Electronic Supplementary Material (ESI) for Green Chemistry.
This journal is © The Royal Society of Chemistry 2016
Chlorohydrination of Allyl Chloride with HCl and H2O2 to Produce
Dichloropropanols Catalyzed by Hollow TS-1 Zeolite
Xinxin Peng1, Changjiu Xia1*, Min Lin1*, Hui Yuan1, Bin Zhu1, Yao Zhang1, Baorong Wang2,
Xingtian Shu1
1. State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of
Petroleum Processing, SINOPEC, 100083 Beijing, P. R. China
2. National Engineering Research Center for Carbohydrate Synthesis, Jiangxi Normal University,
330027, Nanchang, P. R. China.
To whom: [email protected], [email protected]
1. Experimental
1.1 Catalyst preparation
a)
Liquid TiCl4 was commercially obtained from Sigma Aldrich compamy, with purity ≥99.0%.
b)
Amorphous TiO2 was synthesized by hydrolysis of tetrabutyl titanate (TBOT). 8.5 g TBOT
was dissolved into 78g 1M NaOH solution with vigorous stirring at room temperature for 3
hours. Then, the mixture was filtered and washed with distilled water until the pH of the
filtrate below 9. Finally, the solid was dried at 110oC for 6 hours.
c)
Amorphous TiO2-SiO2 was prepared by hydrolysis of both tetraethyl orthosilicate (TEOS)
and TBOT. 31.25g TEOS and 2.12g TBOT were mixed and stirred for 5 min. Then, the
mixture was slowly added in 56.16g 1M NaOH aqueous solution with vigorous stirring at
room temperature. After that, the product was filtered and washed by distilled water until pH
of the filtrate below 9. The filter cake was then dried at 110oC for 6 hours.
d)
Crystalline TiO2 powders, including anatase, rutile, brookite, were synthesized by
hydrothermal treatment. 42.61g TBOT, 58.96g distilled water and 101.85g TPAOH(25wt%)
were mixed and stirred vigorously for 3 hours, and then the temperature was raised to 60oC
and stirred for 2 hours to remove alcohol. After that, the mixture was transferred into a
Teflon-lined stainless-steel autoclave for hydrothermal treatment at 170oC for 24 hours. The
product was then filtered, washed by distilled water and dried at 110oC for 6h. The material
was then split into two part and calcined at 550 oC for 4h and 800 oC respectively to obtain
anatase and rutile. Synthesis of brookite. 8.5g TBOT was added into 75g 0.1M NaOH
aqueous with stirring for 1 hour. After that, the mixture was transferred into a Teflon-lined
stainless-steel autoclave for hydrothermal treatment at 180oC for 24 hours. The product was
filtered and washed by distilled water until pH of the filtrate below 9. The filter cake was
then dried at 110oC for 6 hours.
e)
TiO2/S-1 was prepared by impregnation of TiCl4 on commercial S-1 zeolite. S-1 zeolite was
supplied by Sinopec Hunan Jianchang Petrochemical Co., Ltd. To obtain TiO2/S-1 sample,
0.71g TiCl4 was dissolved in 15.26g HCl aqueous (10wt %) and stirred for 30 min. Then the
liquid was slowly added into 15g S-1 to obtain a mixture. After S-1 was impregnated in the
liquid at room temperature for 4 hours, the mixture was dried at 110oC for 6 hours and
calcined at 550oC for 4 hours.
f)
TS-1 zeolite was synthesized according to the method reported by Thangaraj. 20.74g TPAOH
was added into 35.42g TEOS with stirring for hydrolysis. After stirring for 3 hours, TBOT
dissolved in anhydrous isopropyl alcohol was dropped into the hydrolyzed solution. Finally,
45.70 g distilled water was added and the mixture was stirred at 80 oC for 3 hours to remove
alcohol. The chemical composition of the final gel was SiO2: TiO2: TPAOH: H2O=1: 0.01:
0.3: 20 and it was transferred into a Teflon-lined stainless-steel autoclave. The crystallization
was carried out under autogenous pressure at 170 oC for 3 days. The mixture obtained was
filtered, washed with distilled water, dried at 110 oC for 6 h, and calcined at 550 oC for 5 h.
g)
HTS zeolite was supplied by Sinopec Hunan Jianchang Petrochemical Co., Ltd.
1.2 Catalyst characterization methods
X-ray diffraction (XRD) patterns were collected on a Philips Panalytical X'pert diffractometer
with nickel-filtered Cu Kα radiation (40 kV, 250 mA). The 2θscanning ranged from 5°to 35°, and
the scanning rate was 0.4° min-1. X-Ray Fluorescence (XRF) experiments were conducted on a
Rigaku 3721E spectrometer with W radiation (40 kV). The X-ray photoelectron spectroscopy
(XPS) spectra were recorded on a Thermo-Fischer-VG ESCALAB250 with Al Kα radiation, and
the framework titanium content and extra-framework titanium content were integral results of the
Ti 2p3/2 peaks at 460.3 eV and 458.7 eV.
N2 adsorption–desorption isotherms were collected at 77 K on a Micromeritics ASAP 2405
apparatus. The samples were previously dried under vacuum (0.1 Pa) at 300 oC for 6 h. The
surface properties were derived from the isotherms using BET and t-plot methods.The UV-visible
(UV-Vis) spectra were recorded on a JASCO UV-visible 550 spectrometer. The samples were
pressed into a self-supported wafer, and the spectra was recorded from 200 nm to 800 nm.
Scanning electron microscopy (SEM) images were taken from a Hitachi 4800 microscope (20
kV).
1.3 Catalytic evaluations
1.3.1 Chlorohydrination of AC with H2O2 and HCl
Chlorohydrination reaction was carried out in a three necked flask equipped with a condenser and
a magnetic stirrer. In a typical reaction, 2.60g catalyst, 83.86g 10wt% HCl aqueous and 17.60g
AC was added in the flask. Then 26.07g H2O2(30%) was added in by peristaltic pump with a
speed of 5 mL/min. For the reaction catalyzed by TiCl4, only 0.37g TiCl4 was added to keep
equivalent active center compared with HTS. The reaction temperature was controlled at 30oC,
and the total reaction time was 120min. Then the product was filtrated and the liquid was collected
for GC analysis.
1.3.2 Ring-opening of ECH with HCl
Ring-opening reaction was carried out in a three necked flask equipped with a condenser and a
magnetic stirrer. Firstly, 2.60g HTS and 21.49g ECH was added in 83.86g HCl(10%) aqueous.
Then the mixture was reacted at 30oC for 1.5 hour. After reaction was finished, the product was
filtrated and the liquid was collected for GC analysis. A control group was carried out at the same
condition except for no catalyst was added in.
1.3.3 Chlorohydrination of AC with 1wt % Cl2
Chlorohydrination of AC with 1vol % Cl2 diluted in N2 was carried out in a three necked flask
equipped with a condenser and a magnetic stirrer at atmospheric pressure. Cl2 was fed in through a
Teflon pipe from a Cl2 cylinder. Before the experiment start, 100g distilled water and 17.60g AC
were added. After that, Cl2 was fed in for 120 min. The molar ratio of AC to Cl2 is 5:1. The offgas was absorbed by 1M NaOH aqueous.
2. Results and discussion
(A)
100
Conversion of AC/%
80
60
40
20
0
(B)
HCl+ 2% HTS
HCl
H2O+2% HTS
100
TCP
DCA
3-CPG
2,3-DCP
1,3-DCP
ECH
80
Product Selectivity/%
H2O
60
40
20
0
TS
%H
l+ 2
C
H
l
HC
S
HT
2%
O+
2
H
O
H2
Fig. S1 AC conversion (A) and Product selectivity (B) of chlorohydrination and epoxidation
reactions in the absence/presence of HTS zeolite catalyst.
100
60
DCA
TCP
3-CPG
2,3-DCP
1,3-DCP
ECH
8
6
40
4
20
2
0
Ti-SBA-15
Ti-MCM-41
TS-2
Ti-β
Conversion of AC/%
Product Selectivity/%
80
10
0
Fig.2 Chlorohydrination of allyl chloride with H2O2 and HCl catalyzed by different Ti-containing
catalysts (TS-2, Ti-β, Ti-MCM-41 and Ti-SBA-15) under the same conditions
Intensity/(a.u.)
HTS
TS-1
TiO2/S-1
Amorphous TiO2-SiO2 gel
Brookite TiO2
Anatase TiO2
Rutile TiO2
Amorphous TiO2
5
10
15
20
25
30
35

2
Fig.S3 XRD spectra of various Ti-containing catalysts for AC chlorohydrination reaction with
HCl and H2O2 under mild conditions
Table S1 Structural parameters of titanosilicates calculated from nitrogen sorption isotherms
Specific area (m2/g)
Pore volume(cm3/g)
Catalysts
BET
Micro
ext
Micro
Total
Amorphous TiO2
6
-
-
-
0.029
Anatase TiO2
9
1
8
0.000
0.036
Amorphous TiO2-SiO2
471
387
85
0.028
0.357
TiO2/S-1
449
399
50
0.191
0.356
TS-1
448
406
42
0.191
0.280
HTS
447
384
53
0.178
0.352
Absorbance/ a.u.
Amorphous TiO2
Anatase TiO2
Amorphous TiO2-SiO2
TiO2/S-1
TS-1
HTS
Brookite TiO2
200
300
400
500
600
（ A（
700
800
Wavelength/ nm
Intensity/ a.u.
（ B（
Brookite TiO2
TS-1
TiO2/S-1
Amorphous TiO2-SiO2
Anatase TiO2
Amorphous TiO2
200
400
600
800
1000
1200
-1
Raman shift/ cm
(C)
Transmittance
HTS
TS-1
Ti-β
TS-2
Ti-SBA-15
Ti-MCM-41
TiO2/S-1
A-SiO2-TiO2
Brookite
Rutile
Anatase
A-TiO2
400
600
800
1000
1200
1400
1600
1800
2000
-1
Wavenumber/ cm
Fig. S4 UV-Vis (A) and Raman (B) and FT-IR (C) spectra of various Ti-containing catalysts for
AC chlorohydrination reaction with HCl and H2O2
Fig.S5 Pyridine adsorbed IR spectrum and 29Si MAS NMR spectra of HTS zeolite
Fig.S6 Characterization of TS-1 and HTS zeolites, (A) TEM image of TS-1 zeolite; (B) TEM
image of HTS zeolite; (C) BET analysis of TS-1 and HTS zeolites; (D) 3D-TEM image (electron
tomography) of HTS zeolite : From a representative crystal, a tilt series of about 141 images was
taken from about ‡-70o to +70o at 1o intervals of magnification 15 k or 20 k on one of two
microscopes (Philips CM 200 FEG or a Tecnai 20) at 200 kV and with software for automated
electron tomography.
100
100
90
90
70
DCA
TCP
3-CPG
2,3-DCP
1,3-DCP
ECH
60
50
40
80
70
30
20
60
Conversion of CH3H5Cl/%
Product selectivity/(%)
80
10
0
10
20
30
40
50
50
Reaction temperature/oC
Fig. S7 Catalytic performance of HTS zeolite in AC chlorohydrination with HCl and H2O2 at
different reaction temperature
C3H5Cl conversion and product selectivity/%
100
99.95
90
conversion
ECH
1,3-DCP
2,3-DCP
3-CPG
TCP
80
70
60
50
88.79
40
30
20
10
0
1:1:1
2:1:1
Molar ratio of HCl:H2O2:C3H5Cl
Fig. S8 catalytic performance of HTS zeolite in AC chlorohydrination under different HCl/ H2O2
molar ratio
1.39
2.73
5.5
100
DCA
TCP
3-CPG
2,3-DCP
1,3-DCP
ECH
80
60
80
60
40
40
20
20
0
Water
Methanol
Acetone
Conversion of ally chloride/%
Product selectivity distribution/%
100
0
Solvent
Fig. S9 Catalytic performance of HTS zeolite in AC chlorohydrination with HCl and H2O2 in
different solvent systems
Cl3-
non-catalyst
ClO4-
Cl2
40 min
Intensity/ a.u.
30 min
25 min
20 min
10 min
5 min
2 min
200
400
600
800
1000
1200
-1
Raman shift/ cm
Cl3-
HTS as catalyst
Cl2
ClO440 min
Intensity/ a.u.
30 min
20 min
15 min
10 min
5 min
2 min
200
400
600
800
1000
1200
-1
A[Cl]ox/AHClO4
Raman shift/ cm
1.0
0.8
0.6
0.4
0.2
0.0
without HTS
1.0
0.8
0.6
0.4
0.2
0.0
HTS
Cl2
Cl3-
0
10
20
30
40
Reaction time, min
Fig. S10 Characterization of Chloride-containing species by UV-Raman spectroscopy (with
325nm irradiation light)
Pathway I:
Cl
Cl2
+
Cl
Cl
Cl
Cl
+
Cl
OH
+
H2O
Cl
Cl
Cl
Cl
+
Cl
OH
Cl
Pathway II:
Cl
+
Cl
Cl
H
O
Cl
H
O
OH
Cl
O
H
Cl
Cl
Cl
+
Cl
Cl
+
Cl2
Cl
Cl
Fig. S11 Reaction mechanism of AC chlorohydrination with Cl2 in industry
OH
100
80
80
60
60
DCA
TCP
2,3-DCP
1,3-DCP
ECH
40
20
0
1
2
4
40
Selectivity / %
3-Chloropropene conversion / %
100
20
0
Catalyst content / %
Fig. S12 Conversion and product selectivity in AC chlorohydrination as a function of catalyst
amount
100
80
98
3-CPG
2,3-DCP
1,3-DCP
60
96
40
94
20
92
0
None catalyst
2% HTS
ECH Conversion/%
Product Selectivity/%
100
90
Fig. S13 Conversion and product selectivity of ring-opening reaction of ECH with aqueous HCl
solution with and without HTS zeolite catalyst
Table S2 Conversion and product selectivity in AC chlorohydrination with Cl2 in the absence or
presence of HTS zeolite catalyst
Catalyst
Mass of
Mass of
Flow rate
Conv.
S1,3-
S2,3-DCP/%
STCP/
H2O/ g
HCl/g
of 1% Cl2
AC/%
DCP/%
None
100
0
0.5
0.13
0
100
0
None
100
0
0.5
0.44
8
91.44
0.56
None
90
10
0.5
0.73
20.49
79.35
0.16
HTS
100
0
0.5
0.61
11.11
86.76
2.14
HTS
90
10
0.5
0.53
14.73
81.72
3.55
%
100
100
80
80
TCP
3-CPG
DCP
ECH
60
60
40
40
20
20
0
5
10
15
20
Allyl Chloride conversion/%
Product Selectivity/%
(A)
0
25
HCl treating time/day
100
100
Product Selectivity/%
80
DCA
TCP
3-CPG
2,3-DCP
1,3-DCP
ECH
60
80
60
40
40
20
20
0
Untreated
5
Conversion of AC/%
(B)
0
HCl treatment time/ day
Fig. S14 Catalytic performance of acid-treated HTS (A) and TS-1 (B) zeolites in
chlorohydrination of AC with HCl and H2O2 under optimized conditions
25 day
20 day
Intensity
15 day
10 day
5 day
0 day
5
10
15
20
25
30
35
2 (°)
XRF, %
Sample
R.C.,%
SiO2
TiO2
0day
93.5
6.24
100.00
5day
93.6
6.11
100.55
10day
93.3
6.08
101.38
15day
93.0
6.03
99.59
20day
93.0
6.11
101.38
25day
-
-
100.69
0.7
Framework Ti
Absorbance (a.u.)
0.6
0.5
0day
5day
10day
15day
20day
25day
Anatase
0.4
0.3
0.2
0.1
0.0
200
250
300
350
400
450
500
Wavelength (nm)
Fig. S15 Characterization of acid-treated HTS zeolites with different treatment time
H
SiO
SiO
Ti
OH
O
SiO
H2O2
SiO
SiO
H
Ti
SiO
O
O
H
H
C
Cl
C
H2
H2C
H
H
O
SiO
Ti
SiO
SiO
O
H2C
H2C
H
C
Cl
H
Cl
Ti
O
O H
C
H2C
H
C
H2
Cl
O
+ HCl
Cl
SiO
H
H
CH2
H+
H2C
SiO
O
CH
H2C
O
SiO
H
C
CH2
H2C
H
C
Cl
OH Cl
SN2
H
- H+
H2C
Cl
H
C
CH2
OH
Cl
H
O
SN1
CH2
H2C
Cl
H
C
CH2
OH
+ HCl
- H+
H2C
Cl
H
C
CH2
OH
Cl
Fig. S16 Proposed mechanism of novel chlorohydrination of AC with HCl and H2O2 catalyzed by
HTS zeolite