JP3289326B2 - Production method of hydrogenated petroleum resins - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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 a long catalyst life when hydrogenating petroleum resins having an aromatic nucleus and / or an olefinic unsaturated bond.

[0002]

2. Description of the Related Art Spent fractions of C4 to C6 aliphatic olefins and Cs having an olefinically unsaturated bond obtained by the thermal cracking of petroleum naphtha or the catalytic cracking using a catalyst.
Among the eight or more aromatic hydrocarbon spent fractions, a resin obtained by homopolymerizing or copolymerizing one or more compounds contained in those fractions with a Friedel-Crafts type catalyst or heat Are called C5, C9 and C5 -C9 petroleum resins, respectively. These petroleum resins usually have a softening point of 60 to 140 ° C. and a molecular weight of 6
It is about 00 to 10000, and is widely used mainly for adhesives and plastic modifiers. These petroleum resins are generally colored yellow to light brown, and additionally have a unique odor. Therefore, it is difficult to use in the food field, sanitary field and printing applications where cleanliness is required,
There is a disadvantage that the working environment deteriorates. Therefore, a so-called hydrogenated petroleum resin has been developed in which these petroleum resins are hydrogenated in the presence of a catalyst to solve the above-mentioned disadvantages. This hydrogenated petroleum resin is usually transparent to white, has no odor, and has excellent properties in heat stability and weather resistance. Further, since it has excellent compatibility with various plastics, for example, rubber, polyolefin, ethylene-vinyl acetate copolymer, etc., it is used for hot melt adhesives and various plastic modifiers.

[0003] In producing hydrogenated petroleum resins by hydrogenating the above-mentioned petroleum resins, 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 a C9 petroleum resin containing an aromatic nucleus requires more severe conditions than that of a C5 petroleum resin. For example, Japanese Patent Publication No. 49-32438, column 2, 2-4
In the row, in the production of a C9-based hydrogenated petroleum resin using a Ni-diatomaceous earth catalyst, it is strict that a reaction temperature of 300 ° C., a hydrogen pressure of 200 kg / cm ² , and a reaction time of 6 hours or more are required in the presence of a catalyst concentration of 10% by weight. The conditions are described. Under such severe reaction conditions, the active sites of the hydrogenation catalyst often cause a melting phenomenon (sintering). As a result, the number of catalyst particles increases and the activity is rapidly lost.

On the other hand, since various spent fractions are used as petroleum resins, sulfur compounds contained in the raw material monomers are incorporated into petroleum resins. The amount of the sulfur compound varies depending on the source of the raw material naphtha, the kind of spent fraction and the polymerization conditions of petroleum resin.
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. 49-32438 discloses Ni-
A diatomaceous earth catalyst is disclosed. This discloses a technique for producing a highly active Ni-diatomaceous earth catalyst for hydrogenated petroleum resins,
No mention is made of catalyst sintering prevention technology or sulfur poisoning resistance technology. In addition, Japanese Patent Publication No. 62-612
No. 01 and JP-B-62-61202 disclose a technique for producing a hydrogenated petroleum resin using a platinum group catalyst. However, as shown in the examples, the catalytic activity decreases in a short period of time, and it is economically difficult to put it into practical use considering that the platinum group catalyst is expensive.

[0006]

As described above, the catalyst for hydrogenating petroleum resins has a high activity and a long catalyst life even under the above-mentioned severe reaction conditions, that is, it has no catalyst sintering, There is a demand for a catalyst for hydrogenated petroleum resins which is sulfurous, has a high catalytic activity, and has a long catalyst life, but a catalyst satisfying these performances has not yet been found. SUMMARY OF THE INVENTION An object of 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. is there.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have made intensive studies on catalysts for producing hydrogenated petroleum resins which are excellent in sulfur resistance without sintering of the catalyst. As a result, instead of a catalyst in which a single metal is supported on a carrier as in the past,
When a catalyst supporting two or more kinds of predetermined metals is used in a hydrogenation reaction of petroleum resins, a novel fact that can achieve the above object has been found, and the present invention has been completed.

That is, in the present invention, when hydrogenating a petroleum resin having an aromatic nucleus and / or an olefinic unsaturated bond, a catalyst having Ni and Cu supported on a carrier is used as a catalyst. Is manufactured. Hereinafter, the present invention will be described in detail.

Examples of the catalyst carrier usable in the present invention include diatomaceous earth having a large surface area, such as silica, alumina, silica alumina, activated carbon, and carbon black used for rubber or color.
Particularly, diatomaceous earth is preferred.

Ni is a metal element itself or N
i-metal halides, oxides, hydroxides, acid chlorides,
Nitrates, sulfates, carbonates and the like can be used. Of these, nitrates are more preferably used. The amount of Ni metal supported on the carrier is 1 to 300% by weight, preferably 10 to 200% by weight per carrier. If the amount of Ni to be supported is 1% by weight or less, the catalytic activity decreases, and the required number of used catalyst parts increases. As a result, the apparent viscosity of the raw petroleum resin solution containing the catalyst increases,
Stirring becomes difficult and it is not preferable in 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 diameter becomes large, and the catalytic activity decreases.

As Cu, an inorganic salt such as a halide, an oxide, a hydroxide, and a nitrate is used as the metal element itself. By adding Cu, the hydrogenation activity of Ni can be increased and maintained. That is, the growth (sintering) of Ni particles due to heat can be suppressed, and the poisoning by sulfur derived from the raw petroleum resin can be suppressed.

In the present invention, in addition to Cu , a Ni catalyst in which at least one selected from metals of Group IIa of the periodic table is supported on a carrier can be used. In this case, sintering suppression and sulfur poisoning suppression are further improved, and the hydrogenation activity of Ni can be increased and maintained. The metals of Group IIa of the periodic table include Be, Mg, Ca,
Sr, Ba , and Ra. Of these, preferably, M
g , Ca , Sr, and Ba. These elements alone do not have hydrogenation activity or have very low activity. As in the case of Ni, halides, oxides, hydroxides, acid chlorides, nitrates, sulfates, carbonates and the like of these metals can be used. Cu, Periodic Table I
The loading amount of the Ia group metal is 0.1 to 100 with respect to the Ni metal.
%, Preferably from 1 to 25% by weight.

As a method of supporting Ni and Cu and a metal of Group IIa of the periodic table on a carrier, an ordinary method for preparing a catalyst supported on a carrier may be used. For example, the desired catalyst can be obtained by dropping a precipitant into an aqueous solution of Ni or Cu, a metal salt of Group IIa of the Periodic Table , immersing the carrier, collecting the resulting solid by filtration, washing with water, drying, calcining and hydrogen reducing. can get. As the precipitant used here, for example, an aqueous solution of sodium hydroxide, potassium hydroxide, ammonia, sodium carbonate, potassium carbonate, ammonium carbonate or the like can be used. The shape of the catalyst is not particularly limited, but powder, extruded product, spray molded product,
Any shape such as a sphere-formed product and a tablet-formed product can be used. The catalyst thus obtained can be used for hydrogenating petroleum resins. The amount used is preferably in the range of 0.1 to 20% by weight per petroleum resin, more preferably 0.5 to 10% by weight.

The petroleum resins having an aromatic nucleus and / or an olefinically unsaturated bond according to the present invention may be a petroleum resin obtained by pyrolysis of petroleum naphtha or catalytic cracking using a catalyst.
Among the spent fractions of aliphatic olefins having 4 to 6 carbon atoms and those of aromatic hydrocarbons having 8 or more aromatic hydrocarbons having an olefinically unsaturated bond, one or more compounds contained in those fractions are used. C5 series, C9 series, and C5 to C5 series obtained by homogenization or copolymerization with a Friedel-Crafts type catalyst such as aluminum chloride and boron trifluoride or by heat.
It is a 9 series petroleum resin.

The compounds contained in the spent fraction of C4 to C6 aliphatic olefins include, for example, butene, pentene, hexene, heptene, butadiene, pentadiene, cyclopentadiene, dicyclopentadiene and the like. Examples of compounds contained in the spent fraction of C8 or higher aromatic hydrocarbons include styrene, α and β-methylstyrene, vinyl toluene, vinyl xylene, propenylbenzene, indene, methylindene, ethylindene, and the like. No.

The petroleum resins referred to in the present invention include not only polymers of spent fractions formed by thermal cracking or catalytic cracking of petroleum naphtha, butene, pentene, hexene, heptene, butadiene, pentadiene, cyclopentadiene, 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, a solvent which does not affect the catalytic performance and dissolves both the raw material and the hydrogenated petroleum resin is preferable. As this solvent, for example, isopentane, n-hexane, n-hexane
Examples include paraffins such as heptane, n-octane and n-decane, and cycloparaffins such as cyclopentane and cyclohexane, but the type of these solvents is not particularly limited. The amount of the solvent used is preferably 1 to 300% by weight, and more preferably 10 to 200% by weight, based on the petroleum resin.

The type of the hydrogenation reaction of the petroleum resin is not particularly limited, and examples thereof include a batch type suspension bed system, a flow type suspension bubble column, and a flow type fixed bed type. In this case, the reaction temperature is from 150 to 350 ° C, preferably from 200 to 300 ° C. Above 350 ° C., 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 . 3
If it is more than 00 kg / cm ² , it is not practical in terms of facilities and economy. Depending on the type of reaction, appropriate conditions described above can be selected.

[0019]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples unless the gist is exceeded.

Reference Example 1 (Preparation of Ni-Cu / diatomaceous earth catalyst) 247.6 g of nickel nitrate hexahydrate was dissolved in about 1 liter of water, and the solution was heated at a temperature of 50 liters.
After heating to ６０60 ° C., 100 g of diatomaceous earth was mixed, and 79 ml of a 2N—Cu (NO ₃ ) ₂ aqueous solution prepared in advance was added thereto, and a sodium hydroxide aqueous solution was added dropwise as a precipitant with stirring to cause a reaction. . After the completion of the dropwise addition, stirring was continued for another 1 hour at the same temperature. Then, the stirring was stopped and the resulting precipitate was allowed to stand for 30 minutes to mature the precipitate. The resulting precipitate was filtered off with suction and washed several times with 1 l of water.
Finally, it was washed and filtered with distilled water, and dried at 110 to 120 ° C. The dried product was calcined at 500 ° C. for 3 hours under nitrogen, and then reduced at 450 ° C. for 1 hour under a hydrogen stream to prepare a catalyst.

Reference Example 2 (Preparation of Ni-Cu-Mg / diatomaceous earth catalyst) 2N-Cu
At the same time as the (NO ₃ ) ₂ aqueous solution, 64 ml of a 1N-MgSO ₄ aqueous solution was added, and the same operation as in Reference Example 1 was performed.
A u-Mg / diatomaceous earth catalyst was prepared.

Reference Example 3 (Preparation of Ni / diatomaceous earth catalyst)
A Ni / diatomaceous earth catalyst was prepared by performing the same operation except that no (NO ₃ ) ₂ aqueous solution was used.

Example 1 A commercially available petroleum resin ("Petcoal 12" manufactured by Tosoh Corporation)
0 "Sulfur content 120ppm, Hue Gardner-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 placed in a 200-ml stainless steel pressure-resistant vessel equipped with a stirrer and a heater, and the atmosphere was replaced with nitrogen and then hydrogen, and then pressurized with hydrogen. 10
After a hydrogenation reaction was performed at 0 kg / cm ² H ₂ pressure at 290 ° C. for 4 hours, the mixture was allowed to cool. Of H ₂ Pas at room temperature - and di, the reaction product was removed, and the catalyst was removed by filtration. The solvent was distilled off from the reaction product under a nitrogen atmosphere to obtain a hydrogenated petroleum resin.

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

The catalyst of this example maintained a high degree of hydrogenation of about 96% even though it was repeatedly used four times, and the deterioration of the activity of the catalyst was very small. Further, the growth rate of the Ni metal crystallite diameter in the catalyst was low, and sintering was suppressed.

In the present example, the hydrogenation rate was determined by measuring the absorbance at 274.5 nm using an ultraviolet spectrometer and using the following equation. In the formula, A indicates the absorbance of the raw petroleum resin, and B indicates the absorbance of the petroleum resin after hydrogenation.

(A−B) × 100 / A (%) 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 equation. Where K is a constant, λ is the wavelength of the X-ray, and Δ (2
θ) indicates the diffraction line width, and θ ₀ indicates the diffraction angle.

Kλ / Δ (2θ) cosθ ₀ Example 2 In Example 1, a Ni—Cu / diatomaceous earth catalyst was used.
A hydrogenation reaction was carried out in the same manner as in Example 1, except that the catalyst was replaced with the Ni-Cu-Mg / diatomaceous earth catalyst prepared in the above. Table 2 shows the analysis result of the obtained hydrogenated petroleum resin and the crystallite diameter of Ni metal.

In this example, the catalyst was not deteriorated despite repeated use four times, the high hydrogenation rate of about 97% was maintained, and the catalyst activity was maintained. In addition, the growth rate of the Ni metal crystallite diameter in the catalyst was small, and almost no sintering occurred, which was higher than that of Example 1.

Comparative Example In Example 1, a Ni—Cu / diatomaceous earth catalyst was used.
A 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 used. Table 3 shows the analysis results of the obtained hydrogenated petroleum resins and the crystallite diameter of Ni metal.

In the comparative example, even when the catalyst was used only three times, the activity of the catalyst was significantly deteriorated, and the hydrogenation rate was about 90%. Also, the growth rate of Ni crystallite diameter in the catalyst is remarkable,
Intense sintering was noted.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

Thus, the novel Ni-based catalyst of the present invention is
Compared to the catalyst used in the conventional method, sintering is remarkably suppressed, excellent in sulfur resistance, high activity and long catalyst life, so that hydrogenated petroleum resins which are inexpensive and excellent in quality can be stably prepared. Can be given.

Claims (4)

(57) [Claims] 1. A hydrogenated petroleum resin characterized in that, when hydrogenating a petroleum resin having an aromatic nucleus and / or an olefinically unsaturated bond, a catalyst having Ni and Cu supported on a carrier is used as a catalyst. Manufacturing methods. 2. A catalyst comprising Ni , Cu and Periodic Table II.
The method according to claim 1, wherein a catalyst is used in which at least one member selected from the group a metals is supported on a carrier. 3. The method according to claim 2, wherein at least one selected from metals of Group IIa of the periodic table is at least one selected from Mg, Ca, Sr, and Ba. 4. The petroleum resin having an aromatic nucleus and / or an olefinically unsaturated bond is a C9 petroleum resin.
The method according to any one of claims 1 to 3.