RESEARCH ON AN EFFICIENT CATALYTIC ALKYLATION METHOD OF

NAPHTHOLS WITH LOW MOLECULAR MASS ALCOHOLS

Mushkunaz Kichmirza Nazarova
Mahal Mayil Muradov
Irada Eyvaz Garayeva
Sumgait State University, Sumgait city, Azerbaijan
[email protected]
Abstract

The alkylation reaction of 1-naphthol with methanol and ethanol was studied in the presence
of H-mordenite and its modified samples. The amount of modifier (Pd, Ni, Sr) in the catalyst was
varied within the range of 0.1 -2.0 wt % and the catalytic properties of H-mordenite with a modulus
of 24 were studied in detail. The results of the study were analyzed and it was found that increasing
the degree of dealuminization in H-mordenite increased the concentration of 2-ethyl-1-naphthol in
the obtained mononaphthol mixture. The concentration of 2-ethyl-1-naphthol in the obtained
mixture was 89.8% in H-mordenite when x=10 was taken, and 94.0% in zeolite when x=24. Taking
this into account, 1.5 wt % Zr, H-mordenite (x=24) was selected as a more active and selective
catalyst in the alkylation reaction of 1-naphthol with methanol and ethanol, and it was found that it
exhibited special properties in the production of monomethyl and monoethyl-1-naphthols, mainly 2-
methyl (ethyl)-1-naphthols. Thus, it was found that the selected SrH-mordenite catalyst showed
high selectivity (86.5-90.5%) and activity (39.8-41.1%) in the synthesis of 2-methyl-1-naphthol and
2-ethyl-1-naphthol.

Extra words:naphthalene, naphthols, methanol, ethanol, methylnaphthols, ethylnaphthols, H-

mordenite, SrH-mordenite, monoethyl-1-naphthols, monomethyl-1-naphthols, H-mordenite

Object and subject of research. The object of the study was the catalytic alkylation of 1- and
2-naphthols with ethanol. The development of an effective method for obtaining methyl and ethyl
homologues of naphthols in the presence of selected and justified catalytic systems from among the
obtained oxide-containing catalysts and modified H-mordenites was revealed as the subject of the
research work.
Research methods.The research was carried out using modern equipment, devices and
programs. Experiments were conducted in a reactor of the extraction type, a differential reaction
apparatus, gas-liquid chromatography (GLC), NMR spectroscopy were used as physicochemical
analysis methods, and MATLAB programs were used for kinetic calculations.
In most of the methods of obtaining naphthol and alkylnaphthols, naphthalene or its alkyl
homologues are taken as the starting material. Their raw material base is coal, oil and biomass.
Rectification of resins obtained from coal coking produces a fraction of naphthalene and
methylnaphthalenes (200-2300C) containing up to 80-85%. This fraction can be subsequently
purified by hot pressing to obtain naphthalene with a purity of 98%.
Naphthalene can be obtained from oil in two ways: from catalytic cracking gas oil and from
heavy pyrolysis resins formed from the pyrolysis of gasoline. The concentration of naphthalene in
both fractions is 20-25.0%. Considering the increase in the scale of the pyrolysis process of oil
fractions in our country, which does not have coal reserves, the production of naphthalene by the
second way seems more realistic, despite the somewhat higher cost.
The raw material base of naphthols and low molecular weight (C1-C2) alcohols is available in
Azerbaijan, including Sumgayit. Naphthalene and its homologues are abundant in liquid pyrolysis
products. There are few applications of naphthalene hydrocarbons. However, the world's production
of naphthalene40% is used for the synthesis of naphthol and its numerous derivatives. Naphthols
and their methyl and ethyl homologues are considered valuable by-products of organic synthesis.
All K-type vitamins (K1 (2-methyl-3-phytyl-1.4-naphthoquinone), K2 (3-difarnesyl-2-methyl-1.4-
naphthoquinone), K3 (menadione, 2-methyl-1.4-naphthoquinone), K4 (2-methyl-1.4-
diacetoxynaphthalene and menadiol (2-methyl-1.4-dioxynaphthalene), K5 (4-amino-2-methyl-1-
naphthol), K6 (2-methyl-1.4-methylenediamine)) widely used in veterinary medicine are produced
on their basis. On the other hand, azoid dyes, vitamins, fragrances, adhesives, pesticides,
pharmaceuticals, emulsifiers, dispersants, stabilizers, preparations used in color photography,
hydraulic fluids, as well as additives to food products, including bakery products, beverages,
confectionery and chewing gums, are produced on the basis of methyl and ethyl naphthols.1.

Materials and methods:

Material

The method considered suitable for methyl- and ethyl homologues of naphthols is based on
the alkylation reaction of naphthols with methanol and ethanol. The production method, mainly
created with the participation of alumina, has been operating in a number of countries (USA, Japan,
China) since the end of the last century. There is a need to improve these ortho-tonnage
productions, which have low economic and technological indicators, and to create an effective
catalyst. Taking this into account, we have extensively studied the alkylation process with the
participation of zeolites, including modified H-mordenites3. Zeolites with moduli of 18, 24 and 32
were synthesized as a result of decationization and dealumination of H-mordenites. The ratio of
silica to alumina in the initial H-mordenite was 10. The experiments were carried out under the
following reaction conditions: T-3400C, υ – 1.0 st-1, ν = 1:5 mol/mol.As mentioned above, the ratio
was carried out in the department under laboratory conditions in a flow-type reactor.
The liquid mixture of naphthol-ethanol (naphthol-methanol) taken as raw material is fed to the
reactor at different volume rates, regulated by a pump. In order to ensure the conversion of the
naphthol-ethylene (naphthol-methanol) mixture in the catalytic process, naphthol is liquefied in a
heater placed before the reactor and enters the reactor at the required volume rate. The rate of
ethylene and other gases (H2, N, O2, air) supplied to the reactor from the cylinder is controlled by a
gas flow regulator. A potentiometer equipped with a magnetic switch is used to regulate and record
the temperature of the process occurring in the reactor. Before entering the reactor, the raw material
is evaporated and heated to the required temperature. There is also an evaporator and a directing
zone in the upper part of the reactor.
 Figure 1.Used to carry out the alkylation reaction
laboratory equipment diagram

1. Raw material capacity; 2. Pump; 3. Liquid feeder; 4. Check valve; 5. Reactor;

6. Furnace for heating the reactor; 7. Nitrogen cylinder; 8. Air cylinder; 9. Valve;
10. Manometer; 11. Gas filter; 12. Gas transmitter; 13. Gas flow regulator
14. Cooler; 15. Separator with a transmitter for liquid level;
16. Valve for draining the liquid; 17. Cooling receiver; 18. Ethyl alcohol-
holder; 19. Gas meter; 20. Buffer; 21. NOC. Scheme of a reactor unit without

The reaction products (catalyst) leaving the reactor pass through the cooler and enter the
separator. Here, the liquid reaction products are separated and collected. To condense the ethanol
that is not converted in the reaction, acetone-dry ice, alcohol-dry ice, and in some cases liquid
nitrogen are used. The gaseous products (CH4, C2-C4 hydrocarbons) pass through the buffer and
gas meter and enter the gasometer.
Kinetic studies of the catalytic alkylation reaction of naphthols with ethanol (methanol) were
carried out in a differential reactor.

The results of the research were analyzed andAnalysis of the results shows that (Table 1) the
increase in the degree of dealuminization in H-mordenite also increases the concentration of 2-
ethyl-1-naphthol in the resulting mixture of monoethyl-naphthols. At this time, the concentration of
the first isomer in the mixture of 2-ethyl-1-naphthol and 4-ethyl-1-naphthol is 89.8% in H-
mordenite with x=10 and 94.0% in zeolite with x=24.
Further increase in the modulus in H-mordenite has little effect on the results of the alkylation
reaction of 1-naphthol with ethanol. Most likely, in mordenites with modulus 24 and 32, there is
little change in the adsorption volume of reagents and the size of the pores of the catalyst, as well as
the number and strength of acid centers. As can be seen, in both cases most of the indicators are
very close. Thus, it was possible to tune the catalytic properties of H-mordenites with modulus 24
and 32.

Table 1
Catalytic properties of H-mordenite in the alkylation reaction of 1-naphthol with ethanol
Reaction conditions: T-3400C, υ-1.0 st-1, ν = 1:5 mol/mol

Name of indicators The value of the modulus in H-mordenite

(SiO2/Al2O3)
10 18 24 32
Yield of the main reaction products,
calculated based on the converted 1-
naphthol, in %,
including
1-ethoxynaphthalene 8.0 8.5 8.0 7.1
Monoethyl-naphthols 66.0 70.5 74.5 75.0
Diethylnaphthols 4.0 3.0 2.4 2.0
1-oxo compounds 7.5 7.2 7.0 6.5
Methyl and ethyl homologues of 11.0 9.0 6.5 5.0
naphthalene
Conversion of 1-naphthol, % 52.8 49.5 45.0 45.0
Yield of monoethyl naphthols, calculated 41.4 35.0 33.5 33.8
based on the starting 1-naphthol, %
Concentration of 2-ethyl-1-naphthol in the 89.8 92.5 94.0 94.0
mixture of monoethyl naphthols, %

In order to increase the performance properties, catalytic activity and selectivity of the H-
mordenite catalyst, its modification with various ions (nickel, palladium, zirconium) was carried
out. For this purpose, the concentration of modifiers in H-mordenite was increased to 2.0 mass %
and the tendency of the yield of the converted monoethyl-1-naphthols obtained was analyzed,
calculated based on the initial 1-naphthol. In order to more accurately and comparatively analyze
this dependence given in Figure 1, analogous indicators obtained from the same reaction in the
presence of H-mordenite (x=24) are given on the ordinate axis.
 Figure 1 Effect of modifier concentration in mordenite on the calculated yields of monoethyl-1-
naphthols obtained from the alkylation of 1-naphthol with ethanol, based on converted (1,2,3) and
initial (1/, 2/, 3/) 1-naphthol
1, 1/ - Pd, H-mordenite, 2, 2/ - Zr, H-mordenite, 3, 3/ - Ni, H-mordenite
When the modifier concentration in H-mordenite is 0.5 mass %, the selectivity for
monoethylnaphthols in zeolites modified with palladium and zirconium increases to 76.1 and
78.0%, respectively. A further increase in the concentration of palladium is appropriate. Thus, the
selectivity for monoethylnaphthols obtained in the presence of 1.0 mass % Pd, H-mordenite reaches
82.0%, while a further increase in the concentration practically does not increase this indicator (1.5
Pd, H-mordenite – 81.5%), and vice versa, when the palladium concentration is 2.0 mass %, it even
decreases it (80.0%). In the presence of zirconium, increasing its concentration to 1.5 mass %
increases the selectivity for the target product to 86.5%. A further increase in the modifier leads to
an increase in selectivity by only 1.5%. In the Ni, H-mordenite catalyst, increasing the modifier
concentration to 0.5 wt %, unlike other catalysts, reduces the selectivity of monoethylnaphthols
compared to H-mordenite from 74.5% to 71.5%, and a further increase in the nickel concentration
changes this indicator first to 73.0% (1.0 wt % Ni, H-mordenite) and then to 78.0% (1.5 wt % Ni,
H-mordenite). Increasing the nickel concentration in mordenite to 2.0 wt % has little effect on this
indicator (78.5%).
Similar patterns are observed in the yields of monoethylnaphthols formed on the basis of 1-
naphthol and ethanol in the presence of palladium, zirconium and nickel-modified mordenites.
Thus, when the concentration of zirconium in mordenite is increased to 0.5 wt %, the yield of
monoethylnaphthols calculated on the basis of the initial 1-naphthol decreases from 33.5% to 31.5%
compared to H-mordenite. When palladium and nickel-modified mordenites are taken, the yield
increases to 34.0 and 37.4%, respectively. Increasing the modifier concentration to 1.0 wt %
increases the yield to 34.9% in the case of palladium zeolite. In Ni, H-mordenite, this indicator is
39.5%, and in zirconium zeolite it increases to 37.5%. A further increase in the concentration of
palladium in the catalyst (1.5-2.0 wt %) reduces the yield of monoethylnaphthols first to 34.0%,
then to 32.5%. In the other two catalysts, a further increase in the concentration of the modifier
affects the yield of the target product in its own way. Thus, in 1.5 wt % Ni, H-mordenite, the yield
of monoethylnaphthols practically does not change, but increasing the concentration of the modifier
in the catalyst to 2.0 wt % leads to a partial (2.0%) decrease in the yield. As a result of increasing
the concentration of the modifier to 1.5 wt % in zirconium H-mordenite, the yield of
monoethylnaphthols increases significantly and amounts to 41.1%.
As a result of the conducted studies, compared to H-mordenite, zeolites with a concentration
of 1.5 mass % from nickel and zirconium modified samples, and 1.0 mass % Pd in palladium
modified mordenites, H-mordenite was selected as a more active and selective catalytic system.
The results obtained in the alkylation reaction of 1-naphthol with ethanol in the presence of
these catalysts are given in Table 2.
As can be seen, the composition of the products obtained from the alkylation reaction of 1-
naphthol with ethanol varies slightly depending on the catalyst used. These products include 1-
ethoxynaphthalene, monoethylnaphthols (2- and 4-isomers), diethylnaphthols, 1-oxo compounds,
and methyl and ethyl homologues of naphthalene. Condensation products of unknown composition,
although in small quantities, are found in alkylates. Zirconium mordenite catalysts show high
activity and selectivity in the ortho-alkylation reaction of 1-naphthol, while Ni,H-mordenite zeolites
show low catalytic properties. These catalytic systems also have suitable properties in the
production of diethyl naphthols by sequential alkylation of 1-naphthol with respect to carbon.
Regarding the composition of the obtained 1-oxo compounds, it should be noted that the
concentration of 1-oxo-2,2-diethyl-1,2-dihydronaphthalene in the mixture obtained in the presence
of Ni,H-mordenite is 88.7%, while in the zirconium-modified zeolite this indicator is 96.5%.

Table 2
Results of the study of the alkylation reaction of 1-naphthol with ethanol in the presence of H-
mordenite catalyst modified with zirconium, palladium and nickel
Reaction conditions: T-3400C, υ-1.0 st-1,ν = 1:5 mol/mol
Catalyst composition, mass %
Name of indicators 1.5 – Ni, 1.5 – Zr, 1.0 – Pd,
98.5-H- 98.5-H-mordenite 99.0-H-mordenite
mordenite
Yield of the main reaction products,
calculated based on the converted 1-
naphthol, in %, including
1-ethoxynaphthalene 1.5 1.0 0.7
2- and 4-ethylnaphthols 78.1 86.5 82.0
diethylnaphthols 3.0 1.5 2.4
1-oxo compounds 5.0 1.8 3.0
Methyl and ethyl homologues of 9.5 6.5 10.0
naphthalene
Conversion of 1-naphthol, % 50.0 47.5 42.5
Yield of mono-ethyl naphthols,
calculated based on the initial 1- 39.1 41.1 34.9
naphthol,%
In a mixture of monoethyl naphthols
Concentration of 2-ethyl-1-naphthol, % 91.5 96.0 94.2

In the mixture of 1-oxo compounds obtained in the presence of Pd,H-mordenite catalyst, the
concentration of another isomer, 1-oxo-4,4-diethyl-1,4-dihydronaphthalene, is 4.5%. One of the
interesting results is the difference in the composition and yield of methyl and ethyl naphthalenes
obtained during the process. Unlike zirconium mordenite, alkylnaphthalenes formed in zeolites
modified with nickel and palladium contain methyl homologues. High selectivity for
alkylnaphthalenes (9.5%) is achieved with nickel mordenite, while low selectivity is achieved with
Zr,H-mordenite (6.5%).
In the alkylation process carried out in the presence of modified mordenite catalysts, the
conversion of 1-naphthol decreases in the following order.

Ni, H-mordenite > Zr, H-mordenite > Pd, H-mordenite

The highest values of the yields of the obtained monoethyl-1-naphthols converted and
calculated with respect to the initial 1-naphthol are attributed to the zirconium-modified mordenite
and are 86.5 and 41.1%, respectively. In Ni, H-mordenite, these indicators are 78.1 and 39.1,
respectively. When Pd, H-mordenite is taken, the selectivity for monoethyl-1-naphthols is 82.0, and
the yield is 34.9%.
The selected catalytic system in the alkylation reaction of 1-naphthol with methanol4also
demonstrated high activity and selectivity. Table 3 presents comparative results of the interaction of
1-naphthol with C1 and C2 alcohols in the presence of zirconium H-mordenite (Table 3).
Table 3
Comparative table of studies of the alkylation reaction of 1-naphthol with methanol and
ethanol in the presence of zirconium-modified H-mordenite catalyst
Reaction conditions: T-3400C, υ-1.0 st-1, ν = 1:5 mol/mol

Raw material composition

Name of indicators 1-naphthol: 1-
methanol naphthol:ethanol
Yield of the main reaction products, calculated
based on the converted 1-naphthol, in %,
including
1-ethoxynaphthalene 1.0
1-methoxynaphthalene 1.5
2- and 4-ethylnaphthols 86.5
2- and 4- methylnaphthols 90.5
 diethylnaphthols 1.5
dimethylnaphthols 2.0
1-oxo compounds 1.0 1.8
Methyl and ethyl homologues of naphthalene 4.0 6.5
Conversion of 1-naphthol, % 44.0 47.5
Yield of mono-ethyl naphthols, calculated based
on the initial 1-naphthol,% 41.1
Yield of mono-methyl naphthols, calculated based 39.8
on the initial 1-naphthol,%
In a mixture of monoethyl naphthols
Concentration of 2-ethyl-1-naphthol, % 96.0
In a mixture of monoethyl naphthols 98.0
Concentration of 2-methyl-1-naphthol, %

As the molecular weight of the alkylating agent, i.e., the alcohol, increases, the alkylation due
to oxygen increases in part. The share of alkylation due to carbon in the nucleus increases. The
amount of alkyl homologues of naphthalene decreases. From the comparison of the results, it can be
seen that in the presence of ethanol, the conversion of naphthol and the yield of monoalkylnaphthols
obtained increase. However, the concentration of 2-methyl-1-naphthol in the mixture of
monoalkylnaphthols is slightly higher than the concentration of 2-ethyl-1-naphthol. The results
obtained show that in the alkylation process, the concentration of ortho-methyl and ethyl
homologues of 1-naphthol predominates. This is explained by the structure, composition, and
adjustment of acid-base properties of the selected zirconium mordenite catalyst.
PMR of Naphtali derivatives (Proton magnetic resonance) spectra study It was found that the
protons of substituted naphthalene usually resonate in the region of 6.5-8.0 mh. The shift of the
relative resonance signals of simple olefin protons to the weak field is attributed to the ring current
effect present in conjugated systems. Therefore, the protons of the naphthalene nucleus resonate at δ
= 7.27 mh.

Figure 2.PMR spectrum of 1-methoxynaphthalene

Figure 3.PMR spectrum of 2-ethoxynaphthalene

Figure 4.PMR spectrum of 2-methyl-1-naphthol

Figure 5.PMR spectrum of 4-methyl-1-naphthol

 Figure 6.PMR spectrum of 1-ethyl-2-naphthol
PMR spectra were recorded in various solvents on a Bruker Fourier spectrometer (frequency
300 MHz). Internal standard - hexamethyldisiloxane, chemical shifts of signals are given on the
δ(mH) scale.
The physical properties and elemental composition of ethyl derivatives of naphthols were as
follows.

1-ethoxynaphthalene: Tgay -2800C, (760mm.cs) Terim-5.50C, -1.06g/cm3

2-ethoxynaphthalene: Tgay -2830C, (760mm.cs) Terim-370C, -1.049g/cm3

1-ethyl-2-naphthol: Tgay -3120C, (760mm.cs) Terim-650C, -1.10g/cm3

2-ethyl-1-naphthol: Tgay -3080C, (760mm.cs) Terim-530C, -1.12g/cm3

Calculated, % C 81.08; H 8.11; O 10.81

Found, % C 81.12-81.30; H 8.01-8.10; O-10.65-10.77

Thus, 1.5 wt % Zr, H-mordenite (x=24) was selected as a more active and selective catalyst in
the alkylation reaction of 1-naphthol with methanol and ethanol, and its practical importance in the
preparation of monomethyl and monoethyl-1-naphthols, especially 2-methyl (ethyl)-1-naphthols,
was determined. 2.
Results: An effective method for obtaining alkyl homologues of 1-naphthol has been
developed, patented, and scientific articles published in a number of prestigious journals.
 Conclusion

1. The effect of their concentrations (0.5-2.0 wt %) on the performance of the

alkylation process of naphthols with ethanol on the occurrence of primary and side
transformations was revealed in the modification of H-mordenite with nickel,
zirconium, and palladium, which had a more favorable modulus (SiO2/Al2O3 =18-
24).
2. It was shown that zirconium and nickel containing 1.5 wt% and palladium
containing 1.0 wt% allowed for better results, and it was determined that 1.5 Zr, H-
mordenite exhibited higher catalytic properties in the presence of modified
mordenites.
3. The regularities of the alkylation reaction of 1-naphthol with ethanol in the
presence of zirconium-containing mordenites have been determined. It was found that
O- and C-parallel alkylation, C-sequential alkylation occur in the process, oxo
compounds are obtained from naphthols, albeit in small amounts, and ethylation
accompanied by dehydroxylation also occurs in the reaction medium.

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