US-12616962-B2 - Catalyst for hydrogenation reaction and method for producing same

US12616962B2US 12616962 B2US12616962 B2US 12616962B2US-12616962-B2

Abstract

The present invention can facilitate the reduction of nickel by using copper as an accelerator when a hydrogenation catalyst including nickel is produced by using a deposition-precipitation (DP) method. According to an embodiment of the present invention, provided is a catalyst for a hydrogenation reaction that includes 40-80 parts by weight of nickel as a catalyst active component, 0.01-5 parts by weight of copper as an accelerator, and 10-30 parts by weight of a silica support based on 100 parts by weight of the entire catalyst. Therefore, although a high content of nickel is supported, the catalyst has a small crystal size of an activated metal and a high degree of dispersion and provides excellent hydrogenation activity. In addition, silica with a controlled particle size distribution is used as a support, so that the produced catalyst also has a uniform particle size distribution and is suppressed from being smashed at a high-speed rotation in the hydrogenation reaction, thereby providing a high filtration rate.

Inventors

Bong Sik Jeon
Yong Hee Lee
Woo Jin Park
Eui Geun JUNG
Wan Jae Myeong
Joung Woo HAN

Assignees

Hanwha Solutions Corporation

Dates

Publication Date: 20260505
Application Date: 20191029
Priority Date: 20181228

Claims (9)

1 . A catalyst for a hydrogenation reaction, comprising, based on 100 parts by weight of the entire catalyst, 60.9-80 parts by weight of nickel as a catalyst active component, 0.01-5 parts by weight of copper as an accelerator, and 10-30 parts by weight of silica as a support, wherein the silica as the support has a specific surface area of 300-400 m 2 /g and an average particle size of 3-10 μm, wherein a crystal size of the nickel is 4.9-6.6 nm.
2 . The catalyst of claim 1 , wherein an average particle size (d 50 ) of the catalyst is 3-10 μm, and a volume ratio of the catalyst having a particle size of 1 μm or less is 10% or less.
3 . The catalyst of claim 1 , wherein the catalyst has a specific surface area of 150-300 m 2 /g.
4 . A method for producing a catalyst for a hydrogenation reaction, the method comprising: preparing a first solution by dissolving a nickel precursor in a solvent so that a weight concentration (g/L) of nickel in a solution is 25-250; preparing a second solution by adding a copper precursor to the first solution so that a weight concentration (g/L) of copper in a solution is 0.01-5; preparing a third solution by dispersing a silica support in the second solution so that a weight concentration (g/L) of silica in a solution is 10-40; adding the third solution to a precipitation container, stirring the third solution, and heating the third solution to a temperature of 50-120° C.; adding a pH control agent to the heated third solution, causing the nickel and copper precursors to form a precipitate, and depositing the precipitate on the solid silica support; washing and filtering the supported catalyst and drying the supported catalyst at 100-200° C. for 5-24 hours; sintering the dried catalyst in air at a temperature of 200-500° C.; and activating the sintered catalyst by reducing the sintered catalyst at a temperature of 200-500° C. in a hydrogen atmosphere.
5 . The method of claim 4 , further comprising passivating the activated catalyst.
6 . The method of claim 5 , wherein the passivating is performed by passivating the activated catalyst with a nitrogen mixed gas including 0.1-20% oxygen.
7 . The method of claim 4 , further comprising passivating the activated catalyst by depositing the activated catalyst in a solution including a hydrocarbon resin.
8 . The method of claim 4 , wherein the precipitation is performed at pH 7-9.
9 . A method for hydrogenating a hydrocarbon resin, wherein the hydrocarbon resin is brought into contact with hydrogen in the presence of the catalyst produced by the method of claim 4 .

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application is a National Stage of International Application No. PCT/KR2019/014327 filed Oct. 29, 2019, claiming priority based on Korean Patent Application No. 10-2018-0173034 filed Dec. 28, 2018. TECHNICAL FIELD The present invention relates to a nickel hydrogenation catalyst and a method for producing the same, and more particularly, to a catalyst with improved activity, in which copper is used as an accelerator when a hydrogenation catalyst including nickel is produced using a deposition-precipitation (DP) method. Accordingly, the catalyst according to the present invention may be provided in a hydrocarbon resin hydrogenation process. BACKGROUND ART Naphtha cracking is an important process for the production of basic intermediates, such as lower olefins (i.e., ethylene, propylene, butylene, and butadiene) and aromatic compounds (i.e., benzene, toluene, and xylene), which are widely used in the petrochemical and chemical industries. Thermal cracking or steam pyrolysis is the main type of process that is typically performed for forming these materials in the presence of steam and in the absence of oxygen. The feedstock may include, in addition to naphtha, petroleum gases and distillates such as kerosene and gas oil. At this time, naphtha or the like may be pyrolyzed to produce materials such as C4 fraction including ethylene, propylene, butane, and butadiene, C5 fraction including dicyclopentadiene, isoprene, and piperylene, cracked gasoline (including benzene, toluene, and xylene), cracked kerosene (C9 or more fractions), cracked heavy oil (ethylene bottom oil), and hydrogen gas. Of these materials, hydrocarbon resins may be produced by polymerizing C5 and C9 fractions. Hydrocarbon resins among the C5 fractions include dicyclopentadiene (DCPD) as a main ingredient and may copolymerize propylene, isoprene, styrene, and the like. However, since hydrocarbon resins include unsaturated bonds in part, hydrocarbon resins have a yellow or orange color and have a peculiar bad smell of hydrocarbon resins. At this time, if a hydrogenation process of adding hydrogen is performed, unsaturated bonds are removed so that the color becomes brighter and the odor peculiar to hydrocarbon resins decreases, resulting in an improvement in quality. Hydrocarbon resins, from which unsaturated bonds are removed, are called water-white resins because they are colorless and transparent, and are distributed as high-quality resins with excellent heat resistance and ultraviolet (UV) stability. In the hydrocarbon resin hydrogenation process, the application of a hydrogenation catalyst is essential. As a hydrocarbon resin hydrogenation catalyst, noble metals such as palladium, platinum, and rhodium or transition metals such as nickel and cobalt are used as active ingredients, and the form supported by silica, alumina, activated carbon, titania, or the like is applicable. Korean Patent Publication No. 10-2017-0003425 discloses a result of using palladium as a hydrocarbon resin hydrogenation catalyst. In addition, Korean Patent Publication No. 1988-0002906 discloses a results of using a catalyst supporting palladium on a carbon support and a catalyst supporting nickel on an inert support as a hydrocarbon resin hydrogenation catalyst. A catalyst including nickel has an advantage of having high activity in a hydrogenation reaction, compared to catalysts including other transition metals. However, at least 40 wt % of nickel may be included in order to secure the activity of catalyst in a hydrocarbon resin hydrogenation reaction. In the case in which nickel is supported on a support, as the content of nickel is higher, the dispersibility is lowered, resulting in an increase in a crystal size of nickel. Accordingly, the activity of catalyst is decreased. If the content of nickel is lowered in order to prevent the above-described problem, the dispersibility is relatively improved, but the activity is decreased. Therefore, it is necessary to support a high content of nickel and to maintain the crystal of nickel in an appropriate size. On the other hand, a hydrocarbon resin hydrogenation reaction is performed by dispersing a powdery hydrogenation catalyst in a reactant solution, in which a hydrocarbon resin is dissolved, and then rotating at high speed. Since the catalyst is mixed in the solution, a filter is installed at an outlet of a reactor to separate the product solution from the catalyst. Since the product solution is filtered and separated through a catalyst layer on the filter surface, the filterability of the catalyst is one of the important indicators that determine the stable operation of the process. The filterability of the catalyst is generally determined by a catalyst particle size distribution. As a particle size increases, a pore volume between particles increases, resulting in an increase in filterability. In particular, since the pore size of the filter that separates the catalyst fr