JPH05239125A - Production of hydrogenated petroleum resin - Google Patents

Abstract

PURPOSE:To obtain a hydrogenated petroleum resin having high quality at a low cost by using a specific Ni-based catalyst resistant to sintering and having excellent sulfur-resistance, high activity and long catalytic life as a catalyst for the hydrogenation of petroleum resin. CONSTITUTION:A hydrogenated petroleum resin is produced by hydrogenating a petroleum resin having aromatic and/or olefinic unsaturated bonds (especially 9C petroleum resin) at 150-350 deg.C optionally in a solvent in the presence of 0.1-20wt.%, preferably 0.5-10wt.% (based on the petroleum resin) of a catalyst produced by supporting 1-300wt.% of Ni (preferably Ni nitrate) and 0.1-100wt.%, preferably 1-25wt.% of a metal of the group IIa of the periodic table (preferably Mg, Ca, Sr or Ba) on a carrier (preferably diatomaceous earth). The catalyst is resistant to sintering, has excellent sulfur-resistance, high catalytic activity and long catalytic life and is especially effective for hydrogenating a 9C petroleum resin containing aromatic nucleus.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing hydrogenated petroleum resins. More specifically, the present invention relates to a method for producing hydrogenated petroleum resins using an improved Ni-based catalyst having high activity and long catalyst life for hydrogenating petroleum resins having aromatic nuclei and / or olefinic unsaturated bonds.

[0002]

BACKGROUND OF THE INVENTION Spent fraction of C4 to C6 aliphatic olefins obtained by thermal cracking or catalytic cracking of petroleum naphtha and C having olefinic unsaturated bonds.
Among the spent fractions of 8 or more aromatic hydrocarbons, a resin obtained by homopolymerizing or copolymerizing one or more compounds contained in those fractions with a Friedel-Crafts catalyst or heat. Are called C5-based, C9-based and C5-C9-based petroleum resins, respectively. These petroleum resins usually have a softening point of 60 to 140 ° C. and a molecular weight of about 600 to 10,000, and are widely used mainly as adhesives and plastic modifiers. These petroleum resins are generally colored yellow to light brown and have a unique odor. Therefore, it is difficult to use in the food field, sanitary field and printing applications where cleanliness is required, and there is a drawback that the working environment deteriorates. Therefore, so-called loose hydrogenated petroleum resins have been developed which solve the above-mentioned drawbacks by hydrogenating these petroleum resins in the presence of a catalyst. This hydrogenated petroleum resin is usually transparent to white, has no odor, and has excellent heat stability and weather resistance. Furthermore,
Various plastics such as rubber, polyolefin,
Since it has excellent compatibility with ethylene-vinyl acetate copolymer and the like, it is used for hot-melt adhesives and various plastic modifiers.

By the way, in producing a hydrogenated petroleum resin by hydrogenating the above-mentioned petroleum resin, the hydrogenation reaction is much more difficult than the hydrogenation reaction of the monomer, and severe reaction conditions are required. Becomes In particular, hydrogenation of C9 petroleum resin containing aromatic nuclei requires more severe conditions than that of C5 petroleum resin. For example, Japanese Examined Patent Publication No. S49-32438, columns 2 to 4
The line shows that in the production of C9 hydrogenated petroleum resin using Ni-diatomaceous earth catalyst, the reaction temperature is 300 ° C., the hydrogen pressure is 200 kg / cm ² , and the reaction time is 6 hours or more. The conditions are listed. Under such harsh reaction conditions, the active sites of the hydrogenation catalyst often cause a melting phenomenon (sintering). As a result, the catalyst particles increase and the activity is rapidly lost.

On the other hand, since the petroleum resin uses each spent fraction as a raw material, the sulfur compound contained in the raw material monomer is incorporated into the petroleum resin. The amount of the sulfur compound varies depending on the source of the raw material naphtha, the type of the spent fraction, the petroleum resin polymerization conditions, etc.
It is about 0 to 500 ppm. The sulfur compound incorporated in the petroleum resin acts as a catalyst poison on the hydrogenation catalyst in the production of the hydrogenated petroleum resin, deteriorating the catalytic activity and significantly shortening the catalyst life.

As a catalyst for producing a hydrogenated petroleum resin, for example, Japanese Patent Publication No. Sho 49-32438 discloses Ni-.
A diatomaceous earth catalyst is disclosed. This discloses a technology for producing a highly active Ni-diatomaceous earth catalyst for hydrogenated petroleum resin,
No mention is made of catalyst sintering prevention technology and sulfur poisoning resistance technology. In addition, Japanese Examined Japanese Patent Sho 62-61
No. 201 and Japanese Patent Publication No. 62-61202 disclose a technology for producing a hydrogenated petroleum resin using a platinum group catalyst. However, as shown in the examples, the catalytic activity is reduced in a short period of time, and considering that the platinum group-based catalyst is expensive, it is economically unpractical.

[0006]

As described above, the catalyst for hydrogenation of petroleum resin is highly active and has a long catalyst life even under the severe reaction conditions described above, that is, there is no sintering of the catalyst, A catalyst for hydrogenated petroleum resin having sulfur property, high catalytic activity and long catalyst life is required, but a catalyst satisfying these performances has not yet been found. The present invention is to provide a method for producing a hydrogenated petroleum resin having excellent quality, which solves the conventional problems in hydrogenating a petroleum resin having an aromatic nucleus and / or an olefinically unsaturated bond.

[0007]

DISCLOSURE OF THE INVENTION The inventors of the present invention have earnestly studied a catalyst for producing hydrogenated petroleum resins having excellent sulfur resistance without sintering of the catalyst. As a result, instead of a conventional catalyst in which a single metal is supported on a carrier,
The present invention has been completed by finding out the novel fact that the above-mentioned object can be achieved by using a catalyst formed by supporting two or more kinds of predetermined metals in the hydrogenation reaction of petroleum resins.

That is, in the present invention, when hydrogenating a petroleum resin having an aromatic nucleus and / or an olefinically unsaturated bond, at least one selected from Ni and a metal of Group IIa of the periodic table is used as a catalyst as a catalyst. It is characterized in that hydrogenated petroleum resins are produced using the supported catalyst. Hereinafter, the present invention will be described in detail.

Examples of the catalyst carrier which can be used in the present invention include porous diatomaceous earth having a large surface area, silica, alumina, silica-alumina, activated carbon, and carbon black used for rubber or color.
Diatomaceous earth is particularly preferable.

As Ni, the metal element itself or N
i metal halides, oxides, hydroxides, acid chlorides,
Nitrate, sulfate, carbonate, etc. can be used. Of these, nitric oxide is more preferably used. The amount of Ni metal supported on the carrier is 1 to 300% by weight, preferably 10 to 200% by weight, based on the carrier. When the supported Ni content is 1% by weight or less, the catalytic activity becomes small and the required number of used catalyst parts becomes large. As a result, the apparent viscosity of the raw material petroleum resin solution containing the catalyst increases,
Stirring becomes difficult, which is not preferable for handling. On the other hand, when the supported amount is 300% by weight or more, the dispersion of the metal component on the carrier becomes poor, the metal particle size increases, and the catalytic activity also decreases.

The metals of Group IIa of the periodic table are Be and M.
g, Ca, Sr, Ba and Ra, and of these, Mg, Ca, Sr and Ba are preferable. These elements alone have no hydrogenation activity, or have extremely low activity even if they have hydrogenation activity. As in the case of Ni, halides, oxides, hydroxides, acid chlorides, nitrates, sulfates, carbonates and the like of these metals can be used. The loading amount of the group IIa metal of the periodic table is 0.1 to 1 with respect to the Ni metal.
It is in the range of 00% by weight, preferably 1 to 25% by weight.

As a method for supporting Ni and a Group IIa metal of the Periodic Table on a carrier, an ordinary method for preparing a carrier-supported catalyst may be used. For example, the carrier may be added to an aqueous solution of Ni or a Group IIa metal salt of the Periodic Table. It can be easily supported by immersion. Subsequent reduction gives the desired catalyst. The shape of the catalyst is not particularly limited, but powder,
Any shape such as an extrusion molded product, a spray molded product, a ball-forming molded product, and a tablet molded product can be used. The hydrogenation catalyst thus obtained is used for hydrogenating petroleum resins. The amount used is in the range of 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the petroleum resin.

The petroleum resin having an aromatic nucleus and / or an olefinic unsaturated bond according to the present invention is obtained by thermal cracking of petroleum naphtha or catalytic cracking using a catalyst.
Of the spent fractions of C4 to C6 aliphatic olefins and the spent fractions of aromatic hydrocarbons of C8 or more having an olefinic unsaturated bond, one or more of the compounds contained in those fractions are Freeder-Crafts type catalysts such as aluminum chloride and boron trifluoride, and C5 series, C9 series and C5 series obtained by heat or homopolymerization
~ C9 petroleum resin.

Examples of the compound contained in the spent fraction of the C4 to C6 aliphatic olefin include butene, pentene, hexene, heptene, butadiene, pentadiene, cyclopentadiene and dicyclopentadiene. Examples of the compound contained in the spent fraction of C8 or higher aromatic hydrocarbon include styrene, α- and β-methylstyrene, vinyltoluene, vinylxylene, propenylbenzene, indene,
Examples include methylindene and ethylindene.

The petroleum resins referred to in the present invention include not only a polymer of a spent fraction produced by thermal or catalytic cracking of petroleum naphtha, but also butene, pentene, hexene, heptene, butadiene, pentadiene, cyclopentadiene, dipentane. Carbonization obtained by polymerizing one or more polymerizable monomers selected from cyclopentadiene, styrene, α- and β-methylstyrene, vinyltoluene, vinylxylene, propenylbenzene, indene, methylindene, ethylindene, etc. There is no problem even if it is a hydrogen-based polymerization composition.

In the hydrogenation of petroleum resins, the petroleum resins may be used as they are, but an appropriate solvent may be used. As the solvent, those that do not affect the catalytic performance and dissolve both the raw material and the hydrogenated petroleum resin are preferable. Examples of the solvent include isopentane, n-hexane, n
Examples include paraffins such as -heptane, n-octane, and n-decane; cycloparaffins such as cyclopentane and cyclohexane; however, the type of these solvents is not particularly limited. The amount of solvent used is preferably 1 to 300% by weight, preferably 10 to 200% by weight, based on the petroleum resin.

The hydrogenation reaction system of petroleum resins is not particularly limited, and examples thereof include a batch type suspension bed system, a flow type suspension bubble column or a flow type fixed bed system. In this case, the reaction temperature is 150 to 350 ° C, preferably 200 to 300 ° C. If the temperature is higher than 350 ° C, the petroleum resins are decomposed, which is not preferable in terms of quality and yield. The hydrogen pressure is usually in the range of atmospheric pressure to 300 kg / cm ² , preferably 10 to 200 kg / cm ² .
When it is 300 Kg / cm ² or more, it is not practical in terms of equipment and economy. For these, appropriate conditions described above can be selected depending on the type of reaction.

[0018]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Reference Example 1 (Preparation of Ni-Mg / diatomaceous earth catalyst) 247.6 g of nickel nitrate hexahydrate was dissolved in about 1 l of water, and this was heated at a temperature of 50.
After heating to -60 ° C, 100 g of diatomaceous earth was mixed, and 64 m of 1N-MgSO ₄ aqueous solution prepared in advance was mixed with this.
1 was added, and an aqueous sodium hydroxide solution as a precipitating agent (alkali agent) was added dropwise with stirring to react. As the precipitating agent, an aqueous solution of potassium hydroxide, ammonia, sodium carbonate, potassium carbonate, ammonium carbonate or the like can be similarly used. After the dropwise addition was completed, stirring was continued while maintaining the same temperature for another hour. Then, the stirring was stopped and the precipitate formed was allowed to stand for 30 minutes for aging. The obtained precipitate was filtered by suction, washed with 1 l of water several times, finally washed with distilled water, filtered, and dried at 110 to 120 ° C. The dried product was calcined under nitrogen at 500 ° C. for 3 hours, and subsequently reduced under a hydrogen stream at 450 ° C. for 1 hour to prepare a catalyst.

Reference Example 2 (Ni-Ca / diatomaceous earth, Ni-Sr / diatomaceous earth, Ni-B
a / Preparation of diatomaceous earth catalyst) Instead of MgSO ₄ aqueous solution, C
NaCl ₂ solution, SrCl ₂ solution, using BaCl ₂ aqueous solution of sodium carbonate in combination with the same activities as in Reference Example 1 as a precipitating agent, Ni-Ca / kieselguhr, Ni-Sr
/ Diatomaceous earth, Ni-Ba / diatomaceous earth catalyst were prepared.

Reference Example 3 (Preparation of Ni / diatomaceous earth catalyst) In Reference Example 1, MgS
A Ni / diatomaceous earth catalyst was prepared by performing the same operation except that the O ₄ aqueous solution was not used.

Example 1 Commercially available petroleum resin (PETCOL 12 manufactured by Tosoh Corporation)
0 "Sulfur content 120 ppm, Hue guarder color number 1
2) 50 g was dissolved in 50 g of cyclohexane. This solution and 2.5 g of the catalyst prepared in Reference Example 1 were charged into a pressure-resistant stainless steel container having an internal volume of 200 ml equipped with a stirrer and a heater, and the atmosphere was replaced with nitrogen and then with hydrogen, and hydrogen was pressurized. 8
After hydrogenation reaction was carried out at 0 Kg / cm ² H ₂ pressure, 290 ° C. for 4 hours, the mixture was allowed to cool. H ₂ was purged at room temperature, the reaction product was taken out, and the catalyst was filtered off. For the reaction product, the solvent was distilled off under a nitrogen atmosphere to obtain a hydrogenated petroleum resin.

Next, the catalyst recovered by filtration was repeatedly used in the hydrogenation reaction of petroleum resin. Table 1 shows the analysis results of the hydrogenated petroleum resin obtained by repeated use of the catalyst and the crystallite size of Ni metal in the catalyst.

[0024]

[Table 1] Although the catalyst of this example was repeatedly used 5 times,
The high hydrogenation rate of about 95% was maintained, and the activity deterioration of the catalyst was very small. In addition, the growth rate of the Ni metal crystallite diameter in the catalyst was small, and sintering hardly occurred.

In the present example, the hydrogenation rate was determined by the following equation by measuring the absorbance at 274.5 nm using an ultraviolet spectroscope. In the formula, A represents the absorbance of the raw material petroleum resin, and B represents the absorbance of the petroleum resin after hydrogenation. (A−B) × 100 / A (%) Further, the crystallite diameter of Ni metal was 39 using an X-ray diffractometer.
The X-ray diffraction intensity at -50 ° was measured, and the crystallite diameter was calculated by the following formula. Kλ / Δ (2θ) cos θ _{0 In the} equation, K is a constant, λ is the wavelength of X-rays, Δ (2θ) is the diffraction line width, and θ ₀ is the diffraction angle.

Example 2 In Example 1, a Ni-Mg / diatomaceous earth catalyst was used as a reference example 2.
The hydrogenation reaction was carried out in the same manner as in Example 1 except that the Ni-Ca / diatomaceous earth and Ni-Ba / diatomaceous earth catalysts prepared in 1. were used. Table 2 shows the analysis results of the obtained hydrogenated petroleum resin and the crystallite diameter of Ni metal.

[0027]

[Table 2] In this example, the catalyst was not deteriorated even though it was repeatedly used four times, and the high hydrogenation rate of about 95% or more was maintained.
Persistence of catalytic activity was observed, the growth rate of the Ni metal crystallite diameter in the catalyst was small, and sintering hardly occurred. Moreover, the same result was shown also when using a Ni-Sr / diatomaceous earth catalyst.

Comparative Example In Example 1, a Ni-Mg / diatomaceous earth catalyst was used as Reference Example 3.
The hydrogenation reaction was carried out in the same manner as in Example 1 except that the Ni / diatomaceous earth catalyst prepared in step 1 was replaced. Table 3 shows the analysis results of the obtained hydrogenated petroleum resin and the crystallite diameter of Ni metal.

[0029]

[Table 3] In the comparative example, even when it was repeatedly used only three times, the activity of the catalyst was severely deteriorated and the hydrogenation rate was about 90%. Further, the growth rate of the Ni crystallite diameter in the catalyst was remarkable, and intense sintering was observed.

[0030]

Thus, the novel Ni-based catalyst of the present invention is
Compared with the catalysts used in conventional methods, sintering is significantly suppressed, sulfur resistance is excellent, high activity and long catalyst life make it possible to stabilize hydrogenated petroleum resins that are inexpensive and excellent in quality. Can be given.

Claims (3)

[Claims] 1. When hydrogenating a petroleum resin having an aromatic nucleus and / or an olefinic unsaturated bond, at least one selected from Ni and a metal of Group IIa of the periodic table is supported on a carrier as a catalyst. A method for producing a hydrogenated petroleum resin, which comprises using a catalyst. 2. The method according to claim 1, wherein the petroleum resin having an aromatic nucleus and / or an olefinically unsaturated bond is a C9 petroleum resin. 3. The method according to claim 1 or 2, wherein at least one selected from the metals of Group IIa of the periodic table is Mg, Ca, Sr or Ba.