ISSN 2070-0504, Catalysis in Industry, 2019, Vol. 11, No. 2, pp. 113–118. © Pleiades Publishing, Ltd., 2019.

Russian Text © The Author(s), 2018, published in Kataliz v Promyshlennosti.

CATALYSIS IN CHEMICAL
AND PETROCHEMICAL INDUSTRY

Methods for the Synthesis of Triethanolamine

D. Yu. Yushchenkoa, *, E. G. Zhizhinaa, **, and Z. P. Paia, ***
a
Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia
*e-mail: dyy@catalysis.ru
**e-mail: zhizh@catalysis.ru
***e-mail: zpai@catalysis.ru
Received May 18, 2018; revised June 20, 2018; accepted June 21, 2018

Abstract—Triethanolamine (TEA) is a highly demanded product in medium- and low-tonnage chemistry

used in many fields of production (textile and cement industry, production of coolant-lubricants, cosmetics,
household chemicals, pharmaceuticals, etc.), which dictates wide requirements to its quality. The quality of
the product and its consumer properties depend on the production technology. The review considers various
methods for TEA production, including catalytic processes, from the viewpoint of product purity and appli-
cations. Some possible methods for further improving the consumer properties of TEA were also discussed.

Keywords: triethanolamine, ethylene oxide, ammonolysis

DOI: 10.1134/S2070050419020120

INTRODUCTION For particular applications of TEA, it should meet

certain requirements. For example, for absorption of
Triethanolamine (TEA)—N,N-(2-hydroxyethyl)- acidic gases, it can be used in a mixture of ethanol-
2-aminoethanol—belongs to the class of amino alco- amines, while its use as a plasticizer requires low color
hols and is a popular product used to solve various index and high (over 90%) content of the main sub-
problems. The addition of TEA to building mixtures stance. For the use of TEA in fine organic synthesis, for
increases their stability [1, 2]. It can be used, both in example, in the synthesis of physiologically active sub-
pure form and in mixtures with ethanolamines, as a stances, the requirement is at least 99% main substance.
corrosion inhibitor [3]; absorbent of “acidic” gases, At the same time, the quality of the product and its con-
for example, hydrogen sulfide and carbon dioxide [4, sumer properties depend on its production technology.
5]; and a source of hydrogen in photocatalytic synthe- Along with a great variety of applications, the liter-
sis [6]. TEA has good complexing properties, due to ature presents a significant number of synthetic proce-
which it is used for modification of carbon nanotubes dures. However, these methods are mainly aimed at
for subsequent extraction of lead(II) [7]; as a chelating the synthesis of the product in the form of mixtures of
compound for zinc and copper electroplating [8]; in ethanolamines [24–26], rather than pure TEA. The
the synthesis of nanosized silver particles [9]; and in descriptions do not always give the specific characteris-
the synthesis of membranes that allow the separation tics of the product that hint at its possible applications.
of xylose from glucose [10]. The applications of TEA The present review considers the available
in portable power systems for the synthesis of nano- approaches to the synthesis of TEA with the aim of
sized alumina—a component of lithium batteries [11], choosing the best method for the synthesis TEA with
or as an additive that increases the service life of alka- given characteristics.
line batteries [12] was also described. In addition, TEA
is used in fine organic synthesis (FOS), in the synthe-
sis of ionic liquids [13–15], and as a catalyst for a num- PRINCIPLES OF TEA SYNTHESIS
ber of processes: carbocyclization at atmospheric The methods for the synthesis of TEA described in
pressure [16], synthesis of bicyclic systems [17], and the literature are based on the reaction of ethylene
synthesis of organosilatranes [18–20]. In medicine, it oxide (EO) with ammonia proposed by Knorr (Fig. 1)
is used for the synthesis of amphiphilic polymers— [27] or the reaction of ethylene chlorohydrin with
promising drug carriers that increase their bioavail- ammonia proposed by Wurtz [28, 29].
ability [21] and for the synthesis of physiologically As EO is commercially available, the reaction of
active compounds [22], including hepatitis B virus ammonia and EO is preferable and has long been the
inhibitors [23]. basis of ethanolamine synthesis [1]. The synthesis of

113
114 YUSHCHENKO et al.

HCHO
OH
H2 N

C2H4 + O2 + H2
OH O O

2
+O
N
O
R

4
C2 H
R = H,
O
CH2CH2OH
oxazolidines
NH3
N O O
HO OH
OTEA HO

O H HCHO
O
N N
HO OH HO OH
TEA DEA

Fig. 1. Possible methods for the synthesis and purification of TEA.

TEA in this case occurs sequentially (Scheme 1): at plates to ensure more complete conversion of the mix-
first, monoethanolamine (MEA) is obtained, then ture of amines. MEA is further separated in the same
diethanolamine (DEA), and then TEA. The addition column. The mixture that does not contain MEA
of water greatly accelerates the process [2]. The corre- interacts again with EO, and the reaction products are
sponding activation energies and pre-exponential fac- separated in the distillation columns. This gives DEA,
tors of the Arrhenius equation are given in Table 1. TEA, and ethylene glycol.
The synthesis of triethanolamine has a number of As mentioned above, the applications of TEA dic-
specific features, which will be discussed below. tate the requirements to the quality of this product. In
some processes, only high-purity TEA can be used
SYNTHESIS OF TRIETHANOLAMINE (transparent, with an improved color index). To
FROM MONOETHANOLAMINE obtain a pure product, a method can be used in which
AND DIETHANOLAMINE TEA is obtained from a mixture of DEA + MEA [33].
In this method, ethylene oxide is added to the starting
The simplest method to obtain TEA is the interac- mixture together with hydrogen, the amount of which
tion of MEA or DEA with EO [31]. The reaction is is equivalent to that of EO. The procedure can be used for
performed at atmospheric pressure, and EO is bubbled processing the residues obtained in the TEA synthesis
through the mixture of ethanolamines. TEA obtained from ethylene oxide and ammonia. The idea of this
by this procedure does not require further purification. method was partially used in the separation of the reac-
Synthesis of TEA from a mixture of ethanolamines tion mixture after the synthesis of ethanolamines [34].
obtained by the interaction of EO and ammonia was
described in the patent [32]. The authors proposed
that the starting mixture be supplied to the middle part SYNTHESIS OF TEA DIRECTLY
of the distillation column containing 20 theoretical FROM ETHYLENE OXIDE AND AMMONIA
A mixture of products generally forms in this pro-
cess [35–37], which can be separated into ethanol-
Table 1. Arrhenius parameters for oxyethylation of ammo-
nia [3, 29] amines [38]. To obtain TEA as the main product,
ammonia and ethylene oxide should be taken in equal
Reaction Ea, kJ/mol k0, L/(mol min) proportions, 1 : 1. To reduce the formation of by-pro-
ducts, e.g., O-(hydroxyethyl)-triethanolamine (OTEA),
EO + NH3 → MEA 61.1 4.11 × 108 however, an excess of ammonia is often used (see the
EO + MEA → DEA 65.7 1.13 × 1010 oxyethylation of TEA, Fig. 1 and Table 1). In this case,
EO + DEA → TEA 63.2 the excess disposal problem arises. The excess NH3 is
2.94 × 109
absorbed by water in an absorber, as described in [39].
EO + TEA → OTEA 53.1 4.23 × 106 The ammonia absorber is installed after the reactor in

CATALYSIS IN INDUSTRY Vol. 11 No. 2 2019

 METHODS FOR THE SYNTHESIS OF TRIETHANOLAMINE 115

Water
NH3−H2O MEA
4 NH3 DEA
TEA

1 6 6 7 8 8 8

2 Techn.-grade
TEA

Fig. 2. Diagram of a unit for the reaction of ethylene oxide with ammonia [24, 45–47]: (1) supply of ammonia, (2) feeding of EO,
(3) container with water, (4) reactor, (5) heat exchanger, (6) distillation columns for separating ammonia and water, (7) column
for water separation, and (8) columns for fractional vacuum distillation.

which EO reacts with aqueous ammonia. The absorbed of alkene oxide. The products are separated by vacuum
ammonia can be recycled into the synthesis of ethanol- distillation (Fig. 2).
amines. An evaporation column was used to remove When performing the reaction of EO with aqueous
ammonia in [40]. More convenient recycling of NH3 was ammonia, the elements of the unit for the synthesis of
proposed in [41], where ammonia was absorbed by mon- ethanolamines are generally arranged in such a way that
oethanolamine at a pressure of 2–4 atm. ammonia could be recycled to the synthesis of ethanol-
Another attractive method is the two-stage addi- amines and, if necessary, the intermediate DEA and
tion of ethylene oxide, when 57–80% of the required MEA could be separated [24]. The TEA product can be
amount of EO is added to the reaction mixture at the obtained of both technical and high purity (Fig. 2).
first stage. The fractional introduction of EO makes it In addition to vacuum distillation, other methods
possible to reduce the amount of oligomer by-prod- for the removal of the MEA and DEA impurities and
ucts formed during the synthesis of TEA [42]. the accompanying secondary and primary amino alco-
hols can be used, for example, the removal of the corre-
To obtain a mixture of alkanolamines, it was pro- sponding oxazolidines (Fig. 1) obtained in the reaction
posed that a reactor connected to a reflux condenser with formaldehyde and precipitating as flakes [34].
be used [43]. Initially, some part of reagents is loaded
in the reactor. After some time, the other part of For the synthesis of TEA, both batch reactors and
reagents is additionally loaded through the upper part flow systems can be used. For example, it was indi-
of the reflux condenser. After the reaction was com- cated that the synthesis can be performed in a tubular
pleted, the products are separated using a vacuum still. reactor [35]. Later, it was proposed that a sequence of
In this case, the yield of alkanolamines increases, and tubular reactors be used, where EO is mixed with
the scheme of their synthesis is simplified. aqueous ammonia (5–30% NH3). A distinction of this
process is that the ammonia solution is introduced at
It was suggested that EO be mixed with aqueous the start of the reactor, while EO is fed in the reactor
ammonia in a mixer installed before the reactor in through special devices along its entire length [48].
which ethanolamines are synthesized [38]. After the
reaction, superstoichiometric ammonia is forwarded A recent publication of researchers from the Insti-
to the mixer and recycled. The product containing tute of Catalysis, Siberian Branch, Russian Academy
99.2–99.9% TEA is isolated from the reaction mix- of Sciences, described a method for TEA synthesis in
ture. This method is very promising for low-tonnage which high technical characteristics are achieved by
production because it is simple and allows quick syn- using a microreactor equipped with microchannel
thesis of high-quality TEA. plates [49]. This method allows synthesis of TEA with
improved properties: low color index and low content
The three-stage synthesis of alkanolamines was of oxyethylation products (including oligomers). The
described in [44]. An the first stage, alkene oxide best yield of TEA (80%, based on loaded ethylene
reacts with aqueous ammonia, forming a mixture of oxide) was achieved in the microchannel reactor at a
alkanolamines, which is separated from NH3. Then temperature of 180°C and a contact time of 3.3 min
alkanolamines are treated with an additional portion (Table 2).

CATALYSIS IN INDUSTRY Vol. 11 No. 2 2019

116 YUSHCHENKO et al.

Table 2. Effect of the contact time and reaction tempera- catalysts are used (the temperature is 70°C for the
ture on the yield of triethanolamine in a microchannel flow incoming ammonia flow and 25°C for ethylene oxide;
reactor [49] the reagents are fed in gaseous form), TEA is obtained
Yield of TEA, % with an unsatisfactory yield (maximum 46%). If water
Contact time, min is used as a cocatalyst (15 wt %) in the synthesis of eth-
95°С 180°С anolamines, then the mixture of products contains
0.8 8 56 55% TEA, 28% DEA, and 17% MEA. This also con-
firms that it is advisable to add water to the reaction
1.7 35 70 mixture in order to increase the yield of TEA.
3.3 40 80 Methods for the preparation of zeolite catalysts
were also described in patents [62–64].
This approach was later reproduced in the inven- It was suggested that alkanolamines (propanol-
tion of the Chinese authors, with the difference that amine included) be prepared using aqueous NH3 and
the mixer and the channels inside the reactor were zig- zeolite catalysts of the ZSM-5 and ZSM-10 type with
zag-shaped [50]. deposited lanthanum or ZSM-11 with deposited
yttrium [65]. The pore diameter of these catalysts for
In our opinion, the use of microchannel reactors is the synthesis of ethanolamines is 0.45–0.80 nm [66].
promising for micro- and low-tonnage productions.
Medium-tonnage production can be arranged by The liquid-phase synthesis of ethanolamines with
increasing the number of the microchannel reactors water being both the solvent and the cocatalyst was
used [51, 52]. described in [67]. The scheme of the process provides
for ammonia and EO recycling.
In addition to the above-described methods, oxida- The above-described catalysts make it possible to
tive amination can be used at temperatures of 25–500°C solve both the target problem, namely, synthesis of
and pressures of 1–200 atm (Fig. 1). Oxides of transition TEA as the main product, and to obtain reaction mix-
metals can be used as catalysts of the reaction [53]. tures enriched with MEA and DEA. To obtain TEA as
the main product, water should be added as a cocatalyst.
CATALYSTS FOR THE REACTION From the data presented in the above patents, it can
OF ETHYLENE OXIDE WITH AMMONIA be concluded that it is reasonable to use heterogeneous
catalysts to obtain MEA and DEA and that water
The use of water as a catalyst for this reaction is very should be used as a cocatalyst in order to obtain TEA
convenient; however, the isolation of ethanolamines as the main product.
in pure form requires additional energy in this case
because of the necessity of water separation by distilla-
tion [25]. Therefore, it was proposed that Lewis acids METHODS FOR IMPROVING THE COLOR
be used as catalysts instead of water for obtaining a INDEX OF TRIETHANOLAMINE
mixture of ethanolamines, for example, oxides of the The resulting ethanolamines often have an unsatis-
elements of the main subgroups of Groups I–III of the factory color index; i.e., they are strongly colored
periodic table [54], a mixture of silica and alumina because of their ability to form the products of the
[55], and heterogeneous silicates with a composition Mayer reaction—conjugated compounds that are
SiO2 : Al2O3 = (2.5–9) : 1 [56]. To obtain TEA from Schiff bases or polymers—during the decomposition
DEA and EO, a mixture of sodium, silicon, and alu- [68]. To assess the degree of coloring of the products,
minum oxides was used as a catalyst [57]. The reaction various standards are used, which are reference sam-
was performed at temperatures of 100–250°C, prefer- ples of colored solutions prepared according to the
ably 150–200°C [54–58]. The spent catalysts were ASTM International (American Society for Testing
proposed to be regenerated by heating them to 450°C. and Materials) standards. The most commonly used
The use of the described heterogeneous catalysts for references are the Gardner Scale (ASTM standard
the preparation of a mixture of ethanolamines is very D1544) and the platinum–cobalt scale also known as
promising due to their availability. the Apha-Hazen Scale (ASTM standard D1209), or
Some patents described homogeneous catalysts for the iodine scale corresponding to GOST 14871–76
the synthesis of TEA. For example, to increase the (foreign analog DIN 6162). These scales make it pos-
TEA selectivity, it was proposed that aqueous ammo- sible to compare the yellowish-brown colors and are
nium carbonate be added [59]. In other inventions, most suitable for evaluating the color index of ethanol-
carbon dioxide was used along with ammonium car- amines.
bonate for the same purpose [60]. The color index of TEA can be improved, for
It was proposed that ethanolamines be obtained in example, by adding ammonium salts (nitrate, sulfate)
the presence of zeolite catalysts of the ZBM-10 type into the autoclave for the synthesis of ethanolamines
[61]. The same patent described the methods for the [69]. In this case, the index is improved due to the
preparation of these catalysts. However, when these decrease in the amounts of dissolved oxygen and tar

CATALYSIS IN INDUSTRY Vol. 11 No. 2 2019

 METHODS FOR THE SYNTHESIS OF TRIETHANOLAMINE 117

products. In [70], the purified mixture of ethanol- discoloration of the reaction mixture is caused by the
amines was separated by fractional distillation under destruction of the compounds containing conjugated
reduced pressure at 100°C. It was also proposed that bonds under the action of UV irradiation [77], which
carbon dioxide be introduced in the reaction mixture, impart the product the yellowish color [68].
thus displacing oxygen from it [38]. This method is pref-
erable because of accessibility of CO2. The authors [71]
showed that the use of a reactor of stainless steel without CONCLUSIONS
nickel addition makes it possible to obtain products with Thus, the review considered various methods for
a satisfactory color index, at the level of 7–15 units on the the synthesis of TEA depending on the product purity
iodine scale instead of 120 units in the case of a reactor and purposes of synthesis. Methods for purification
made of a nickel-containing material. and processing of the TEA product were also analyzed
Another approach to the improvement of the color in order to ensure high quality of the product, for
index is to add phosphorous acid (or its salts) to the example, its color index. In general, analyzing the
crude product (mixture of ethanolamines). The latter material on the methods for TEA synthesis, we can
is further forwarded to the fractional distillation stage, draw the following conclusions:
at which the addition of 2000–10000 ppm of acid (1) For organization of large-scale processes, it is
allows the isolation of ethanolamines with a color reasonable to use ammonolysis of ethylene oxide in
index of 3–0.2 units on the Gardner color scale, the presence of water.
respectively [72].
(2) For organization of low-tonnage production of
Instead of fractional distillation to improve the TEA, the most effective method is the use of flow
color index, ethanolamines (e.g., TEA) can be treated microchannel systems, which are advantageous over
with hydrogen at a pressure of 2 MPa for 4 h in the periodic methods in view of the possibility of immedi-
presence of the Cu, Ru, Rh, Ag, Os, Ir, and Pt cata- ately obtaining a high-purity product (according to the
lysts deposited on layered binary hydroxides (Mg/Al, color index) that is ready for use.
Pd/Al, Ni/Al, and Zn/Al, including those with plati-
num and palladium additions). This processing per- (3) To obtain dehydrated TEA, it is recommended
formed at temperatures of up to 120°C allows us to to use zeolite-supported catalysts (ZSM-5); the prod-
improve the color index to 20–60 units on the plati- uct is subsequently adjusted to the specified require-
num–cobalt scale, even if its initial value was 500 units ments by vacuum distillation, which provides almost
(Pt/Co scale) [73]. The described methods can be pure TEA possessing a low color index, or by treat-
used as reserve because the use of gaseous hydrogen ment with reducing agents.
requires increased safety measures.
In [74], it was proposed that TEA be treated with FUNDING
phosphine (introduced as a gas in TEA) or phosphides
after the synthesis. The color index of the resulting This study was performed within the framework of
mixtures ranges from 0 to 10–20 units on the Hazen the state assignment at the Institute of Catalysis, Sibe-
scale. In view of the cost of these phosphorus com- rian Branch, Russian Academy of Sciences (project
pounds and their high toxicity, this method cannot be no. 17-117041710081-1).
considered acceptable.
In [75], the color index of ethanolamines was sug- REFERENCES
gested to be improved by heating ethanolamines with 1. Yaphary, Y.L., Yu, Z., Lam, R.H.W., and Lau, D.,
activated carbon at temperatures of up to 200°C for the Constr. Build. Mater., 2017, vol. 141, pp. 94–103.
required time. This approach can reduce the color
2. Wang, X.Y., Lan, M.Z., Hou, W.F., Xiang, B.F., and
index to 20 units on the platinum–cobalt scale. Zhao, X.D., Mater. Sci. Forum, 2017, vol. 898,
The most ingenious method for improving the pp. 2010–2017.
color index of TEA is its treatment with electromag- 3. Xhanari, K., Grah, N., Finšgar, M., Fuchs-Godec, R.,
netic radiation (light) with a wavelength of 100–1200 and Maver, U., Chem. Pap., 2017, vol. 71, no. 1, pp. 81–89.
nm (preferably 280–520 nm) at a temperature of 20– 4. Saidi, M., J. Taiwan Inst. Chem. Eng., 2017, vol. 80,
190°C (preferably 25–60°C); the details of the pp. 301–313.
method are described in patent [76]. Irradiation is per- 5. Saghafi, H. and Arabloo, M., Int. J. Greenhouse Gas
formed for a period of time sufficient for TEA discol- Control, 2017, vol. 58, pp. 256–265.
oration. The same patent describes the diagram of the 6. He, K., Xie, J., Li, M., and Li, X., Appl. Surf. Sci., 2018,
unit for the preparation of a mixture of ethanolamines, vol. 430, pp. 208–217.
in which a source of electromagnetic radiation is pro- 7. Chen, N., Teng, J., Jiao, F.-P., Jiang, X.-Y., Hao, X.,
vided that decolorizes TEA after its separation by dis- and Yu, J.-G., Desalin. Water Treat., 2017, vol. 71,
tillation. This method is most promising because it pp. 191–200.
does not require the introduction of additional 8. Ramírez, C. and Calderón, J.A., J. Electroanal. Chem.,
reagents in the synthesis products. In this case, the 2016, vol. 765, pp. 132–139.

CATALYSIS IN INDUSTRY Vol. 11 No. 2 2019

118 YUSHCHENKO et al.

9. Maleki, B., Baghayeri, M., Sheikh, S., Babaee, S., and 32. US Patent 3849262, 1974.
Farhadi, S., Russ. J. Gen. Chem., 2017, vol. 87, no. 5, 33. GB Patent 1453762, 1976.
pp. 1064–1072. 34. US Patent 6353138, 2002.
10. Roli, F.M., Yussof, H.W., Saufi, S.M., Seman, M.N.A., 35. US Patent 5545757, 1996.
and Mohammad, A.W., Chem. Eng. Trans., 2017, 36. SK Patent 282747, 1998.
vol. 56, pp. 1507–1512.
37. RF Patent 2176636, 2001.
11. Masoud, E.M., El-Bellihi, A.-A., Bayoumy, W.A., and
Mousa, M.A., J. Alloys Compd., 2013, vol. 575, 38. WO Patent 0153250, 2001.
pp. 223–228. 39. US Patent 4119670, 1978.
12. Kelly, M., Duay, J., Lambert, T.N., and Aidun, R., 40. US Patent 4355181, 1982.
J. Electrochem. Soc., 2017, vol. 164, no. 14, pp. A3684– 41. RF Patent 2162461, 2001.
A3691. 42. RF Patent 2052450, 1996.
13. Gruzdev, M.S., Shmukler, L.E., Kudryakova, N.O., 43. US Patent 2004068143, 2004
Kolker, A.M., and Safonova, L.P., J. Mol. Liq., 2018, 44. BR Patent 0303716, 2005.
vol. 249, pp. 825–830. 45. US Patent 6388137, 2002.
14. Kondratenko, Y., Kochina, T., Fundamensky, V., 46. US Patent 7164044-B2, 2007.
Ignatyev, I., Panikorovskii, T., and Nyanikova, G., 47. WO Patent 2005035 481, 2005.
J. Mol. Liq., 2016, vol. 221, pp. 1218–1224.
48. CN Patent 101100 433, 2008.
15. Fundamensky, V.S., Kochina, T.A., Kondratenko, Y.A.,
Zolotarev, A.A., Vlasov, Y.G., and Ignatyev, I.S., 49. RF Patent 2605 421, 2016.
J. Mol. Liq., 2017, vol. 230, pp. 113–120. 50. Andreev, D.V., Makarshin, L.L., Gribovskii, A.G.,
16. Zhao, Y., Qiu, J., Li, Z., Wang, H., Fan, M., and Wang, J., Yushchenko, D.Y., Sergeev, E.E., Zhizhina, E.G.,
ChemSusChem, 2017, vol. 10, no. 9, pp. 2001–2007. Pai, Z.P., and Parmon, V.N., Chem. Eng. J., 2015,
17. Khoraamabadi-zad, A., Azadmanesh, M., Karamian, R., vol. 259, pp. 252–256.
Asadbegy, M., and Akbari, M., RSC Adv., 2014, vol. 4, 51. CN Patent 106478430, 2017.
no. 88, pp. 47721–47725. 52. Makarshin, L.L., Pai, Z.P., and Parmon, V.N., Russ.
18. Brennan, B.J., Gust, D., and Brudvig, G.W., Tetrahe- Chem. Rev., 2016, vol. 85, no. 2, pp. 139–155.
dron Lett., 2014, vol. 55, no. 5, pp. 1062–1064. 53. Šalić, A., Tušek, A., and Zelić, B., J. Appl. Biomed.,
19. Alentiev, D.A., Chapala, P.P., Filatova, M.P., Fin- 2012, vol. 10, no. 3, pp. 137–153.
kelshtein, E.S., and Bermeshev, M.V., Mendeleev Com- 54. WO Patent 0132600, 2001.
mun., 2016, vol. 26, no. 6, pp. 530–531. 55. DD Patent 298633, 1992.
20. Bessi, M., Monini, M., Calamante, M., Mordini, A., 56. DD Patent 298634, 1992.
Sinicropi, A., Basosi, R., Di Donato, M., Foggi, P., 57. DD Patent 298635, 1992.
Iagatti, A., Zani, L., and Reginato, G., Synthesis 58. DD Patent 298636, 1992.
(Stuttg.), 2017, vol. 49, no. 17, pp. 3975–3984. 59. EP Patent 0 690043, 1996.
21. Wang, H., Qin, A., Li, X., Zhao, X., Liu, D., and He, C., 60. US Patent 5395973, 1995.
J. Polym. Sci., Part A: Polym. Chem., 2015, vol. 53,
no. 21, pp. 2537–2545. 61. US Patent 7119231, 2006.
22. Adamovich, S.N., Kuznetsova, G.A., Ushakov, I.A., 62. DE Patent 4323774, 1996.
Mirskov, R.G., and Mirskova, A.N., Russ. Chem. Bull., 63. EP Patent 0 652207, 1995.
2016, vol. 65, no. 3, pp. 826–827. 64. EP Patent 0 941986, 1999.
23. Han, A., Li, L., Qing, K., Qi, X., Hou, L., Luo, X., Shi, S., 65. EP Patent 1219592, 2002.
and Ye, F., Bioorg. Med. Chem. Lett., 2013, vol. 23, 66. EP Patent 1104752, 2001.
no. 5, pp. 1310–1314. 67. US Patent 20030065224A1, 2003.
24. Frauenkron, M., in Ullmann’s Encyclopedia of Industrial 68. Yano, H., Noda, A., Hukuhara, T., and Miyazawa, K.,
Chemistry, Weinheim: Wiley-VCH, 2001, pp. 547–572. J. Am. Oil Chem. Soc., 1997, vol. 74, no. 7, pp. 891–893.
25. Tsuneki, H., Kirishiki, M., and Oku, T., Bull. Chem. 69. US Patent 3151166, 1964.
Soc. Jpn., 2007, vol. 80, no. 6, pp. 1075–1090. 70. GB Patent 1092449, 1967.
26. Zahedi, G., Amraei, S., and Biglari, M., Korean J. 71. US Patent 4567303, 1986.
Chem. Eng., 2009, vol. 26, no. 6, pp. 1504–1511.
72. US Patent 6291715, 2001.
27. Knorr, L., Ber. Dtsch. Chem. Ges., 1899, vol. 32, no. 1,
pp. 729–732. 73. WO Patent 2005058795, 2005.
28. Wurtz, A., Ann. Chem. Pharm., 1860, vol. 114, no. 1, 74. US Patent 2007270 615, 2007.
pp. 51–54. 75. US Patent 2006142615, 2006.
29. Wurtz, A., Ann. Chem. Pharm., 1862, vol. 122, no. 3, 76. WO Patent 03048105, 2003.
pp. 354–359. 77. MacCallum, J.R., Compr. Polym. Sci., Suppl., 1989,
30. Miki, M., Ito, T., Hatta, M., and Okabe, T., J. Jpn. Oil vol. 74, no. 7, pp. 529–537.
Chem. Soc., 1966, vol. 15, no. 5, pp. 215–220.
31. GB Patent 825 475, 1958. Translated by L. Smolina

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