Investigation of 3,3′,5,5′-tetra-tert-butyl-4,4′-stilbenequinone-based catalyst in the reaction of liquid-phase oxidation of inorganic sulfides

Article abstract of DOI:10.1080/17415993.2017.1397153

In this paper, the intermediate and final reaction products of catalytic oxidation of inorganic sulfides in the presence of oxygen dissolved in the kerosene fraction and 3,3′,5,5′-tetra-tert-butyl-4,4′-stilbenequinone were investigated. The thiosulfate and sulfate are major products of the oxidation of sodium sulfide under these conditions. The intermediate and final products in the catalytic oxidation of sulfide sulfur do not affect the rate of its oxidation. The yield of catalytic oxidation products depends on the nature of the sulfide and on the pH of the solution. The catalytic cycle for sulfide oxidation in the presence of 3,3′,5,5′-tetra-tert-butyl-4,4′-stilbenequinone is shown. The role of 3,3′,5,5′-tetra-tert-butyl-4,4′-stilbenequinone is to create a new and a more effective way of electron transfer from the reducing agent (sulfide) to the oxidant (oxygen).

Full text of DOI:10.1080/17415993.2017.1397153

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Journal of Sulfur Chemistry
ISSN: 1741-5993 (Print) 1741-6000 (Online) Journal homepage: http://www.tandfonline.com/loi/gsrp20
Investigation of 3,3′,5,5′-tetra-tert-butyl-4,4′-
stilbenequinone-based catalyst in the reaction of
liquid-phase oxidation of inorganic sulfides
Hien Y. Hoang, Renat Maratovich Akhmadullin, Farida Yunusovna
Akhmadullina, Rustem Kayumovich Zakirov, Dinh Nhi Bui, Alfiia Garipova
Akhmadullina & Almir Sabirovich Gazizov
To cite this article: Hien Y. Hoang, Renat Maratovich Akhmadullin, Farida Yunusovna
Akhmadullina, Rustem Kayumovich Zakirov, Dinh Nhi Bui, Alfiia Garipova Akhmadullina & Almir
Sabirovich Gazizov (2017): Investigation of 3,3′,5,5′-tetra-tert-butyl-4,4′-stilbenequinone-based
catalyst in the reaction of liquid-phase oxidation of inorganic sulfides, Journal of Sulfur Chemistry,
DOI: 10.1080/17415993.2017.1397153
To link to this article: http://dx.doi.org/10.1080/17415993.2017.1397153
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JOURNAL OF SULFUR CHEMISTRY, 2017
https://doi.org/10.1080/17415993.2017.1397153
Investigation of 3,3ꢀ,5,5ꢀ-tetra-tert-butyl-4,4ꢀ-
stilbenequinone-based catalyst in the reaction of liquid-phase
oxidation of inorganic sulfides
Hien Y. Hoang a, Renat Maratovich Akhmadullinc, Farida Yunusovna Akhmadullinaa,
Rustem Kayumovich Zakirova, Dinh Nhi Buib, Alfiia Garipova Akhmadullinac and Almir
Sabirovich Gazizovd
aDepartment of Industrial Biotechnology, Kazan National Research Technological University, Kazan, Russia
Federation; bDepartment of Environmental Technology, Viet Tri University of Industry, Viet Tri, Viet Nam;
cR&D Center ‘AhmadullinS – Science & Technology’, Kazan, Russian Federation; dKazan Scientific Centre
Russian Academy of Sciences, Laboratory of Elementoorganic Synthesis, A.E. Arbuzov Institute of Organic and
Physical Chemistry, Kazan, Russia Federation
ABSTRACT
ARTICLE HISTORY
Received 21 July 2017
Accepted 22 October 2017
In this paper, the intermediate and final reaction products of catalytic
oxidation of inorganic sulfides in the presence of oxygen dis-
solved in the kerosene fraction and 3,3ꢀ,5,5ꢀ-tetra-tert-butyl-4,4ꢀ-
stilbenequinone were investigated. The thiosulfate and sulfate are
major products of the oxidation of sodium sulfide under these condi-
tions. The intermediate and final products in the catalytic oxidation
of sulfide sulfur do not affect the rate of its oxidation. The yield of cat-
alytic oxidation products depends on the nature of the sulfide and on
the pH of the solution. The catalytic cycle for sulfide oxidation in the
presence of 3,3ꢀ,5,5ꢀ-tetra-tert-butyl-4,4ꢀ-stilbenequinone is shown.
The role of 3,3ꢀ,5,5ꢀ-tetra-tert-butyl-4,4ꢀ-stilbenequinone is to create
anewandamoreeffectivewayofelectrontransferfromthereducing
agent (sulfide) to the oxidant (oxygen).
KEYWORDS
Inorganic sulfides;
3,3ꢀ,5,5ꢀ-tetra-tert-butyl-4,4ꢀ-
stilbenequinone; sodium
thiosulfate; sodium sulfate;
catalytic mechanism
CONTACT Hien Y. Hoang
nhochieny@gmail.com
Graduate Student of Department of Industrial
Biotechnology, Kazan National Research Technological University, 32a st. Tovarischeskaya, Kazan 420097, Russia
This article makes reference to supplementary material available on the publisher’s website at http://dx.doi.org/
10.1080/17415993.2017.1397153.
© 2017 Informa UK Limited, trading as Taylor & Francis Group

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H. Y. HOANG ET AL.
2
1. Introduction
One of the main environmental problems in oil refining and the petrochemical indus-
try is the treatment and utilization of highly toxic sulfurous alkaline wastes (SAW) with
high concentrations of inorganic sulfides. The current effluent guidelines do not allow the
discharges of these pollutants into water or their treatment together with other industrial
wastewater even after their considerable dilution. It is advisable to create separate systems
for the collection and the purification of SAW [1].
A number of processes have been developed for treating SAW. Some of the inorganic
sulfide can be removed by simple stripping, especially at high pH values (≥9); however,
oxidation of the sulfide is very necessary for complete removal.
The chemical oxidation of the sulfide can be achieved by strong agents such as potassium
permanganate, potassium dichromate, chlorine, bleaching powder, ozone and hydrogen
peroxide. However, the cost of the chemicals and possible pollution by the oxidation agents
are serious disadvantages [1].
Nowadays, a common method of SAW treatment is their liquid-phase catalytic oxida-
tion in an atmosphere of air in the presence of various catalysts [2]. Many authors have
investigated the oxidation of sulfide in water by oxygen in the presence of activated carbon
[3,4]. The reaction rate strongly depends on the pH of the solution and the mass transfer
of oxygen to the aqueous suspension of activated carbon.
The liquid-phase oxidation of sulfide was found to be much faster in the presence
of transition-metal complexes [5–7]. Currently, transition-metal oxides based on a poly-
mer matrix are the main heterogeneous catalysts used in the oxidation of sulfide and
hydrosulfide anions. Transition-metal oxides were distributed evenly on the catalyst sur-
face and were strongly adhered. During the catalyst process, the complexes between
transition-metal oxides and sulfide ions on the catalyst surface were formed [8].
The main disadvantages of the proposed methods in the previous studies are the low
activity of catalysts and the contamination of the treated effluents. In order to eliminate the
above disadvantages, we propose a new heterophase process in the presence of a catalyst
based on 3,3ꢀ,5,5ꢀ-tetra-tert-butyl-4,4ꢀ-stilbenequinone (here in after stilbenequinone) that
is dissolved in the kerosene fraction. The hydrocarbon phase (kerosene fraction) simulta-
neously performs both the role of the catalyst carrier and the role of the oxygen deposition.
The purpose of this study is to investigate the role of the stilbenequinone-based catalyst in
the liquid-phase oxidation of inorganic sulfides, and to evaluate the factors that affect the
reaction.
2. Results and discussion
2.1. The reaction products of the liquid-phase oxidation of sodium sulfide in the
presence of catalyst based on stilbenequinone
The process of liquid-phase oxidation of sulfide sulfur with oxygen depends on a number
of factors: temperature, pH, the oxygen concentration, the nature of inorganic sulfides, the
nature of catalyst, etc., where upon various products are formed (Scheme 1). In the course
of this reaction, the oxidation number of sulfur varies from −2 to +6.
In the presence of catalysts, the main products of the sulfide sulfur oxidation are thiosul-
fate, sulfite and sulfate [9]. Figure 2 shows the change in sodium sulfide concentrations and

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JOURNAL OF SULFUR CHEMISTRY
3
Scheme 1. Products of the oxidation of sulfide by oxygen.
Figure 1. The lab. unit of sulfide oxidation.
products of its catalytic oxidation in the presence of stilbenequinone. As can be seen from
Figure 2, sodium thiosulfate and sodium sulfate are the main products of the oxidation of
sulfide sulfur in the presence of stilbenequinone. The mass ratio of sulfate to thiosulfate is
4:3 after oxidizing for 600 min.
Oxidation of sulfide sulfur in the presence of stilbenequinone proceeds through two
stages: the first stage is the oxidation of sulfide sulfur with stilbenequinone to 3,5,3ꢀ,5ꢀ-
tetra-tert-butyl-4,4ꢀ-dihydroxy-1,2-diphenylethylene (here in after diphenylethylene); the
second stage is the regeneration of the catalyst by oxidation of diphenylethylene to
stilbenequinone in alkaline medium (Scheme 2).
To confirm the mechanism, the possibility of the reaction of sodium sulfide oxidation
with stilbenequinone in the range 70–110°C in an oxygen-free environment was studied
with subsequent analysis of the light yellow powder precipitated after the reaction at room
temperature that presumably was diphenylethylene (Table 1). It is shown that the reac-
tion rate of the oxidation of sodium sulfide with stilbenequinone increases with increasing
temperature.
In the stilbenequinone spectrum, there−a1re peaks for the stretching vibrations of the
−1
=
=
=
conjugated diene (Ar C–C Ar) 1605 cm and the carbonyl group (C O) 1605 cm
,