.3 93.0%). For compounds 1,2 and 1,3-DCB the recovery in DM 1.2 is
quite high compared to other survey solvents (83 -85%) and the lowest
in DM 2.1 solvent (65.2 - 67.6%). Thus, to be able to simultaneously
identify 7 CBz, the thesis selected solvent extracting sample DM1.1
for high recovery evenly with all CBz, with relatively small standard

(1 :1)
CH 2 (mL)
40
60
120
78,6
79,1 64,9
75,7
79,6 63,1
79,8
79,5 64,4

Aceton : hecxan
(1 :2)
CH 3 (mL)
40
60
120
73,3 81,2
67,7
72,6 79,1
61,2
78,3 81,7
73,7

78,3

86,8

79,4


PeCB

81,2

83,6

72,0

71,4

75,7

70,2

77,5

79,8

72,6

HCB

80,5

87,2

80,2

73,6

80%) within the allowable limits according to EPA 8121 method
guidelines (with the recovery range from 59 to 116%).

16


140
120
100
80
60
40
20
0

Florisil

1

2

Silicagel + than hoạt tính

3

4

5

6

0,26
1,2-DCB
0,039
0,117
6,2
0,39
1,2,4-TCB
0,018
0,054
7,4
0,18
1,2,4,5-TeCB 0,016
0,050
8,0
0,16
1,2,3,4-TeCB 0,023
0,069
7,4
0,23
PeCB
0,019
0,057
4,8
0,19
HCB
0,021
0,062
4,7
0,21


79,7 –
77,0- 102
28,8
0,117 0,391
107,8
78,5 –
59,0
24,4
0,054 0,180
85,2
82,0 –
102
28,3
0,050 0,168
94,8
81,6 –
104
26,9
0,055 0,184
92,7
83,9 –
PeCB
73,0 -129
19,6
0,078 0,290
108
80,1 –
HCB
84,0 -116
25,8

3.4.2. The level of pollution and emissions of chlorobenzene in
industrial solid waste samples
3.4.2.1. The level of pollution and emissions of chlorbenzenes in the
metallurgy industry
From the research results, there are significant differences in the
average content of CBz in the metallurgy industry (zinc oxide
production - NMLK2) and the black metallurgy industry (pig iron,
steel-NMLK3; NMLK4) Content. The CBz in fly ash samples and
bottom ash is shown in Figure 3.3

Figure 3.3. Concentration of CBz in metallurgical plants
3.4.2.2. The level of pollution and emissions of chlorbenzenes in
some construction materials industries
The average total CBz content in solid samples of NVVL1,
NMVL2 and NMVL3 ranged from 2.69 to 22.6 ng / g. In which CBz
content of NMVL1; NVVL3 has a similar content and is smaller than
NMVL2. The CBz content in the two tunnel brick factories was
significantly different, at NMVL2 7 times higher than NMV1. When
compared to the results reported in some countries, the CBz content in
this study is much smaller than in the results obtained in cement plants
in China.
3.4.2.3. The level of pollution and emissions of chlorbenzenes in waste
incinerators
From the results of the research, the average content of CBZ in
3 types of industrial, medical and urban incinerators ranges from 26.4
to 34.7 ng / g dry samples and the difference is not significant. With
19


LDCN ranging from 6.27 to 58.1 ng / g; Health insurance from 4.54 54.7 and LDSH from 23.5 to 46.0 ng / g. The concentration fluctuates

29,6
15,8 2)
( - ) : no analysis; (TN : Thai Nguyen ; HP : Hai Phong ; QN :
Quang Ninh ; BN : Bac Ninh)
Table 3.8 results show that the CBz content in the provinces
varies quite significantly in incinerators, with CBz concentration range
fluctuating quite wide, the lowest is 15.3 ng / g and the highest is 405
ng / g. In general, the CBz emission level of TN is lower than that of
other provinces in Northern Vietnam
3.5. CHARACTERISTICS OF ACCUMULATION OF
CONGENERS OF CHLORBENZENESIN WASTE OF SOME
INDUSTRIAL ACTIVITIES
20


NMLK5

3.5.1. Characteristics of accumulation of congeners of
chlorbenzenes in solid waste of metallurgy and production of tunnel
bricks
3.5.1.1. Metallurgical industry
Tro đáy

Tro đáy

NMLK4

1,2-DCB
1,3-DCB
1,2,4-TCB

- DCB (3.5%)