• Clean Technology
• /
• v.29 no.2
• /
• pp.79-86
• /
• 2023

The homogeneous catalyst, Ru-MACHO-BH, selectively performs hydrogenation reactions only on the carbonyl group of α, β-unsaturated aldehyde compounds with extremely high reactivity and selectivity. However, the hydrogenation of α, β-unsaturated aldehydes involves a heterogeneous Diels-Alder reaction, resulting in the formation of significant amounts of byproducts, such as dimers. In this study, we used the Ru-MACHO-BH catalyst (Carbonyl hydrido (tetrahydroborato) [bis (2-diphenyl phosphino ethyl) amino] ruthenium(II)) to selectively hydrogenate the carbonyl group of a specific type of α, β-unsaturated aldehyde called methacryl aldehyde, leading to the synthesis of methallyl alcohol. Simultaneously, we applied diols to inhibit the formation of byproducts. The results demonstrate that monoethylene glycol can significantly reduce the formation of diols. Based on these results, we effectively suppressed the formation of dimers containing vinyl groups in methacryl aldehyde by using hydroquinone, which can efficiently inhibit the chemical interaction of vinyl groups. Consequently, the conversion rate of methacryl aldehyde was increased. Ultimately, by reducing the amount of the expensive homogeneous catalyst Ru-MACHO-BH to 1/10, we achieved a selectivity of over 90% and a yield of over 80% for the desired product, methallyl alcohol. These results provide a method to minimize yield reduction while reducing the usage of expensive catalysts, thereby improving cost-effectiveness. We expect that the reaction could be applied to various kinds of selective hydrogenation and has been successfully run on an industrial scale.

• Bulletin of the Korean Chemical Society
• /
• v.29 no.2
• /
• pp.328-334
• /
• 2008

The effects of catalyst preparation on the reaction route and the mechanism of biphenol (BP) hydrogenation, which consists of a long series-reaction, were studied. Pd/C catalysts were prepared by incipient wetness method and precipitation and deposition method. The reaction behaviors of the prepared catalysts and a commercial catalyst along with the final product distributions were very different. The choice of the catalyst preparation conditions during precipitation and deposition including the temperature, pH, precursor addition rate, and reducing agent also had significant effects. The reaction behaviors of the catalysts were interpreted in terms of catalyst particle size, metal distribution, and support acidities.

• Bulletin of the Korean Chemical Society
• /
• v.10 no.3
• /
• pp.279-282
• /
• 1989

Two rhodium(I) complexes of the types [Rh(BPPF)(NBD)]$ClO_4$ (10) and [Rh(BPPF)$Cl]_2$ (11) (BPPF = 1,1'-bis(diphenylphosphino)-ferrocene) have been prepared and investigated as catalysts for the regioselective hydrogenation of polynuclear heteroaromatic nitrogen and sulfur compounds such as quinoline (1), acridine (2), phenanthridine (3), 7,8-benzoquinoline (4), benzothiophene (5), isoquinoline (6), indole (7), pyridine (8), and thiophene (9). Both complexes 10 and 11, except for the cases of indole (7) and mononuclear heteroaromatics 8-9, are very efficient in the selective reduction under quite mild hydrogenation conditions to give the corresponding saturated nitrogen and sulfur heterocyclic analogues of 1-6 in fast conversion rates and in excellent yields. Relative rate studies revealed that the reduction depends significantly on the steric and electronic effects of the substrates. Of the two complexes 10-11, the dimeric species 11 gives faster reaction rates in all cases studied.

• Journal of Powder Materials
• /
• v.26 no.4
• /
• pp.290-298
• /
• 2019

$TiO_2$-particles containing Co grains are fabricated via thermal hydrogenation and selective oxidation of TiCo alloy. For comparison, $TiO_2$-Co composite powders are prepared by two kinds of methods which were the mechanical carbonization and oxidation process, and the conventional mixing process. The microstructural characteristics of the prepared composites are analyzed by X-ray diffraction, field-emission scattering electron microscopy, and transmission electron microscopy. In addition, the composite powders are sintered at $800^{\circ}C$ by spark plasma sintering. The flexural strength and fracture toughness of the sintered samples prepared by thermal hydrogenation and mechanical carbonization are found to be higher than those of the samples prepared by the conventional mixing process. Moreover, the microstructures of sintered samples prepared by thermal hydrogenation and mechanical carbonization processes are found to be similar. The difference in the mechanical properties of sintered samples prepared by thermal hydrogenation and mechanical carbonization processes is attributed to the different sizes of metallic Co particles in the samples.

• Korean Journal of Food Science and Technology
• /
• v.25 no.6
• /
• pp.637-642
• /
• 1993

Changes in the physicochemical characteristics and triglyceride molecular species of corn oil under the following condition of hydrogenation; temperature $180^{\circ}C,\;H_{2}$, pressure $2.0{\pm}0.3bar$, the amount of Ni catalyst 0.048%(Ni/oil by wt.) and agitation speed 300 rpm. The rate of hydrogenation, expressed as the reduction rate of the iodine value with respect to time, is first order and high (K>0.01). When the reduction rate of the iodine value was 39.9%, hydrogenation time was 30 min, 18:1 was highest(77.06%), thereafter that was decreased and 18:0 increased. In the triglyceride composition, OLL, LLL were reduced markedly in 10 min, thereafter reduced slightly. And PLO, PLL, OLO were eliminated in first 30 min. On the other hand, POO, PLS(CN52) and OOO, SLO(CN54) were increased sharply, and then that showed little change. The melting point(MP) of hydrogenated corn oil were $27.8^{\circ}C\;and\;44.1^{\circ}C$ after 20 min and 60 min, respectively. Trans isomer content increased to 46.8% during 40 mins of hydrogenation and then decreased insignificantly. The solid fat content were linearly increased with hydrogenation time. Accordingly, it is confirmed that this condition of hydrogenation was selective, preferential elimination of polyunsaturated fatty acid went stepwise and trans isomer was formed promotedly. These results suggest that fat modification techniques can be used for practical application.

• Bulletin of the Korean Chemical Society
• /
• v.33 no.5
• /
• pp.1643-1646
• /
• 2012

Three Ni-based catalysts with different clay as support were prepared and tested in the hydrogenation of maleic anhydride, among which Ni/clay1 showed best activity and selectivity. Over Ni/clay1 catalyst prepared by impregnation method, 97.14% conversion of maleic anhydride and 99.55% selectivity to succinic anhydride were obtained at $180^{\circ}C$ under a pressure of 1 MPa. Catalytic activity was greatly influenced by the temperature and weighted hourly space velocity. Catalyst deactivation studies showed that this catalyst have a long life time, the yield of MA still higher than 90% even after a reaction time of 60 h. X-ray diffraction (XRD) and $H_2$ temperature programmed reduction (TPR) were use to investigate the properties of the catalyst. XRD and TPR studies showed that Ni was present as $Ni^{2+}$ on the support, which indicated that there was no elemental nickel ($Ni^0$) and $Ni_2O_3$ in the unreduced samples. The formation of Ni was strong impact on catalytic activity.

• Applied Biological Chemistry
• /
• v.36 no.2
• /
• pp.93-98
• /
• 1993

The purpose of this study is to determine the physicochemical properties in soybean oil during the hydrogenation by addition of phosphorus compounds and sulfur compounds is increased in soybean oil, decreased oleic acid and increased linoleic acid and stearic acid contents were found. When the sulfur compounds content is increased, solid fat content is increased at $10.0^{\circ}C$ and $21.1^{\circ}C$ and gradually decreased at $33.3^{\circ}C$ and $37.8^{\circ}C$. Higher melting point in hydrogenated soybean oil is observed on addition of phosphorus compounds compared to addition of sulfur compounds. When the sulfur compounds content is increased, conditions of selective hydrogenation are observed. Lead and arsenic are detected at a concentration of 0.01 ppm in a few kinds at each step of the refining process of soybean oil.

• Asian-Australasian Journal of Animal Sciences
• /
• v.14 no.1
• /
• pp.48-53
• /
• 2001

An in vitro study was conducted to examine the effect of sources and the addition levels of carbohydrates on fermentation characteristics, bacterial growth, and hydrogenation of linoleic acid ($C_{18:2}$) by mixed ruminal bacteria. Starch and cellobiose were added to the 200 ml non-selective basal media at the levels of 0.20 and 0.35% (w/v), respectively. Linoleic acid (66.8~79.6 mg) in the absorbed form into the pieces of nylon cloth was also added to the media of 5 treatments including control which was not added with carbohydrate. Three mls of rumen fluid strained through 12 layers of cheese cloth were added to each medium, and were incubated anaerobically in the shaking incubator of $39^{\circ}C$ for 24 hours. During 24 h incubation the pH in incubation media of all treatments was maintained above 6.6 by the addition of sodium bicarbonate. The pH and ammonia concentration of incubation media were not clearly influenced by the sources and addition levels of carbohydrates while additions of carbohydrates increased (p<0.0001) VFA concentration at the 24 h incubation. Molar proportions of acetate were reduced (p<0.0004) while those of propionate were increased (p<0.0006) by the addition of carbohydrates. But the differences in concentration and molar proportions of the VFA were small between the sources or the addition levels. Bacterial growth was faster (p<0.0004) in the starch added treatments than in the cellobiose added ones and control, but no differences were found between addition levels. Increased (p<0.0487) hydrogenation was observed from the starch added treatments compared to the cellobiose added ones, but there was no difference between addition levels.

• Journal of the Institute of Electronics Engineers of Korea SD
• /
• v.43 no.1 s.343
• /
• pp.7-12
• /
• 2006

In this study, we developed irreversible and stable micro-size ferromagnetic structures utilizing hydrogenation and electron-beam lithography processes. The compositionally modulated (CM) Fe-Zr thin films that had average compositions $Fe_XZr_{100-x}$ with $x=65-85\%$ modulation periods of similar to 1 nm, and total thicknesses of similar to 100 m were prepared. The magnetic properties of CM Fe-Zr thin films were measured using a SQUID magnetometer, VSM and B-H loop tracer. After hydrogenation, the CM films exhibited larger magnetic moment increases than similar homogeneous alloy films for all compositions and かey showed largest increase in $Fe_{80}Zr_{20}$ composition. After aging in air at $300^{\circ}K$ the hydrogenated $Fe_{80}Zr_{20}$ CM films showed much larger magnetic moment increases, indicating that they relax to a stable, irreversible, soft magnetic state. The selective hydrogenation through electron-beam lithographed windows were performed after the circle shaped windows were prepared on $Fe_{80}Zr_{20}$ CM films by electron beam lithography. The hydrogenation through electron-beam resist and W lithographic techniques give a $49\%$ magnetic moment increase. This method can be applied to nano scale structures.

• Bulletin of the Korean Chemical Society
• /
• v.31 no.3
• /
• pp.570-576
• /
• 2010

A variety of ynamides undergo highly regio- and stereoselective radical addition of arenethiols with the aid of triethylborane as a radical initiator. The products, N-[(Z)-2-arylsulfanyl-1-alkenyl]amides, can be reduced with triethylsilane in trifluoroacetic acid to yield N-[2-(arylsulfanyl)alkyl]amides.