Green Chemical Engineering 2 (2021) 187–196

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Green Chemical Engineering

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Article

Green process for hydrogenation of methyl ricinoleate to methyl

12-hydroxystearate over diatomite supported Cu/Ni bimetallic catalyst
Xiao Zhang a, Hong-Ru Li b, *, Feng-Ge Zhao a, Xiao-Ying Cui c, Feng Ye c, Liang-Nian He a, *
a
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, 300071, China
b
College of Pharmacy, Nankai University, Tianjin, 300353, China
c
Nankai University Engineering Research Center for Castor, Tianjin, 300071, China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

Hydrogenation of methyl ricinoleate was

performed using a Cu/Ni bimetallic
catalyst.

The formation of highly dispersed Cu/Ni
alloy on catalyst surface was verified.

Methyl 12-hydroxystearate was obtained
with high yield and selectivity.

This protocol represents a green catal-
ysis for efficient conversion of biomass.

A R T I C L E I N F O A B S T R A C T

Keywords: A series of diatomite supported Cu/Ni bimetallic catalysts were prepared using the co-impregnation method to
Biomass improve the efficiency and selectivity toward methyl 12-hydroxystearate in the hydrogenation of methyl rici-
Green process noleate. The catalysts were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM),
Hydrogenation
scanning electron microscopy and energy dispersive X-ray spectroscopy (SEM-EDS), X-ray photoelectron spec-
Methyl 12-hydroxystearate
troscopy (XPS) and temperature programmed reduction (H2-TPR). All the characterization results verified the
Supported bimetallic catalyst
Sustainable chemistry formation of highly dispersed Cu/Ni alloy on support. Moreover, by subtly regulating the Ni/Cu molar ratio as
well as the reaction parameters, the hydrogenation of methyl ricinoleate to methyl 12-hydroxystearate proceeded
efficiently and selectively, affording 97% yield of methyl 12-hydroxystearate and nearly equivalent conversion of
methyl ricinoleate under 2 MPa H2 pressure and at 130  C in 4 h with only 1 wt% of the catalyst Ni7Cu1/diatomite
(based on methyl ricinoleate). Besides, the supported Cu–Ni bimetallic catalyst is stable during recycle and reuse.
After five cycles of reuse, much catalytic activity is still preserved. Therefore, this low-cost and stable bimetallic
catalyst would be promising for the hydrogenation of methyl ricinoleate to methyl 12-hydroxystearate, repre-
senting an example of green catalysis for efficiently conversion of biomass to value-added chemicals and
materials.

1. Introduction increasingly serious with the rapid development of global industry. In this
context, the renewable biomass has attracted much concern as the alter-
The resource depletion and environmental pollution are becoming native to non-renewable fossil resources [1,2]. By now, many chemicals,

* Corresponding author.
E-mail addresses: lihongru@nankai.edu.cn (H.-R. Li), heln@nankai.edu.cn (L.-N. He).

https://doi.org/10.1016/j.gce.2020.09.011

Available online 28 September 2020

2666-9528/© 2020 Institute of Process Engineering, Chinese Academy of Sciences. Publishing services by Elsevier B.V. on behalf of KeAi Communication Co. Ltd. This
is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
X. Zhang et al. Green Chemical Engineering 2 (2021) 187–196

which were traditionally obtained from fossil fuels, a depleting resource,

can be derived from biomass such as cellulose, lignin and vegetable oil [3].
Moreover, for certain specific chemicals with unique structure and prop-
erties, biomass serves as the only source [4,5].
The castor oil, which is produced from castor beans of Ricinus com-
munis, has become an appealing non-food biomass for its unique structure
and properties [6–8]. The main component exists in castor oil is triglyc-
eride 12-hydroxy-9-octadecenoic acid (ricinoleic acid) [9]. The unique
structure of ricinoleic acid, for example, the unsaturated bond as well as a
secondary –OH group at its 12 carbon, makes castor oil a useful platform
chemical. Up to now, the derivatives of castor oil have been applied in
many nonfood fields [10–13], whereby methyl 12-hydroxystearate is an
important basic raw material used in medicine, cosmetics and other in-
dustries for synthesizing surfactants, thickeners, and dispersants [14,15].
Up to now, methyl 12-hydroxystearate is produced via trans-
esterification and subsequent hydrogenation or hydrogenation followed by
transesterification starting from castor oil as shown in Scheme 1, wherein
the hydrogenation step has been intensively investigated to improve the
efficiency and selectivity toward the target product. So far, the Pd/C Fig. 1. XRD patterns of Ni7Cu1/diatomite, Ni/diatomite, calcined diatomite and
untreated diatomite.
catalyst [16], nickel supported catalyst [17] and Pt-based catalysts
[18–20] have already been developed for the hydrogenation of castor oil
or methyl ricinoleate to produce the hydrogenated castor oil or methyl
12-hydroxystearate. However, the product via Pd/C catalysis generally
contains dehydration impurities albeit the reaction can proceed at mod- hydrogenation of C– – C bond in methyl ricinoleate to produce methyl
erate H2 pressure. The nickel monometallic supported catalyst has good 12-hydroxystearate.
selectivity but the product yield and catalyst reusability need to be further In this work, the supported Cu/Ni bimetallic catalyst was prepared
improved. On the other hand, Pt-based catalysts are expensive and not using the cheap and available support diatomite and applied in the hy-
applicable for commercial production. As a consequence, developing drogenation of methyl ricinoleate. As expected, almost equivalent con-
inexpensive catalysts with high efficient and selectivity for industrial version of methyl ricinoleate and 97% yield of methyl 12-hydroxystearate
production of methyl 12-hydroxystearate is still highly desired. were obtained. In addition to the remarkable catalytic activity and selec-
Here we focus attention on bimetallic supported catalysts. As tivity, the bimetallic catalyst also showed excellent reusability. The high
compared to monometallic supported catalyst, the bimetallic supported efficiency and selectivity of this catalyst can be rationalized by the for-
catalysts demonstrate enhanced activity, product selectivity, and catalyst mation of alloy on the surface of catalyst, which has been confirmed by
stability. For example, the Ni/Cu bimetallic catalysts supported onto different characterization methods. Moreover, the stability of the Cu/Ni
Al2O3 and zeolite have been applied in oleic acid and palm oil hydro- bimetallic supported catalyst in reuse was also verified by catalyst char-
genation [21,22] and hydrogenation of furfural to 2-methylfuran as well acterization and related study.
[23]. The results of these examples show that regulating the composition
of catalysts may facilitate H2 dissociation and selective substrate 2. Experimental
adsorption and thus enhance the catalytic activity and product selec-
tivity. The in-depth mechanism study reveals that doping a second metal 2.1. Materials
can alter the surface properties by forming alloy, therefore resulting in
surprising effect [24–27]. In view of this, we envisioned that the Cu/Ni Nickel sulfate, copper sulfate and sodium carbonate were pur-
supported bimetallic catalysts may efficiently work for the selective chased from Tianjin Guangfu Technology Development Co. Ltd.

Scheme 1. Synthesis of methyl 12- hydroxystearate from castor oil.

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X. Zhang et al. Green Chemical Engineering 2 (2021) 187–196

Fig. 2. (a) (b) SEM images of Ni7Cu1/diatomite catalyst at different magnifications, (c) (d) EDS mapping images of Ni and Cu in Ni7Cu1/diatomite catalyst.

Fig. 3. (a) (b) SEM images of Ni/diatomite catalyst at different magnifications, (c) (d) EDS mapping images of Ni and Si in Ni/diatomite catalyst.

Diatomite was bought from Energy Chemical. Methyl ricinoleate was supported by Tianjin No. 6 chemical reagent Factory and H2 with a
prepared by the transesterification of castor oil with methanol and purity of 99.99% was supplied by Liquefied Air (Tianjin). All chem-
purified by distillation (for details, see SI). The castor oil was icals were used as received.

189
X. Zhang et al. Green Chemical Engineering 2 (2021) 187–196

Fig. 4. (a) (b) TEM images of Ni7Cu1/diatomite catalyst at different magnifications, (c) (d) TEM images of Ni/diatomite catalyst at different magnifications.

Fig. 5. Nitrogen adsorption-desorption isotherms and pore size distribution of (a) (b) Ni7Cu1/diatomite catalyst and (c) (d) Ni/diatomite catalyst .

2.2. Cu/Ni/diatomite catalyst preparation
A series of diatomite supported bimetallic Cu/Ni catalysts with
different Cu/Ni molar ratio and monometallic Ni or Cu catalyst were
synthesized via a co-impregnation method [28]. Briefly, 8.805 g
diatomite and 50 mL 1 mol L1 Na2CO3 were added to a three-necked
flask and stirred at 70  C for 0.5 h. Then the pre-prepared 0.6 mol L1
nickel sulfate aqueous solution and 0.2 mol L1 copper sulfate aqueous
solution were mixed well according to the calculated volume and
added dropwise to the above diatomite suspension under vigorous
stirring. After that, the pH of the suspension was adjusted to 8–9 using
1 mol L1 Na2CO3 aqueous solution. Then the precipitate was aged for

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Table 1
The physicochemical properties of Ni/diatomite and Ni7Cu1/diatomite catalysts.
Catalyst SBET/(m2 Pore volume /(cm3 Pore size Metal
g1) g1) /nm loadinga
/(wt%)
Ni
Ni/SiO2 17.2 0.04 4.82 16.5
Ni7Cu1/ 19.8 0.06 5.47 17.2
SiO2
a
Metal loading determined by ICP-OES. The deviations between the actual and
calculated values originate from the metal loss in precipitation process and the
different precipitate rates between the Cu, Ni in catalyst preparation.
4 h at 70  C and the resulting dark green suspension was filtered and
the precipitate was washed with distilled water repeatedly to neutral,
followed by drying at 120  C for 4 h in a vacuum oven to remove the
residual moisture. Next, the catalyst was transferred to a tube furnace
and dried at 70  C for 2 h, followed by calcined at 340  C for 2 h in
nitrogen atmosphere and reduced in hydrogen at 360  C for 2 h. Then
the resulting supported catalyst was cooled under N2 flow. In the
supported catalyst preparation, the total metal Cu and Ni loading was
fixed at 20 wt% and the catalyst with different Cu/Ni ratio can be
prepared by changing the volume of nickel sulfate and copper sulfate
aqueous solution.
2.3. Catalyst characterization techniques
A MimFLex600 diffractometer was used to record the X-ray diffrac-
tion (XRD) patterns of the catalysts. In the characterization, Cu Kα ra-
diation is at 45 kV and 200 mA and a scanning rate of 0.5 min-1 was set
in the 2θ range of 5 ~ 80 . Scanning electron microscopy and energy
dispersive X-ray spectroscopy (SEM-EDS) of the supported catalyst were
performed on JEOL-JSM Model 6380 LA instrument with a 200 kV
operating voltage. To avoid the charges accumulation and improve the
conductivity, gold spraying was performed before placing on the sample
table. Transmission electron microscopy (TEM) was carried out on a
Tecnai G2 F20 transmission electron microscopy, operating at 200 kV.
Before TEM analysis, the sample particles were dispersed in ethanol and
then loaded on carbon-coated copper grids to evaporate the solvent. X-
ray photoelectron spectroscopy (XPS) analysis was performed on a Kratos
Axis Ultra DLD spectrometer with a monochromatized Al Kα X-ray source
(hn ¼ 1486.6 eV). The C 1s peak (284.6 eV) was used as the reference
standard for the binding energy.
The nitrogen adsorption desorption experiment was performed on
BELSORP Max instrument. Before the experiment, a vacuum pretreat-
ment was applied to the samples at 423 K for 8 h first and then the
adsorption desorption isotherms was determined at 77 K. The specific
surface area and pore volume and pore size distribution were calculated
according to the Brunauer–Emmett–Teller (BET) model and nonlocal
density functional theory (NLDFT) method respectively. The inductively
coupled plasma-optical emission spectroscopy (ICP-OES) was used to
measure the actual loading of metal Cu and Ni in different catalysts on an
Agilent 730 device. Before analysis, a mixture of HCl and HNO3 with
molar ratio of 3:1 was employed to dissolve the catalysts.
The H2 temperature programmed reduction of the catalyst (H2-TPR)
was recorded on a Micromeritics Chemisorb 2750 device equipped with a
thermal conductivity detector (TCD) from Micromeritics Instrument
(Shanghai) Ltd. In the characterization, the samples were firstly pre-
treated at 350  C for 2 h, and then the temperature decreased to 25  C
with an argon flow of 10 mL min-1. After that, the atmosphere was
switched to 10% hydrogen/90% argon and the reactor was heated to
800  C at a ramp rate of 10  C min-1 to begin the H2 temperature pro-
grammed reduction.
Green Chemical Engineering 2 (2021) 187–196
2.4. General procedure for hydrogenation of methyl ricinoleate
The catalytic activity was evaluated by the yield and selectivity to-
ward methyl 12-hydroxystearate in the hydrogenation of methyl
ricinoleate.
Cu The prepared catalysts were pelleted, crushed, and screened out with
–
20–40 meshes. The hydrogenation reaction was performed in batch
2.3 mode with a magnetically stirred 50 mL autoclave. Before the reaction,
about 1 g methyl ricinoleate and a certain amount of the supported
catalyst were loaded in the autoclave, then the air in the reactor was
expelled and pure H2 was fed into the reactor to maintain a reaction
pressure. Subsequently, the reactor was heated to the preset temperature
to begin the reaction. After a period of reaction, the reactor was cooled to
room temperature. The resulting mixture was dissolved in ethyl acetate
and the solid catalyst was separated by filtration. The reused catalyst was
characterization by SEM, TEM, XRD and XPS. The filtrate was analyzed
by GC and GC-MS to determine the conversion of methyl ricinoleate and
the yield of methyl 12-hydroxystearate as well as the composition of the
crude reaction mixture respectively. To test the reusability of the sup-
ported catalyst, the catalyst recovered by filtration was washed with
ethanol and dried under vacuum, and then used for next cycle. Simul-
taneously, the recovered catalyst was also characterized using different
technique to inspect its stability in reuse.
2.5. Analysis method
The conversion of methyl ricinoleate and yield of products were
determined by gas chromatography equipped with SH-Rtx-5 capillary
column and a FID detector using biphenyl as internal standard (Shi-
madzu, GC-2014). The carrier gas was nitrogen, and the temperature of
the injector and detector were 280  C and 300  C respectively. The
temperature program was from 120  C to 280  C at a ramp of 10  C min-1,
holding 20 min at 280  C. The composition of the reaction mixture after
hydrogenation was identified on a GC-MS system (Shimadzu GCMS-
QP2010) in the electronic impact ionization mode at 70 eV and equip-
ped with a RTX-5 MS capillary column. The temperature of the oven was
programmed from 50  C to 300  C at a ramp of 20  C min-1, and kept at
300  C for 30 min. The data are given as mass units per charge (m/z). FT-
IR was performed on Bruker Tensor 27 FT-IR instrument spectropho-
tometer with KBr pellets and the wavenumber range of 4000-400 cm1.
1
H NMR and 13C NMR were recorded on 400 MHz and 100.6 MHz
spectrometers using CDCl3 as solvent referenced to CDCl3 (7.26 ppm for
1
H NMR and 77.00 ppm for 13C NMR). The high resolution mass spec-
trometry was used to determine the molecular weight of analyte on a
Varian 7.0 T FTICR-MS with ESI technique.
3. Results and discussion
3.1. Catalyst characterization
To investigate the surface morphology and composition of the cata-
lysts, the XRD patterns of the as-synthesized Ni7Cu1/diatomite (the
subscript means the molar ratio of the two metals in the catalyst), Ni/
diatomite, calcined diatomite and untreated diatomite powders were
detected and depicted in Fig. 1. It can be seen that the structure of
diatomite is retained in the catalyst preparation process. For the Ni/
diatomite catalyst, the characteristic peaks for metallic nickel phase
(JCPDS #04–0850) at 2θ ¼ 45 , 53 , 78 are observed, which reveals the
existence of metallic Ni(0). After doping a certain amount of copper, the
shift and attenuation of the crystal diffraction peak were observed in
Fig. 1, which means that the copper-nickel bimetal alloy was formed and
the formed metal particles are too small to be detected. Thus we inferred
that the metal dispersion on the carrier was enhanced by doping a small
amount of copper.
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X. Zhang et al.
Fig. 6. (a) XPS survey spectra of Ni/diatomite and Ni7Cu1/diatomite, (b) XPS spectra for Cu 2p of Ni7Cu1/diatomite, (c) XPS spectra for Ni 2p of Ni/diatomite, (d) XPS
spectra for Ni 2p of Ni7Cu1/diatomite.
The micromorphology and structures of the Ni7Cu1/diatomite and
Ni/diatomite catalysts were determined by SEM-EDS and TEM. The SEM-
EDS results in Fig. 2 and Fig. 3 showed that there were uniformly
distributed nano-scale open pores in the surface of disk-like diatomite,
which can endow the supported catalyst with sufficient specific surface
area. For Ni7Cu1/diatomite catalyst, EDS mapping indicated that Cu and
Ni X-ray signals were uniformly mixed together. The consistent distri-
bution of Cu and Ni hinted a good fusion performance of Ni and Cu in the
Ni7Cu1/diatomite catalyst, which was in consistence with the XRD re-
sults. By contrast, for the Ni/diatomite catalyst, the relative large Ni
metal particles can be found on the surface of carrier, which indicated
poor dispersion of metal on diatomite. Therefore, it was concluded that
the dispersion of metals on the support is improved with the addition of
Cu.
The TEM results in Fig. 4 also confirmed that Ni/Cu alloy homoge-
neously dispersed on the diatomite with an average particle size of
20 nm. As compared with the monometallic Ni/diatomite catalyst, the
Ni/Cu alloy particle was much smaller, which implies that the addition of
the Cu can reduce the particle size and increase the dispersion of metals
on the carrier.
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Green Chemical Engineering 2 (2021) 187–196
The specific surface area, pore volume and average pore diameter of
Ni7Cu1/diatomite and Ni/diatomite catalysts were calculated according
to the nitrogen adsorption desorption results. As shown in Fig. 5, the
isotherm of Ni7Cu1/diatomite and Ni/diatomite exhibit typical IUPAC
type IV pattern with H1-type hysteresis loop, which indicates a meso-
porous nature of the supported catalyst. As shown in Table 1, the specific
surface area, pore volume and average pore diameter of the Ni7Cu1/
diatomite catalyst were slightly larger than those of Ni/diatomite, which
was supposed to benefit from the enhanced metal dispersion on the
carrier for Ni7Cu1/diatomite catalyst.
The XPS analysis was performed to obtain the detailed information on
the surface chemical composition and chemical states in the reduced
supported catalyst. The XPS survey spectra showed that both supported
metal and SiO2 coexist on the catalyst surface. The high resolution
spectra of Ni 2p and Cu 2p photoelectron lines for Ni7Cu1/diatomite and
Ni/diatomite were shown in Fig. 6. Two peaks can be found for the Cu
2p3/2 spectra of Ni7Cu1/diatomite catalysts. The peak at 932.4 eV rep-
resents metallic Cu, and the peak at 933.7 eV is associated with Cu2þ in
CuO. Similarly, for the Ni 2p3/2 spectra, two peaks at 852.7 eV and
858.9 eV were detected, which can be related to metallic Ni and Ni2þ in
X. Zhang et al. Green Chemical Engineering 2 (2021) 187–196

part of Ni, which confirmed the formation of the Cu–Ni alloy. The other
two minor reduction processes occurred between 140 ºC-150  C might be
ascribed to the reduction of copper oxide [29] and the reduction peak
presented at 375  C, being associated with the reduction of NiO.

375 oC 3.2. Hydrogenation of methyl ricinoleate to methyl 12-hydroxystearate

Intensity/a.u.

3.2.1. Performances of different catalysts

Having obtained the supported monometallic and bimetallic cata-
150 oC Ni/diatomite lysts, the hydrogenation of methyl ricinoleate was performed under a
Ni7Cu1/diatomite
233 oC
relatively low pressure (2 MPa). And the results were listed in Table 2. It
140 oC 199 oC
can be seen that in the absence of catalyst or using Cu/diatomite as
catalyst, no hydrogenation occurred (entries 1–2). The Ni/diatomite and
100 200 300 400 500 600 700 800
Ni/Cu/diatomite catalyst can promote the hydrogenation. However, the
T/oC
usage of monometallic catalyst should be much higher than that of the
Fig. 7. H2-TPR profiles of Ni7Cu1/diatomite and Ni/diatomite catalysts. bimetallic ones (entries 3–5 vs. 6–8，Table 2) to achieve comparable
conversion and yield. This meant that the catalytic activity was enhanced
by adding Cu. It was also noteworthy that the disparity between the
conversion of methyl ricinoleate and the yield of methyl 12-hydroxystea-
NiO, respectively. The results of XPS analysis showed that Ni0 and Ni2þ
rate can be observed for some reactions (entries 3–7), which means the
species coexist on the surface of supported Ni/diatomite and Ni0, Ni2þ,
by-product formation. Gratifyingly, by regulating the content of Cu in the
Cu0 and Cu2þ species present on the surface of Ni7Cu1/diatomite. The
bimetallic catalyst, the by-product can be reduced (entries 8–11). When
existence of oxidized metal on the catalyst surface is ascribed to the re-
the Ni/Cu atom ratio was 7:1, nearly equivalent conversion and up to
oxidation of reduced metal when exposed to air as well as the incom-
97% yield of product can be obtained. Therefore, the catalyst Ni7Cu1/
plete reduction in the tube furnace. In XRD characterization, no oxide
diatomite was optimum for this reaction. The results showed that both
species were detected due to the good dispersion of these species on the
the efficiency and selectivity of the catalyst toward methyl 12-hydroxys-
catalysts surface.
tearate was improved by doping a small amount of Cu. The enhanced
To detect the change of atomic environment in Ni/diatomite and
activity and selectivity of the bimetallic catalyst may be originated from
Ni7Cu1/diatomite catalysts, the H2-TPR analysis was carried out before
its improved ability to activate hydrogen and the specific site adsorption
the reduction of catalysts and the resulting profiles are shown in Fig. 7.
of the substrate on the alloy surface.
For Ni/diatomite, a single reduction peak between 170  C and 358  C
With Ni7Cu1/diatomite as catalyst, we further studied the effect of
with a reduction in the approximate temperature of 233  C was observed.
catalyst amount on the hydrogenation reaction. It was found that both of
For bimetallic Ni7Cu1/diatomite catalyst, four isolated reduction peaks
the conversion of methyl ricinoleate and the yield of methyl 12-hydrox-
were observed, which implied a complex composition on the surface of
ystearate decreased when reducing the catalyst amount (entries 8–11).
the bimetallic catalyst; presumably due to different precipitate rates be-
Even so, 82% yield of product can still be obtained when the catalyst was
tween the Cu, Ni. Although different metal oxide species coexisted on the
reduced to 0.2 wt%, being corroborated the high efficiency of the
diatomite surface, the shift of main reduction peak (at 199  C) toward
bimetallic catalyst. To maintain a high conversion and product yield, 1 wt
low temperature meant the change of atomic environment for at least
% Ni7Cu1/diatomite was used as catalyst in the following experiments.

Table 2
Catalyst screening for hydrogenation of methyl ricinoleate.

Entry Catalyst Catalyst, wt% Conversion, %a Yield, %a

1 None – 0 0
2 Cu/diatomite 1 0 0
3 Ni/diatomite 1 47 40
4 Ni/diatomite 5 92 85
5 Ni/diatomite 8 > 99 93
6 Ni3Cu1/diatomite 1 > 99 91
7 Ni5Cu1/diatomite 1 > 99 95
8 Ni7Cu1/diatomite 1 > 99 97
9 Ni7Cu1/diatomite 0.5 88 87
10 Ni7Cu1/diatomite 0.3 85 83
11 Ni7Cu1/diatomite 0.2 83 82

Reaction conditions: methyl ricinoleate (3.2 mmol, 1.00 g), H2 (2 MPa), 130  C, 10 h.
a
Determined by GC with biphenyl as internal standard.

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X. Zhang et al.
Fig. 8. Effect of reaction parameters on the hydrogenation of methyl ricinoleate. Reactions were performed with methyl ricinoleate (3.2 mmol, 1.00 g), Ni7Cu1/
diatomite (1 wt% relative to methyl ricinoleate).
3.2.2. Effect of the reaction parameters
With the selected catalyst in hand, we further optimized the other
reaction conditions containing the hydrogen pressure, temperature and
reaction time for the reaction.
The effect of H2 pressure on the hydrogenation of methyl ricinoleate
was investigated with the reaction temperature and reaction time set at
130  C and 9.5 h. Similarly, the reaction temperature was screened by
fixing the H2 pressure and reaction time at 2 MPa and 9.5 h, respectively.
The results in Fig. 8 showed that the reaction is sensitive to the H2
pressure as well as the reaction temperature. When the H2 pressure is
below 1 MPa and the temperature is less than 100  C, the hydrogenation
of methyl ricinoleate cannot occur. Increasing the H2 pressure and re-
action temperature improved the conversion of methyl ricinoleate.
However, the H2 pressure higher than 2 MPa and temperature above
130  C reduced the product selectivity. Therefore, the optimal H2 pres-
sure and reaction temperature were set at 2 MPa and 130  C, respec-
tively. Under these optimized conditions, up to 97% yield of target
product can be obtained.
In the subsequent investigation of reaction time, an obvious induction
time was observed. After the induction time, the conversion of methyl
ricinoleate and yield of methyl 12-hydroxystearate increased sharply.
When the reaction time was prolonged to more than 4 h, the conversion
Fig. 9. Reusability of the Ni7Cu1/diatomite catalyst. Reaction conditions:
methyl ricinoleate (3.2 mmol, 1.00 g), Ni7Cu1/diatomite (10 mg), H2 (2 MPa),
130  C, 4 h.
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Green Chemical Engineering 2 (2021) 187–196
remained unchanged but the product yield decreased. Simultaneously,
the by-product methyl stearate was detected (the by-product has been
verified by GC-MS spectra of the crude reaction mixture and the details
can be found in SI). It is inferred that the induction time is the result of
catalyst reactivation as the bimetallic catalyst exposed to air can be easily
deactivated. Actually, in the XPS characterization of the catalyst, the
oxidized Cu and Ni species was detected. After the catalyst was reac-
tivated in the reaction system, the hydrogenation proceeded quickly and
almost equivalent conversion of methyl ricinoleate can be achieved. With
the increase of reaction time, side reactions occurred and the yield of
target product decreased.
3.2.3. Reusability of the supported Cu/Ni bimetallic catalyst
As the recyclability and reusability are the key features for the
heterogeneous catalyst, the stability and reusability of the Ni7Cu1/
diatomite catalyst was assessed for this hydrogenation reaction and the
results were presented in Fig. 9. In this set of experiments, the hy-
drogenation reaction was conducted under the optimal conditions.
When the reaction was completed, the mixture was dissolved in ethyl
acetate. Then the catalyst was recovered by filtrating the reaction
mixture. After appropriate treatment (as mentioned in Section 2.3), the
catalyst was reused in the next run. It can be seen from Fig. 9 that after
five runs of reaction, 92% of the catalytic activity was retained, which
means that the supported bimetallic catalyst has satisfying stability
and reusability.
To further verify the stability of the catalyst in reused, the Ni7Cu1/
diatomite catalyst after five rounds of recycle was characterized by SEM,
TEM, XRD and XPS. The results in Fig. 10 showed that the morphology
and composition of the catalyst were stable during the reuse, which
supported the excellent reusability of the supported bimetallic catalyst.
The improved stability of this bimetallic catalyst can be attributed to the
formation of Cu/Ni alloy, which inhibited the migration and aggregation
of Ni atom during the exothermic process and thus keep the even dis-
tribution of catalytic sites on the surface of support.
4. Conclusions
In summary, a high efficient diatomite supported Cu/Ni bimetallic
catalyst was developed for selective hydrogenation of methyl ricino-
leate to methyl 12-hydroxystearate. The results showed that the Cu/Ni
ratio of 7:1 in the supported bimetallic catalyst is optimum and the
characterization results of XRD, SEM-EDS, TEM, XPS and H2-TPR
showed that the highly dispersed Cu/Ni alloy was formed on the
surface of carrier, which might promote double bond adsorption and
X. Zhang et al. Green Chemical Engineering 2 (2021) 187–196

Fig. 10. (a) SEM, (b) TEM images of reused Ni7Cu1/diatomite catalyst after five catalytic cycles, (c) XRD spectra of fresh and used Ni7Cu1/diatomite catalyst, (d) XPS
survey spectra for Cu 2p and (e) Ni 2p of the reused Ni7Cu1/diatomite catalyst after five catalytic cycles.

H2 activation on the catalyst and therefore result in its superior cata-
lytic activity and selectivity as compared with the supported Ni
monometallic catalyst. Under the optimal reaction conditions, i.e.
2 MPa of H2 pressure, 130  C and 1 wt% catalyst, up to 97% yield of
methyl 12-hydroxystearate and equivalent conversion of methyl rici-
noleate can be achieved in 4 h. In addition, the heterogeneous Ni7Cu1/
diatomite catalyst could be easily recovered and reused without sig-
nificant loss of activity. Therefore, this Cu/Ni bimetallic supported
catalyst proves to be efficient for commercial production of methyl 12-
hydroxystearate from methyl ricinoleate. Therefore, this work will
pave new avenue for developing green process for upgrading of
biomass to industrial useful chemicals and materials.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was financially supported by the National Program on Key
Research Project (2016YFA0602900) and Nankai University Engineering
Research Center for Castor and also supported by "the Fundamental
Research Funds for the Central Universities", Nankai University
(000082).

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