Reductive dimerization and oligomerization of alcohols, ketones, and aldehydes to hydrocarbons on a promoted, fused iron catalyst

Article abstract of DOI:10.1134/S0965544114040045

A new reductive dimerization and oligomerization reaction of (C₅ and C₆) cycloalkanols and cycloalkanones, benzaldehyde, and benzyl alcohol to hydrocarbons containing as many, or more, carbon atoms as the reactant oxygenated compound on a promoted, fused iron catalyst proceeds at a temperature of 250-350°C, a hydrogen pressure of 0.1-1 MPa, a specific feed rate of oxygenated reagent of 80-320 g h^-1kg^-1Ct, and a hydrogen space velocity of 1 × 10³ to 20 × 10³ h^-1. Possible reaction mechanisms have been considered.

Full text of DOI:10.1134/S0965544114040045

ISSN 0965ꢀ5441, Petroleum Chemistry, 2014, Vol. 54, No. 4, pp. 296–308. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © L.S. Glebov, V.G. Zaikin, A.I. Mikaya, G.A. Kliger, 2014, published in Neftekhimiya, 2014, Vol. 54, No. 4, pp. 295–308.
Reductive Dimerization and Oligomerization of Alcohols, Ketones,
and Aldehydes to Hydrocarbons on a Promoted, Fused Iron Catalyst
L. S. Glebov, V. G. Zaikin, A. I. Mikaya, and G. A. Kliger
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia
eꢀmail: glebovl@list.ru
Received December 30, 2013
Abstract—A new reductive dimerization and oligomerization reaction of (C and C ) cycloalkanols and
5
6
cycloalkanones, benzaldehyde, and benzyl alcohol to hydrocarbons containing as many, or more,
carbon atoms as the reactant oxygenated compound on a promoted, fused iron catalyst proceeds at a temperꢀ
ature of 250–350°C, a hydrogen pressure of 0.1–1 MPa, a specific feed rate of oxygenated reagent of 80–
–1
–1
3
3 –1
3
20 g h kg Ct, and a hydrogen space velocity of 1
× 10 to 20 × 10 h . Possible reaction mechanisms have
been considered.
Keywords: oligomerization, alcohols, ketones, aldehydes, fused iron catalyst
DOI: 10.1134/S0965544114040045
Reduction of carbonyl compounds and alcohols
The reductive dehydration of aliphatic alcohols
with hydrogen in the presence of various heterogeꢀ and their mixtures with cyclopentanol yielding satuꢀ
neous catalysts involves Н2 addition to the C=O bond rated hydrocarbons in the presence of polymetallic
to form alcohols or hydrogenolysis of the C–OH or ironꢀcontaining systems was considered in [12–15].
C=O bond to form hydrocarbons [1–4]. For preparaꢀ
tive synthesis and structural analysis in organic chemꢀ
istry, the hydrodeoxygenation (HDO) reaction of carꢀ
bonyl compounds and alcohols to hydrocarbons is
used:
The objective of this work was to study in detail this
reaction in the alcohol, aldehyde, and ketone series on
reduced promoted, fused iron catalysts.
EXPERIMENTAL
O
OH
The reaction of the oxygenated compounds with
hydrogen was carried out in a catalytic fixedꢀbed flow
reactor with or without hydrogen circulation, wherein
the products were recovered with cooled receiverꢀsepꢀ
arators [8]. The RPFIC samples taken for examinaꢀ
tion were prepared from different kinds of magnetite
with various promoters. The reactions were carried out
+
H2
+H2
R C R1
1
RCH
R1
2
R CH R
–H O
2
+H2
–H O
2
This reaction on an iron catalyst at a temperature
above 550 and a 20 MPa pressure was first observed
°
C
in the temperature range of 250–350
°C
at a hydrogen
by Ipatiew [5]. Later, it was found that aliphatic and
alicyclic alcohols, aldehydes, and ketones are qualitaꢀ
tively converted to corresponding hydrocarbons, preꢀ
serving their skeleton, on a reduced promoted, fused
iron catalyst (RPFIC) at a temperature of 250–350°C,
a hydrogen pressure of 0.1–0.3 MPa, and a hydrogen:
substrate ratio of 100 [6, 7].
pressure of 0.1–1 MPa, a specific oxygenatedꢀreactant
–1
–1
feed rate of 80–320 g h kg Ct, and a hydrogen space
3
3
–1
velocity of
1
×
10 –20 10 h .
×
A magnetite mixture (Table 1) with a promoter
V2O5 or others) was fused in a waterꢀcooled crucible
(
lined with kaolin and asbestos. Electricꢀarc melting
was conducted using cooled copper electrodes at
In some experiments with cyclopentanol and 1500–1600
cyclohexanol during a search for optimal conditions of and its 2–3ꢀmm fraction was reduced with Н2 at
the HDO reaction on the RPFIC, the reaction prodꢀ 450 C, 5 MPa for 10–12 h. The degree of catalyst
°C for 60–120 s. The alloy was crushed,
°
ucts along with the anticipated hydrocarbons cycloꢀ reduction was monitored by measuring the amount of
pentane and cyclohexane were found to contain conꢀ water released. The finished RPFIC contained 90–
densation products, such as cyclopentylcyclopentane 95 wt % Fe (the rest was the promoter) and had a speꢀ
°
2
and cyclohexylcyclohexane and even heavier hydroꢀ cific surface area of 10–15 m /g. According to the
carbons, byproducts of the reductive oligomerization selective adsorption and Xꢀray photoelectron specꢀ
reaction [8–13].
troscopy data, the major part of the RPFIC surface
296

REDUCTIVE DIMERIZATION AND OLIGOMERIZATION OF ALCOHOLS, KETONES
297
Table 1. Magnetites for preparation of PFRICs
Composition, wt %
Source material
for magnetite
FeO Fe O3 Fe0 Al O CaO
K O
SiO2 MgO TiO MnO CuO
C
S
P
2
2
3
2
2
2
Armco steel
39.3 57.8 0.5 0.13
35.7 52.5 0.5 0.10
–
–
–
0.13 0.03
0.30 –
–
–
0.11 0.75
0.10 0.60
–
–
–
–
Steel 04 ZhR
0.30
(TU 14ꢀ1158ꢀ75)
Natural magnetite suꢀ
perconcentrate from
the Lebedinskii mining
and processing works*
99.5
99.3
99.3
–
–
–
0.164 0.092 0.098** 0.085 0.072 0.013 0.059 0.003 0.05 0.003 0.007
0.189 0.046 0.07** 0.154 0.054 0.023 0.062 0.002 0.023 0.003 0.002
0.155 0.055 0.067** 0.143 0.059 0.021 0.059 0.002 0.037 0.025 0.034
Natural magnetite suꢀ
perconcentrate from
the Olenegorsk mining
and processing works*
Natural magnetite suꢀ
perconcentrate from
the Kostomuksha minꢀ
ing and processing
works*
Natural magnetite suꢀ 28.7 65.1
perconcentrate (mixꢀ
ture)
–
0.2 <0.1 <0.1**
0.40 0.20 0.021 0.10 <0.10
–
–
–
–
–
–
Carbonyl iron, speꢀ 57.5 41.7 0.6 <0.1
cial purity grade, 13ꢀ2
–
–
<0.1
–
–
–
–
(
TU 6ꢀ09ꢀ3000ꢀ78)
*
GOK is the mining and concentration complex. ** K O + Na O
2 2
.
was coated with the promoters and the minor part was
occupied by ꢀFe [16, 17, 21]. The catalyst is pyroꢀ
phoric (spontaneously ignites in air); therefore, its
RESULTS AND DISCUSSION
α
°
Cyclopentanol and Cyclohexanol
storage and loading/unloading were in a СО2 atmoꢀ
In [8–11, 13], we identified the following hydroꢀ
sphere. The RPFIC composition is given in wt % carbons and oxygenated compounds (Table 2) as the
products of the reaction of cyclopentanol or cyclopenꢀ
tanone with hydrogen in the presence of the RPFIC.
based on the unreduced sample.
Cyclopentanol, cyclohexanol, benzyl alcohol,
cyclopentanone, cyclohexanone, and benzaldehyde
were of the reagent grade or the analytical grade and
had a purity no less than 99% after distillation.
Preliminarily, it has been found that optimal condiꢀ
tions for the synthesis of biꢀ, triꢀ, and polycyclic satuꢀ
rated fusedꢀring hydrocarbons from cycloalkanols are
as follows: a hydrogen pressure (p ) of 0.7 MPa, an
H
2
Gaschromatographic/massspectrometric analysis
was conducted on an LKBꢀ2091 instrument at ion
source and molecularꢀseparator temperatures of
3
–1
Н2 space velocity of 10 h , a specific cycloalkanol
–1 –1
feed rate of 160–180 g h kg Ct, and a reaction temꢀ
perature of 250–270
50 for cyclohexanol. Data on the conversion of
these alcohols on various RPFICs are given in Table 3
°C for cyclopentanol or 300–
250
°C, an ionization energy of 70 eV, and an emission
3
°C
current of 25
µA.
[
8–11, 13].
For GLC, a 3000
packed with 5% Carbowax 20M or 5% SEꢀ30 on
.25–0.31ꢀmm Chromaton NꢀAWꢀDMCS (carrier
gas, He; flow rate, 30 mL/min; temperature programꢀ
ming mode from 80 to 220 at a heating rate of
°C/min) and a 1200 mm column packed with
% SEꢀ30 on 0.15–0.20ꢀmm Chromaton NꢀAWꢀ
DMCS (carrier gas, N2; flow rate, 30 mL/min; temꢀ
perature programming from 50 to 300
rate of °C/min with final holding for 18 min).
×
3 mm stainless steel column,
The data in Table 3 (run 7) show that the best
results were attained on the RPFIC containing the
mixture of oxides 4.7% V2O5 and 1% CuO as promotꢀ
ers. The cyclopentanol conversion on this catalyst was
0
°C
9
9.5% and the selectivity for total biꢀ, triꢀ, and polycyꢀ
10
×
3
clic hydrocarbons was 82%. Table 4 lists the hydrocarꢀ
bons and oxygenated compounds identified among
the products of the cycloxexanone reaction with
5
°C
at a heating hydrogen on RPFICs [8, 9, 11, 13]. It is seen from
Table 5 that the cyclohexanol conversion at 350 was
6
°C
PETROLEUM CHEMISTRY Vol. 54
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298
GLEBOV et al.
Table 2. Products of the reactions of cyclopentanol and cyclopentanone with hydrogen on RPFIC
Product
number
Product
number
Product
Product
I
VII
with one C=C bond
II
VIII
O
OH
O
III
IV
V
IX
X
with one C=C bond
with two C=C bonds
XI
XII
OH
VI
9
9% and the selectivity for total biꢀ, triꢀ, and polycyꢀ various RPFICs was studied under the conditions
clic hydrocarbons was 43% [9].
optimal for the synthesis of fused biꢀ, triꢀ, and polycyꢀ
clic saturated hydrocarbons. The results obtained are
given in Tables 8 and 9 [8, 11, 13]. The data in Tables 8
and 9 show that the RPFIC containing the mixture of
We studied the synthesis of biꢀ and polycyclic
hydrocarbons from a cyclopentanol–cyclohexanol
mixture [9]. Data on the synthesis products and their
yields are given in Tables 6 and 7. It is seen from
Table 7 that the alcohol mixture gives fused biꢀ and triꢀ
cyclic hydrocarbons containing fiveꢀ and sixꢀmemꢀ
bered rings simultaneously with a total selectivity of
4
.7% V2O and 1% CuO as promoters exhibits a high
5
selectivity for fused biꢀ, triꢀ, and polycyclic saturated
hydrocarbons (conversion was 92% for cyclopenꢀ
tanone or 38% for cyclohexanone).
1
8–31.5%.
To reveal the effect of the aforesaid promoters on
the selectivity of the cyclopentanone reaction with
hydrogen, RPFIC specimens containing 4.7–6.0%
V2O5 and 0.5–0.25% CuO were studied (Table 8,
runs 1–7). It turned out that varying the V O /CuO
ratio from 4.7/0.5 to 4.7/2.5 does not affect within
the limits of experimental error the total yield of fused
biꢀ, triꢀ and polycyclic saturated hydrocarbons, which
was 92–95%.
Cyclopentanone and Cyclohexanone
Cyclohexanone (XXII) (about 1%) was found
2
5
among the products of reductive dimerization/oligoꢀ
merization reaction of cyclohexanol (Table 5). Therꢀ
modynamic calculations for the cyclohexanol–Н2 sysꢀ
tem showed that the equilibrium mixture in the temꢀ
perature and reactant ratio ranges typical of the
The data in Tables 8 and 9 show that the products
synthesis conditions (Tables 3, 5, 7) can contain up to include biꢀ and tricyclic oxygenated compounds
0% cycloalkanones. These facts suggest that one of whose formation can be attributed to the condensaꢀ
1
the possible routes for the formation of biꢀ, triꢀ, and tion reactions of cycloalkanones. For example, the
polycyclic hydrocarbons involves the conversion of overall selectivity for oxygenated compounds on the
cycloalkanones. In this connection, the reaction of industrial catalyst SAꢀ1 containing 3.1% Al O
+
2
3
cyclopentanone or cyclohexanone with hydrogen on 2.2% CaO + 0.7% K O as promoters was 56 or 12% in
2
PETROLEUM CHEMISTRY Vol. 54
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REDUCTIVE DIMERIZATION AND OLIGOMERIZATION OF ALCOHOLS, KETONES
Table 3. Synthesis of fused biꢀ, triꢀ, and polycyclic hydrocarbons from cyclopentanol and hydrogen on RPFICs ( H
299
p
= 0.7 MPa,
2
hydrogen space velocity of 10 h , specific cyclopentanol feed rate of 160 g h kg–1 Ct)
3
–1
–1
Alcohol
conversion,
%
Selectivity for products**, %
Run
no.
T,
°C
RPFIC promoter*
Unpromoted
I
II III IV
V
VI VII
Σ
(IX–XII)
1
2
3
4
5
6
7
8
9
250
250
250
250
98
35
0
0
1
0
0
3
0
0
0
0
25 13
15
22
19
36
6
2
0
1
6
1
1
1
0
0
0
6
4
0
7
10
0
9% Al O
99.5
99.5
99.5
96
34
35
40
12
9
1
7
2
3
4.7% V O
38
0
2
5
1% Al O + 1.5% BaO
27
6
2
3
3.1% Al O + 2.2% CaO + 0.7% K O*** 250
23
13 13
41
2
2
3
2
4.5% V O + 3.8% BaO
250
250
270
290
310
99.5
99.5
99.5
99.5
99.5
35
23
32
40
5
2
3
31
40
0
2
5
4.7% V O + 1% CuO
18
0
2
5
4.7% V O + 1% CuO*****
38
19**** 0
0
2
5
4.7% V O + 1% CuO*****
47.5
57.5
30 2.5
33 0.5
0
20
9
0
0
0
2
5
10
4.7% V O + 1% CuO*****
0
0
2
5
*
The RPFIC composition is given on unreduced sample basis, the rest is magnetite to 100%. ** For the product numbers, see Table 2. *** The
13
industrial ammonia synthesis catalyst SAꢀ1, OST (Industry Standard) 6ꢀ03ꢀ78ꢀ80. ****According to C NMR data, product VI (dicycloꢀ
pentylcyclopentane) is a 4 : 1 isomer mixture of 1,2ꢀdicyclopentylcyclopentane and 1,3ꢀdicyclopentylcyclopentane. The spatial conꢀ
figuration of the isomers was not studied because of the difficulty of their chromatographic separation. *****The specific feed rate of
cyclopentanol is 80 g h–1 kg Ct.
–1
the case of cyclopentanone (products IX—XII, which includes parallel and/or consecutive condensaꢀ
Table 2) or cyclohexanone (products XXI and XXIII– tion reactions of the reactant cycloalkanone to biꢀ and
XXV, Table 4), respectively. These values indicate polycyclic oxygenated compounds and the hydrodeꢀ
enhancement of the condensing activity of RPFIC oxygenation of the latter to corresponding saturated
and weakening of its hydrogenating ability by introꢀ hydrocarbons. In view of the bifunctional nature of
ducing the promoters К О, CaO, and Al O into the RPFICs, which is due to the hydrogenating/dehydroꢀ
2
2
3
catalyst. A slight decline in the hydrogenating ability genating (metal) and acid–base (oxide promoters)
of RPFIC is also caused by addition of BaO.
surface properties of these catalysts [20, 21], it may be
suggested that ketone condensation proceeds on the
acid–base RPFIC sites. This assumption agrees with
the published data on cyclopentanone condensation
A comparison of the data in Tables 3, 5, 8 and 9
show that the highest yields of fused hydrocarbons are
achieved in the presence of RPFIC of the same comꢀ
position. Substitution of ketone for alcohol in the
reaction only results in an increase in the total yield of
biꢀ and polycyclic hydrocarbons with fiveꢀmembered
over Al O3 [22]. The hydrogenation reaction presumꢀ
2
ably occurs on the hydrogenating/dehydrogenating
RPFIC sites.
(
from 82 to 95%) and sixꢀmembered (from 10 to 32%)
Along with the mechanism for the formation of
rings. These experimental facts lead to the conclusion fused biꢀ and polycyclic hydrocarbons, which includes
that the synthesis of fused hydrocarbons from cycloalꢀ condensation reactions on RPFICs, the alternative
kanols includes the step of their dehydrogenation to scheme of the conversion of aliphatic alcohols to
corresponding cycloalkanones. In this case, the yields hydrocarbons, including the formation of a carbene
of hydrocarbons in the oneꢀstep gasꢀphase process for complex, was proposed [12, 13].
synthesis from cycloalkanones and hydrogen were an
order of magnitude above those in the known process
in which Ni/kieselguhr was used as the catalyst [18].
Regarding the data on the reaction of cyclopenꢀ
tanone with hydrogen (Table 8), it should be noted
that a marked portion of the ketone does not manage
In order to further optimize the preparation of biꢀ to condense and undergoes hydrodeoxygenation to
and polycyclic hydrocarbons and completely inhibit yield cyclopentane, a route that is probably due to
the hydrodeoxygenation reaction of cyclopentanone quite high hydrogenating activity of the RPFIC as
to cyclopentane, the effect of highꢀtemperature heatꢀ compared with its condensing activity.
ing of RPFIC on its activity and selectivity in the
cyclopentanone reaction with hydrogen was studied
It was assumed that one of the means by which the
hydrogenating activity of RPFIC in the reductive
cyclopentanone dimerization/oligomerization reacꢀ
[
8, 19].
The data presented above allow us to hypothesize tion can be lowered is the highꢀtemperature heating of
the following macroscopic mechanism for preparation the catalyst. This idea also followed from the fact that
of fused biꢀ and polycyclic saturated hydrocarbons, Al O3ꢀ and K Oꢀcontaining RPFICs after heating in
2
2
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300
GLEBOV et al.
Table 4. Products of the reaction of cyclohexanol and cyclohexanone with hydrogen on RPFIC
Product
number
Product
number
Product
Product
XIII
XX
with one C=C bond
OH
XIV
XV
XXI
O
XXII
XXIII
XXIV
XXV
O
XVI
XVII
XVIII
OH
with one C=C bond
O
XIX
hydrogen at 1000°C markedly decreased their activity condensation of cyclopentanone. Thus, the highꢀtemꢀ
in the synthesis from CO and Н2 [23].
perature heating leads to almost complete inhibition
of the hydrogenating properties of the RPFIC and to
the most pronounced enhancement of its condensing
properties. These results indicate that the hydrogenatꢀ
ing properties of the RPFIC can be experimentally
separated from its condensing (acid–base) properties
by varying the conditions of the preliminary heat treatꢀ
ment. It is seen from Table 10 that the highꢀtemperaꢀ
Experiments were conducted on the RPFIC proꢀ
moted with 4.7% V O and 0.5% CuO; on this cataꢀ
2
5
lyst, the overall selectivity for fused biꢀ and polycyclic
saturated hydrocarbons was 95%, whereas the selecꢀ
tivity for cyclopentane was 4.5% (Table 8, run 5). The
heat treatment of the RPFIC was conducted at 600–
1
000
°
C
for 2–60 min in a hydrogen flow at
P
=
H2
ture heating of the catalyst at 600–700°C leads to an
0
.1 MPa. The data in Table 10 clearly show that the increase in the selectivity for monounsaturated (with
highꢀtemperature heating has an extremely strong one C=C bond in molecule) fused biꢀ and tricyclic
effect on the RPFIC activity and selectivity [19]. The hydrocarbons, thereby indicating a significant inhibiꢀ
main products of the cyclopentanone reaction with tion of the hydrogenating properties of the catalyst.
hydrogen on the heated catalyst are oxygenated comꢀ
By varying temperature of the heat pretreatment of
pounds’ i.e., presumably, the products of the aldol the RPFIC, we failed to find the conditions at which
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REDUCTIVE DIMERIZATION AND OLIGOMERIZATION OF ALCOHOLS, KETONES
Table 5. Synthesis of fused biꢀ, triꢀ, and polycyclic hydrocarbons from cyclohexanol and hydrogen on RPFIC ( H
301
p
= 1.0 MPa,
2
3
–1
hydrogen space velocity of 10 h , RPFIC composition is 4.7% V O + magnetite to 100% on unreduced sample basis)
2
5
Selectivity for products*, %
Run
no.
Specific feed rate
Alcohol
T
, °C
of alcohol (g h–1 kg Ct) conversion, %
–1
XIII
XIV
XVI
XIX
Σ
(XVII, XX) XXII
1
2
3
300
350
280
160
160
80
99.5
99
90
26
58
0
30
30
4
12
6.5
1.5
0
4.3
31
5.5
0.2
1.0
0
99.5
0
*
Product numbers are given in Table 4.
the hydrocarbons alone would form, and the oxygenꢀ of IX and XI was determined using the procedure
ated compounds would be completely absent. Thereꢀ involving H/D exchange of H atoms in the ꢀposition
α
fore, in order to enhance the selectivity for fused biꢀ to the carbonyl group in a KODꢀpacked chromatoꢀ
and polycyclic hydrocarbons and inhibit the cyclopenꢀ graphic column [25]. In this case, 2,5,5ꢀtrideuteroꢀ2ꢀ
tanone hydrodeoxygenation reaction to cyclopentane, cyclopentylcyclopentanone (IXꢀD3) and 2,5ꢀdideuꢀ
it was decided to use a twoꢀlayer catalyst. The first layer teroꢀ2,5ꢀcyclopentanone (XIꢀD2) were detected in
of the catalyst to face the cyclopentanone–hydrogen the mass spectra. Thus, bicyclic and tricyclic ketones
vapor–gas mixture was the RPFIC specimen treated IXꢀD3 and XIꢀD2 isolated from the products contain
at a high temperature, and the second layer was the cyclopentyl group in the
catalyst that had not been subjected to the highꢀtemꢀ group.
perature heat treatment (Table 10, runs 7–9). Under
α
ꢀposition of the carbonyl
O
the optimal conditions found for the reductive dimerꢀ
D
ization/polymerization of cyclopentanone, the overall
selectivity for biꢀ and polycyclic hydrocarbons was
higher than 99% (Table 10, run 7).
D
D
IXꢀD3
IXꢀD2.
Reaction Routes of the Reductive
Dimerization/Oligomerization of Cycloalkanones
and Cycloalkanols
D
D
O
The detection of deuteriumꢀlabeled ꢀsubstituted
α
When considering possible routes for the reductive
dimerization and oligomerization of cycloalkanones
and cycloalkanols, we proceeded first of all from the
composition and structure of the intermediate and
final products presented in Tables 2, 4, and 6. The
structures given in these tables were proved by elecꢀ
tronꢀionization mass spectrometry. However, the posiꢀ
tion of the double bond in unsaturated fused hydrocarꢀ
bons IV, V, VII, XVII and XX could not be determined
by this technique.
biꢀ and tricyclic ketones IXꢀD3 and XIꢀD2 allows us to
state with a high degree of confidence that in terms of
the macroscopic mechanism of synthesis of fused
bicyclic and polycyclic hydrocarbons on the RPFIC,
the aldol condensations of the corresponding ketones
is responsible for C–C bond formation in these hydroꢀ
carbons, with the condensations evidently proceeding
with participation of acid–base RPFIC centers. The
bicyclic and tricyclic ketones produced from cycloꢀ
From the products of the cyclopentanone reaction
with hydrogen, cyclopentylcyclopentane (III,
Table 6. Products of the reactions of cyclopentanol and
cyclohexanol with hydrogen on RPFIC
20
20
bp 79
tylcyclopentane (isomer mixture) (bp 143
and bis(cyclopentylcyclopentane) (isomer mixture)
bp 181 C/1 mmHg) were isolated using highꢀperforꢀ
°C/19 mmHg, d4 0.862, nD 1.463), dicyclopenꢀ
Product
Product
number
°C/11 mmHg),
(
°
XXVI
mance rectification [8]. The physicochemical conꢀ
stants of the isolated hydrocarbons were close to those
reported in the literature [22, 24].
It was shown by special experiments that isolated
carbonyl compounds IX and XI react with hydrogen
on the RPFIC to give the same products as those
formed in the reaction of cyclopentanone or cycloꢀ
pentanol with hydrogen. The position of the carbonyl
group relative to the cyclopentyl rings in the molecules
XXVII
XXVIII
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302
GLEBOV et al.
pentanone in the condensation reactions undergo furꢀ which 1,2ꢀdicyclopentylcyclopentane is produced were
ther hydrodeoxygenation yielding fused biꢀ and polyꢀ found. The fact that product XXIX was not detected sugꢀ
cyclic hydrocarbons. The likely routes of the formaꢀ
tion of fused biꢀ and polycyclic hydrocarbons in the
cyclopentanone reaction with hydrogen on the
RPFIC are shown in the scheme.
The macroscopic mechanism proposed explains the
formation of all fused bicyclic and polycyclic saturated
hydrocarbons on RPFICs. At the same time, it should be
noted that not all intermediate oxygenated compounds
shown in scheme 1 could be identified among the prodꢀ
gests either a higher rate of its hydrodeoxygenation to the
corresponding hydrocarbon as compared with the hydroꢀ
deoxygenation rate of tricyclic ketone XI containing the
carbonyl group on the middle ring (Table 2) or that 1,2ꢀ
dicyclopentylcyclopentane is produced via the mechaꢀ
nism other than aldol condensation. It may also be supꢀ
posed that the formation of fused biꢀ and polycyclic
hydrocarbons with sixꢀmembered rings by the cyclohexꢀ
ucts. Neither unsaturated ketones nor 2ꢀ(2ꢀcyclopentylꢀ anone or cyclohexanol reaction with hydrogen follows a
cyclopentylidene)ꢀ1ꢀcyclopentanone (XXIX) from scheme analogous to Scheme 1.
O
OH
O
O
OH
O
O
+
–
H2
H2
Fe
–H O
2
+H2
+
P
P
Fe
O
O
O
O
+
+H2
+H2
–H O
2
–H O
2
Fe
Fe
P
where
:
Fe and
P
O
are hydrogenating/dehydrogenating
and acid–base RPFIC sites, respectively
+
+H2
–
H O
2
–H O
2
Fe
O
(XXIX)
P
O
,
H2 –2H O
2
+
,
H2 –2H O
2
O
+
,
H2
–2H O
2
Scheme 1. Possible routes of the formation of bicyclic and polycyclic hydrocarbons in the reaction of cyclopentanone
with H on RPFIC.
2
Reductive Coupling of Benzaldehyde
(Table 11) [31, 32]. Table 12 presents data on the reacꢀ
tion of benzaldehyde, benzyl alcohol, or related comꢀ
pounds with hydrogen on the RPFIC . It is seen from
Table 12 that the benzaldehyde products include
dibenzyl (XXXII), transꢀstilbene (XXXIII), toluene
and Benzyl Alcohol
Unlike cyclopentanone or cyclohexanone, benzalꢀ
dehyde does not contain H atoms in the ꢀposition to
α
the carbonyl group, and aldol condensation is not posꢀ
sible. At the same time, it is known that dibenzyl is
(
XXXI), benzene (XXX), 1,2,3ꢀtriphenylpropane
produced in the reaction of benzaldehyde or benzyl (XXXIV), benzyl alcohol (XXXVI), and dibenzyl ether
alcohol with hydrogen on iron catalysts [5, 26]. On the (XXXVII). From the data on the products of the benꢀ
other hand, the reductive coupling of benzaldehyde is zaldehyde reaction with Н2, four possible schemes for
conducted in the presence of a WCl ꢀLiAlH , WCl or the formation of dibenzyl (XXXII) can be proposed.
6
4
6
WCI –BuLi metathesis reaction catalyst, resulting in
transꢀ and cisꢀstilbenes, dibenzyl, and other products
4
Scheme A comprises the following macrostages:
benzaldehyde hydrogenation to benzyl alcohol, its
[
27–30]. The products of the reaction of benzaldeꢀ
hyde with hydrogen in the presence of the RPFIC dehydration to give dibenzyl ether, and hydrodeoxyꢀ
were found to include the following compounds genation of the ether to XXXII:
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303
Table 7. Synthesis of fused bicyclic and tricyclic hydrocarbons from a cyclopentanolꢀcyclohexanol mixture and hydrogen
3
–1
–1
–1
on RPFIC (pH2
= 0.5 MPa, hydrogen space velocity of 10 h , specific feed rate of alcohol mixture is 160 g h kg Ct,
RPFIC composition is 4.7% V O + magnetite to 100% on unreduced sample basis)
2
5
Alcohol conversion, %
cyclopenꢀ cyclohexꢀ
Selectivity for products*, %
Run
no.
Cyclopentanol/cyꢀ
clohexanol ratio
T
, °C
total products
I
III VI XVI XXVI XXVII XXVIII
tanol
anol
with C=C bond
1
2
350
300
1 : 10
3 : 1
99**
99**
99
99
25 20 13.5
32 27
5
1
15
6.5
3
0
18.5
8.5
0
15
10
*
Product numbers are as given in Tables 2, 4 and 6. ** Product composition is given on a convertedꢀcyclopentanol basis
+
H2
–H2
+H2
A) PhCHO
PhCH OH
2
B) PhCH OH
2
PhCHO
PhCH CH Ph.
+
PhCH OH
+H2
–H O
2
H O
(
PhCH ) O
2 2
PhCH CH Ph.
2
O OH
PhC CHPh –
–
2
+H
2
2
2
+PhCHO
…
2
2
H O
2
Scheme B includes the following macrostages: benzyl
alcohol dehydrogenation to benzaldehyde, benzoin
condensation of benzaldehyde to benzoin, and subseꢀ
quent hydrodeoxygenation of benzoin to XXXII:
Scheme C suggests the metathesis of benzaldehyde at
the carbonyl group to form the surface benzylidene
intermediate, its conversion to transꢀstilbene, and
hydrogenation of XXXIII to dibenzyl:
O
+H2
Z + H O
2
Z
PhCH
Z
+2Z
C) PhCHO
+
PhCH
H
+
H2
Z
PhC CPh
H
PhCH CH Ph,
2 2
⎯
2Z
where Z is the RPFIC surface.
products of the benzaldehyde reaction with Н2 were
Scheme D includes the reaction of benzaldehyde not found to contain benzoin in any of the runs. 1,2,3ꢀ
with toluene to give XXXII:
Triphenylpropane (XXXIV) present in the products
can be indirect evidence for the benzoin condensation
reaction. Furthermore, the total rate of dibenzyl
+
H2
D
) PhCHO + PhCH3 –
PhCH CH Ph.
2 2
H O
2
(
XXXII) formation from benzaldehyde (Table12,
run 1) is approximately two times that from benzoin
run 6). All these facts suggest that not all amount of
To discriminate each possible mechanism of the
formation of dibenzyl, reactions with hydrogen, we
studied the reduction reactions with hydrogen for
dibenzyl ether, benzyl alcohol, benzaldehyde, a mixꢀ
ture of benzaldehyde and pꢀxylene (toluene analog in
Scheme D), and transꢀstilbene.
On the basis of the results obtained (Table 11), it
can be concluded that the contribution of Scheme A to
the formation of XXXII is insignificant because of a
low yield of dibenzyl (less than 2%) in the reaction of
dibenzyl ether with Н2 (Table12, run 5).
(
dibenzyl detected can be formed according to
Scheme B.
To elucidate the feasibility of the benzaldehyde
reaction with Н2 via Scheme C involving the intermeꢀ
diate formation of transꢀstilbene, experiments were
performed to detect the surface benzylidene species
Z=CHPh using in situ chemical trapping during the
course of the reaction. Diazomethane or D O was used
as a trap. Styrene was supposed to form in the case of
diazomethane:
2
After the reaction of the mixture of benzaldehyde
and
pꢀxylene, 1ꢀphenylꢀ2ꢀ(4ꢀmethylphenyl)ethane
+CH N
2 2
could not be detected even in a trace amount, thus
allowing route D to be rejected.
PhCH
PhCH=CH2,
Z
Benzoin in the reaction with Н2 (Table12, run 6)
transforms into dibenzyl in a 92% yield. However, the and dideuterotoluene in the case of D O
2
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306
GLEBOV et al.
Table 10. Synthesis of fused biꢀ, triꢀ, and polycyclic hydrocarbons from cyclopentanone and hydrogen on the thermally
3
–1
treated RPFIC (pH2
= 1.0 MPa, hydrogen space velocity of 10 h , RPFIC composition is 4.7% V O + 0.5% CuO + magꢀ
2 5
netite to 100% on unreduced sample basis)
Specific feed
Selectivity for products*, %
Catalyst
Run heating
no. temperaꢀ time, min
Synthesis
temperaꢀ
ture, °C
Ketone
rate of keꢀ
Heating
–1 converꢀ
sion, %
tone (g h
kg Ct)
–
1
ture, °C
I
II III IV
V
0
VI VII VIII IX
X
XI XII
1
2
3
4
5
6
7
8
9
1000
1000
700
60
2
220
100
100
100
100
100
100
84
75
0
0
0
1
1
6
0
0
1
0
0
0
0
0
0
0
0
0
0 11
4
1.5 0 27.5 39
8 10
220
220
300
300
300
250
250
250
80
0
7.5 0
3
1
1
6
4
5
1
0
4
0
0
1
2
2
4
3
2
17
5
9
0
0
0
0
0
0
0
54 8.5
2
98
1 11
3 33
0
0
0
0
0
0
0
33
48
49
34
59
61
52
48
1
1
6
2
3
0
0
0
650
10
10
2
99.5
99.5
99.5
99.5
99.5
99.5
1
600
1 41
0
0
600
4 46
0
0
700**
800**
2
19 17
20 16
21 21
0
0
4
108
170
0
0
1000**
8
0
0
*
Product numbers are as given in Table 2. ** Subjected to highꢀtemperature heating was the upper half of the RPFICꢀbed.
+D O
2
is inconsistent with the data of Table 12. Probably,
transꢀstilbene is produced from benzaldehyde accordꢀ
ing to scheme C and dibenzyl forms according to
scheme B. Note that a special experiment showed that
PhCH
PhCHD + H O.
2 2
Z
The products were analyzed using the GC–MS techꢀ transꢀstilbene is quantitatively hydrogenated with
nique; but neither styrene nor dideuterotoluene was hydrogen on the RPFIC. Therefore, dibenzyl in the
detected among the products of the benzaldehyde reaction of benzaldehyde with Н2 can be partially proꢀ
reaction with Н2
.
duced as a result of transꢀstilbene hydrogenation.
At the same time, the admixture of D O lowered
All of the above data on Reductive Dimerization
2
the benzaldehyde conversion from 72% (Table 12, and Oligomerization of cycloalkanones, cycloalꢀ
run 1) to 47% (Table 12, run 3), the selectivity for kanols, benzaldehyde, and benzyl alcohol to fused
dibenzyl from 32 to 4% (by a factor of 8), and the hydrocarbons on the RPFICs are difficult to explain in
selectivity for transꢀstilbene from 6 to 0.1% (by a factor terms of only intermediate condensation reactions
of 60); the selectivity for toluene remained almost (aldol and benzoin condensations). Obviously, a cerꢀ
unchanged, being 60 to 64.8%, respectively. If dibenꢀ tain amount of hydrocarbons and oxygenated comꢀ
zyl resulted from the hydrogenation of transꢀstilbene, pounds in the presence of the RPFIC is produced via
the selectivity for XXXII and XXXIII in the run with other mechanisms. The examined reactions of reducꢀ
D O would decrease to equal extents, an outcome that tive dimerization and oligomerization of carbonyl
2
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307
Table 11. Products of the reactions of benzaldehyde, benzyl alcohol, and related compounds with hydrogen on RPFIC
Product
number
Product
number
Product
Product
CH2 CH CH2
XXX
XXXIV
XXXV
O
CH3
C
XXXI
H
OH
CH2
XXXII
CH2 CH2
XXXVI
H
XXXIII
C
C
XXXVII
CH2 O CH2
H
Table 12. Products of the reactions of benzaldehyde, benzyl alcohol, and related compounds with hydrogen on RPFIC
3
–1
(
hydrogen space velocity of 10 h , RPFIC composition is 5.0% V O + magnetite to 100% on unreduced sample basis)
2 5
Partial pressure,
kPa
Selectivity for products, rel. %
Hydroꢀ
gen space
velocity,
Specificfeed
rate of SS (g
SS conꢀ
version,
wt %
Run Starting
no. substrate (SS) °C
T,
–1
–1
h
L
Ct)
–1
h
p
pSS
H2
1
2
3
4
5
6
PhCHO
PhCHO
PhCHO*
220
250
220
250
96
96
96
4
240
240
210
520
120
90
1000
1000
1000
300
72
97
47
96
38
95
0
60 32
1.5 82.7 15
64.8
0.1 57 29
6
0.6
0.1 0.1
0.1
–
–
–
1
0.4
4
4
0.1 0.5
0
4
0
31
0.1
0.8
–
PhCH OH
54 23
0.1 0.5 12
–
0.1
0
2
(PhCH ) O 220
81
50
4
300
0
0
93.8
5
0.1
0
0
2
1
0
2
2
220
0.7
1000
0.1 97.9
0
PhCHꢀCPh
OH O
*
Run with D O.
2
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308
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compounds and alcohols can be of interesting as
methods for preparing fusedꢀring hydrocarbons in
preparative and industrial petroleum chemistry.
anisma of Catalytic Reactions (Novosibirsk, 2006),
p. 155 [in Russian].
15. F. A. Yandieva, M. V. Tsodikov, V. Ya. Kugel, et al.,
Abstracts XVII International Conference on Chemical
Reactors—CHEMREACTORꢀ17 (AthensꢀCrete, 2006)
p. 314.
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Proceedings of the 7th Russian Conference on the Mechꢀ
Translated by S. Lebedev
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