Chlorohydrination of allyl chloride with HCl and H2O2 catalyzed by hollow titanium silicate zeolite to produce dichloropropanol

Article abstract of DOI:10.1039/c6gc03005j

Overall, over 95% of epichlorohydrin is industrially manufactured via the chlorohydrination route with hazardous Cl₂ as a reagent, which brings serious operation and pollution problems. Herein, we describe a novel Cl₂-free process for the synthesis of dichloropropanols from allyl chloride with H₂O₂ and HCl catalyzed by hollow titanium silicate zeolite under mild conditions. A high conversion and overall dichloropropanol selectivity exceeding 95% are simultaneously achieved, and the heterogeneous catalyst is highly stable and amenable for reuse. Comprehensive experimental and spectroscopic data suggest that the Lewis acidity of the framework Ti species has a synergistic effect with the Br?nsted acidity of HCl that promotes the epoxidation of allyl chloride and the ring opening of the epoxy groups.

Full text of DOI:10.1039/c6gc03005j

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DOI: 10.1039/C6GC03005J
Chlorohydrination of Allyl Chloride with HCl and H2O2 to Produce
Dichloropropanols Catalyzed by Hollow Titanium Silicate 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.
Corresponding author：xiachangjiu@gmail.com，minlin@tom.com
In global, over 95% of epichlorohydrin is commercially manufactured via chlorohydrination route
with hazard Cl2 as raw material, which brings serious operation and pollution problems. Herein,
we describe a novel Cl2-free process for synthesizing dichloropropanols from allyl chloride with
H2O2 and HCl catalyzed by hollow titanium silicate zeolite under mild conditions. High
conversion and overall dichloropropanol selectivity exceeding 95% are simultaneously achieved,
and the heterogeneous catalyst is ultra stable and easy to be reused. Comprehensive experiment
and spectroscopic results infer that Lewis acidity of framework Ti species is synergistic with
Brönsted acidity of HCl to accelerate the epoxidation of allyl chloride and ring-opening of epoxy
groups.
D
ichloropropanols (DCPs) are key precursors for synthesizing epichlorohydrin (ECH), which is
widely used for commercial production of epoxy resins, surfactants, pharmaceuticals and
plasticizers. [1,2] Nowadays, over 95% of ECH is prepared by combining the chlorohydrination of
allyl chloride (AC) with Cl2 to produce DCPs (including 1,3ꢀDCP and 2,3ꢀDCP) and
dehydrochlorination of DCPs with Ca(OH)2 in industry, as shown in Scheme.1(A).[3,4,5] It is
theoretically estimated that about 0.64kg gaseous Cl2 is consumed per kilogram of DCPs, with the
formation of 0.3kg HCl waste. Obviously, it entails many serious disadvantages, including low
atom utilization efficiency, high waste generation, and high energy consumption. [6,7] Especially, to
reduce the formation of trichloropropane (TCP), Cl2 should be diluted by large amount of H2O,
giving birth to large amount of harmful sewage and ultraꢀlow DCPs concentration (<4%).
Although several alternative green approaches has been explored, i.e. glycerol chlorination,[8,9] the
epoxidation of AC catalyzed by Tiꢀcontaining zeolites [10,11,12] and heteropolycompounds[13]. These
novel processes are still far beyond commercialization at large scale, owing to the complex

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operation, high energy consumption, and poor catalyst stability. TSꢀ1 zeolite with MFI topology
has been widely used in the field of the ketone ammoximation,[14,15] phenol hydroxylation[16,17] and
the epoxidation of allylic compounds (allyl alcohol, allyl chloride, mutually alcohol, crotyl alcohol,
and 1ꢀbuteneꢀ3ꢀol), propylene and natural compounds (limonene).[18,19,20,21,22,23,24,25] However,
TSꢀ1 shows low catalytic performance (AC conversion<50%) in the direct epoxidation of AC to
synthesis ECH, due to the electronꢀwithdrawing effect of chloride group on C=C bonds (Fig.
S1).[26,27] During direct epoxidation, we also observed that the polymerization of AC easily
occurred, which causes the blocking of micropores. Moreover, huge methanol solvent is needed,
[28,29]
increasing the solvolysis of ECH and the energy consumption for solvent separation.
Therefore, to develop an environmental friendly process to produce DCPs is still a tremendous
challenge facing green manufacturing of ECH in industry.
Herein, inspired by the elementary steps of chlorohydrination process and catalytic oxidation
mechanism of TSꢀ1/H2O2/H2O system,[3,30,31] an efficient chlorohydrination route to produce DCPs
from AC catalyzed by hollow titanium silicate (HTS) zeolite, with HCl and H2O2 as reactants, has
been developed (Scheme.1B). HTS zeolite is prepared via the post synthesis of traditional TSꢀ1
with organic template under hydrothermal conditions. The chlorohydrination reaction was carried
out at low temperature, with continuous stirring in a threeꢀnecked reactor. Over 85.0% conversion
of AC is observed, with 87.8% selectivity of 1,3ꢀDCP and 1.7% selectivity of 2,3ꢀDCP,
respectively (Fig.1). Importantly, there is almost no TCP observed, and the DCPs concentration is
over 20%, thus this approach shows much greater advantages than traditional routes. And to our
best knowledge, it is the first time to synthesize DCP from AC with inorganic H2O2 and HCl under
the impact of framework Ti species of TSꢀ1 zeolite.

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(A) Traditional chlorohydrination route
OH
Cl
Cl
O
ꢀ HCl
ꢀ HCl
+
Cl
Cl
+
+ H2O
Cl2
Cl
+ Ca(OH)2
HO
Cl
Cl
Cl
(B) Novel chlorohydrination route catalyzed by HTS zeolite
OH
Cl
Cl
chlorohydrination
+
Cl
+
+
H2O2
HO
Cl
Cl
Cl
HCl
ꢀH2O
epoxidation
Cl
OH
O
+ H2O
Cl
Cl
Cl
HO
Cl
Scheme.1 Comparison of the industrial chlorohydrination process and the novel method for production of
dichloropropanol (A) Industrial Cl2 route, (B) Novel Cl2ꢀfree method
100
80
60
40
20
0
100
80
60
40
20
0
DCA
TCP
3-CPG
2,3-DCP
1,3-DCP
ECH
4
l
2
e
e
l
i
t
e
t
i
k
2
1
-
S
1
-
S
T
H
k
s
O
i
O
i
n
C
i
S
T
a
t
/
2
a
l
u
T
T
-
2
o
T
-
a
R
o
r
B
n
O
i
A
A
O
B
T
i
S
-
A
Fig.1 Chlorohydrination of allyl chloride with H2O2 and HCl catalyzed by different Ti-containing catalysts
under the same conditions
Our experiments display that HTS zeolite is the best one among different Tiꢀcontaining catalysts
we tested (Fig.1 and Fig.S2). In principle, HOCl and/or the chloronium ion species derivated from

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Cl2 are considered as the chemical intermediates of the chlorohydrination process,[32,33] while TCP
is produced from the direct chlorination of AC with gaseous Cl2. Apparently, low AC conversion
(<5%) and high TCP selectivity (>14%) are observed over amorphous TiO2 (AꢀTiO2), amorphous
TiO2ꢀSiO2 (Aꢀ TiO2ꢀSiO2), crystalline TiO2 (including Anatase, Rutile, and Brookite), owing to the
diffusion limitation inside condensed phase (Fig.S3 and Table S1). In addition, when enhancing
the accessibility of octahedral Ti specie, far higher AC conversion (>45%) and TCP selectivity
(>65%) are coinstantaneously found over soluble TiCl4 and TiO2/Sꢀ1, while no TCP has been
detected in blank test. It suggests the octahedral Ti species (Fig.S4) favor the generation of Cl2 and
then accelerates the direct chlorination of AC in organic phase, similarly as the Cl2
chlorohydrination reaction we have done. However, interestingly, both TSꢀ1 and HTS show high
total selectivity (>90%) of 1,3ꢀDCP and 2,3ꢀDCP under the same reaction conditions. It indicates
that isolated tetrahedral framework Ti species acted as Lewis acid sites (Fig.S5) are prominently
helpful for the efficient transformation of AC to DCPs through this improved chlorohydrination
route. In addition, HTS presents significantly higher AC conversion (85%) than TSꢀ1 (49%),
which is attributed to the better mass diffusion performance within hollow cavities of zeolite
(Fig.S6). [34,35]
In contrast to the industrial chlorohydrination route, ECH and 3ꢀchlorideꢀ1, 2ꢀpropylene glycol
(3ꢀCPG) are achieved in novel route, especially in low HCl/H2O2 region, via the epoxidation of
AC catalyzed by tetrahedral framework Ti species and hydrolytic ringꢀopening of ECH with H2O,
respectively. Consequently, we can observe that increasing reaction temperature doesn’t enhance
the AC conversion, but it can significantly improve the selectivity of 3ꢀCPG and DCP at the same
time (Fig.S7), without the detection of ECH at relative high temperature (40ꢀ50oC). It is inferred
that H2O and HCl are competitive to react with the epoxy groups of ECH, which further verifies
the existence of ECHꢀintermediated pathway (Fig.S8). Moreover, when H2O is replaced by other
organic solvents (such as methanol and acetone), it causes a sudden drop of AC conversion from
67.3% (in water) to 31.3% (in methanol) and 11.4% (in acetone), respectively (Fig.S9).
Meanwhile, no 3ꢀCPG is formed in organic solvent systems, which is ascribed to the inhibition of
hydrolysis reaction of epoxy groups with H2O. Interestingly, few amount of 1,3ꢀdichloroacetone
(4.31%) was formed in methanol system, which is explained by the deep oxidation of 1,3ꢀDCP by
HTS/H2O2 system. According to these results, we confirm that the formation of ECH and DCPs

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proceeds via the epoxidation of AC and the addition reaction of HCl to ECH, respectively, due to
the high reactivity of epoxide group in acidic conditions.
On the other hand, Cl2 has been characterized as a major intermediate in this route by UVꢀRaman
spectroscopy (of 325nm irradiation wavelength) (Fig.S10). Thus, the other plausible mechanism
involves the electrophilic addition of activated Cl species to the C=C bonds of AC molecules as
industrial chlorohydrin approach (Fig.S11). As the H2O2 solution is continuously added, the
ꢀ
activated Cl species (including HOCl and Cl3 ) are gradually generated, and then they readily react
with AC to produce DCPs, rather than dissolve in organic phase, owing to only trace TCP detected.
However, when reduces the catalyst amount, the selectivity of TCP surprisingly becomes higher,
almost as high as that catalyzed by octahedral Ti species (Fig.S12). That is because, if there are no
enough active sites for generating DCPs, the activated Cl species cannot be readily consumed,
then they will diffuse into the organic phase in the form of Cl2 to accelerate the formation of TCP.
That is why TCP selectivity becoming higher as a function of the increasing of HCl concentration,
owing to the decreasing of H2O content (Fig.2A). Hence, it is of great importance to match the AC
conversion and the formation of Cl2 to enhance the selectivity of DCPs in this route.
To further identify which pathway mainly occurred, the ring opening reaction of ECH with
aqueous HCl catalyzed by HTS was carried out, with high yield of 1,3ꢀDCP (86.32%)(Fig.S13).
Meanwhile, it is observed that the major product is 2,3ꢀDCP (>90% selectivity) for chlorohydrin
route in both our lab and industry (Table S2). As previously mentioned, the major product is
1,3ꢀDCP isomer (>90% selectivity in Fig.2A) in our novel route. Therefore, we infer that DCPs
are preferentially generated via the addition of HCl to epoxy groups of ECH, rather than the direct
electrophilic addition of HOCl to AC molecules.[7] Particularly, in the case of high catalyst amount,
the AC conversion and DCPs yield are closely relevant with the increasing of HCl amount. It
suggests that the addition of HCl to ECH catalyzed by H+ ions can promote the epoxidation of AC
catalyzed by the framework Ti species of TSꢀ1, owing to the promoting of epoxidation reaction
equilibrium by consuming ECH. As a consequence, there is a synergy between the Lewis acid
sites (framework Ti species) and Brönsted acid sites (H+) to enhance the formation rates of ECH
and DCPs.

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100
80
60
40
20
0
100
90
80
70
60
50
（
A
）
TCP
3-CPG
1,2-DCP
1,3-DCP
ECH
10
15
20
25
30
35
40
Concentration of HCl/%
100
80
60
40
20
0
100
90
80
70
60
50
40
30
20
10
0
(B)
TCP
3-CPG
DCP
ECH
1
2
3
4
5
6
Recycle times
Fig.2 Catalytic performance of HTS zeolite in chlorohydrination of allyl chloride: A) Effect of HCl
concentration on the allyl conversion and product selectivity; B) The conversion of allyl chloride and product
distribution in the reuse experiments for 6 times under the same conditions.
Except for the high AC conversion and product selectivity, HTS zeolite shows more promising
stability than TSꢀ1 in this route (Fig.2b), which is of great importance for heterogeneous catalysis
in industry. [36,37] The reuse tests were carried out under optimized reaction parameters for six
times, without calcination treatment to remove the deposited organic compounds. It is clearly

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found that catalyst still remains as high catalytic activity as the fresh one after the sixth recycle,
with >95% AC conversion and >98% DCP selectivity. Moreover, HTS zeolite has been deeply
soaked by 10 wt% HCl solution for three months at room temperature under static state, to
examine its stability (Fig.S14). The acid treated HTS were found to remain as reactive as fresh
HTS, almost with the same AC conversion and product selectivity. After that, both reused HTS
and acid treated HTS zeolites were investigated by multiple characterization methods, such as
XRD, BET and TEM (Fig.S15). And there are almost no changes in physiochemical properties
observed, which is accorded to its excellent resistibility of tetrahedral framework Si and Ti atoms
to H2O and HCl molecules, without the hydrolysis of TꢀOꢀSi bonds (T=Si or Ti) under acidic
conditions. At the same time, both TSꢀ1 and HTS zeolites show high reusability and regeneration
in other catalytic oxidation reactions, carried out by EniChem and SINOPEC, respectively. [38,39]
When substituted olefins are introduced as substrates, it is observed that olefin conversion and
alcohol selectivity are significantly decreasing along with the increasing of molar size (see Table
1). Notably, no alcohol product is detected for cyclooctene, whereas large amount of chloride
substituted products are generated, attributing to the direct chlorination with Cl2. That is because
cyclooctene is too large in size to diffuse into the micropores of TSꢀ1 zeolite, thus it preferentially
reacts with Cl2 in organic phase.[4] Consequently, it further indicates that this improved
chlorohydrination route majorly focuses on the epoxidation of AC with H2O2 and electrophilic
addition of HCl to epoxy groups in the presence of Lewis acid (framework Ti species) and
Brönsted acid sites, rather than the traditional chlorohydrin route (Fig.S16).
Table 1. Substrate scope for catalytic chlorohydrination of substituted olefins over HTS zeolite. The reactions
were carried out in a threeꢀnecked bottom flask at 30oC, with dropꢀwise adding of H2O2 solution within 30
minutes.
%Selectivity for
2
Time
(h)
Substrates
Products % Yield
%Conversion
1
3
0
99.81
2
98.7
0.68

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99.99
2
2
2
86.28
56.09
55.92
13.72
38.08
6.92
0
30.78
5.83
7.53
37.16
From the viewpoint of industrial application, this Cl2ꢀfree chlorohydrination route is quite
available to be carried out at large scale, just like those commercial processes catalyzed by HTS
zeolite we have done.[40,41] Summarily, this process is of high DCPs yield and ultraꢀlong catalyst
lifetime, without the formation of low valueꢀadded TCP byproduct. Additionally, there are no
organic solvents needed, which means it is not necessary to take extra energy consumption for
solvent separation. More importantly, the route we report here provides a novel viewpoint to
catalytically covert olefins to high valued chlorohydrins by rational blending the solid Lewis acid
and liquid Brönsted acid sits, according to their instinct characteristics of chlorohydrination
reactions.
REFERENCE AND NOTES
1 R.A. Sheldon, J.A. Van Doorn, C.W.A. Schram, A.J. De Jong, J. Catal. 31, 438 (1973).
2 J. Li, G. Zhao, S. Gao, Y. Lv, J. Li, Z. Xi, Org. Process Res. Dev. 10, 876 (2000).
3 J. Zhang, J. Tan, K. Wang, Ya. Lu, G. Luo, Ind. Eng. Chem. Res. 51,14685 (2012)
4 Y. Lu, , R. Wang, J. Zhang, Q. Jin, G. Luo, Chinese J. Chem. Eng. 23, 1123 (2015).
5 J. Zhang, Y. Lu, Q. Jin, K. Wang, G. Luo, Chem. Eng. J. 203, 142 (2012).
6 G. S. Sharifov, Kinet. Catal. 42, 615 (2001).
7 R. M. Machado, T. W. Chapman, Ind. Eng. Chem. Res. 28, 1789 (1989).
8 E. Santacesaria, R. Tesser, M. Di Serio, L. Casale, D. Verde, Ind. Eng. Chem. Res., 49, 964 (2010).
9 R. Tesser, E. Santacesaria, M. Di Serio, G. Di Nuzzi, V. Fiandra, Ind. Eng. Chem. Res. 46, 6456 (2007).
10 R. K. Pandey, R. Kumar, Catal. Comm. 8, 379 (2007).
11 L. Wang, Y. Liu, W. Xie, H. Zhang, H. Wu, Y. Jiang, M. He, P. Wu, J. Catal. 246, 205 (2007).
12 M.G. Clerici, P. Ingallina, J.Catal. 140, 71 (1993).
13 Y. Sun, Z. Xi, G. Cao, J. Mol. Catal. AꢀChem. 166, 219 (2001).
14 J Le Bars, J Dakka, RA Sheldon. Appl. Catal. A: General, 136 ,69 (1996).
15 A. Thangaraj, S. Sivasanker, P. Ratnasamy, J. Catal., 131,394 (1991).
16 A. Tuel, S. MoussaꢀKhouzami, Y.Ben Taarit, C. Naccache, J. Mol. Catal. 68, 45(1991).
17 U. Wilkenhöner, G. Langhendries, F.van Laar, G.V. Baron, D.W. Gammon, P.A. Jacobs, E. van Steen, J. Catal.
203, 201 (2001).
18 G.J. Hutchings, D.F. Lee, J. Chem. Soc., Chem. Commun. 1095 (1994).
19 W. Adam, A. Corma, T.I. Reddy, M. Renz, J. Org. Chem. 62, 3631 (1997).
20 A. Wróblewska, J. Mol. Catal. A: Chemical 229, 207 (2005).

Page 9 of 9
Green Chemistry
View Article Online
DOI: 10.1039/C6GC03005J
21 A. Wróblewska, M. Rzepkowska, E. Milchert, Appl. Catal. A: General 294 , 244 (2005)
22 A. Wróblewska, A. Fajdek, J. Hazard. Mater. 179258 (2010).
23 S. Park, K. Min Cho, M. Hye Youn, J. Gil Seo, J. Chul Jung, S.ꢀH. Baeck, T. Jin Kim, Y.ꢀM. Chung, S.ꢀH. Ohc,
I. Kyu Song, Catal. Comm. 9, 2485 (2008).
24 M. Dua, J. Huang, D. Sunb, Q. Lib, Appl. Surf. Sci. 366, 292 (2016).
25 A. Wróblewska, Molecules 19, 19907 (2014).
26 Q. Wang, Z. Mi, Y. Wang, L. Wang, J. Mol. Catal. A 229, 71(2005).
27 H. Gao, G. Lu, J. Suo, S. Li, App. Catal. A 138, 27(1996).
28 D.Kahlich, U.Wiechern, J. Lindner, Ullmann's Encyclopedia of Industrial Chemistry (2000).
29 H. Gao, W. Lu, Q. Chen, Chin. J. Catal. 23, 3 (2002).
30 F. Bonino , A. Damin , G. Ricchiardi, J. Phys. Chem. B 108, 3573(2004).
31 C. Prestipino, F. Bonino, S. Usseglio, A. Damin, A. Tasso, M. G. Clerici, S. Bordiga, F. D′Acapito, A. Zecchina,
C. Lamberti, ChemPhysChem, 5, 1799(2004).
32 V. Russo, R. Tesser, E. Santacesaria, M. Di Serio, Ind. Eng. Chem. Res. 52, 1168(2013).
33 T. A. Nijhuis, M. Makkee, J. A.Moulijin, B. M. Weckhuysen, Ind. Eng. Chem. Res. 45, 3447 (2006).
34 C. Xia, L. Ju, Y. Zhao, H. Xu, B. Zhu, F. Gao, M. Lin, Z. Dai, X. Zou, X. Shu, Chinese J. Catal. 36, 845(2015).
35 C. Xia, L. Long, B. Zhu, M. Lin, X. Shu, Catal. Comm. 80, 49(2016).
36 A. Zheng, C. Xia, Y. Xiang, M. Xin, B. Zhu, M. Lin, G. Xu, X. Shu, Catal. Comm. 45, 34(2014).
37 M. S. Holm, S Saravanamurugan, E Taarning, Science 328, 602 (2010).
38 Y. Wang, S. Zhang, Y. Zhao, M. Lin, J. Mol. Catal. A 385, 1 (2014).
39 A Carati, C Flego, E P. Massara, R Millini, L Carluccio, W.O Parker, G Bellussi, Micro. Meso. Mat. 30,
137(1999).
40 M. Lin, C. Xia, B. Zhu, H. Li, X. Shu, Chem. Eng. J. 295, 370(2016).
41 C. Xia, M. Lin, A. Zheng, Y. Xiang, B. Zhu, G. Xu, X. Shu, J. Catal. 338, 340(2016).