JPH0625323A - Productoin of hydrogenated petroleum resin - Google Patents

Abstract

PURPOSE:To enable inexpensive production of hydrogenated petroleum resins by hydrogenating petroleum resins having aromatic nuclei and olefinic unsaturated bonds in the presence of a catalyst carrying Ni and a specific metal with prolonged catalytic life due to its excellent resistance to sulfur and sintering. CONSTITUTION:A petroleum resin having aromatic nuclei and/or olefinic unsaturated bonds is dissolved in cyclohexane and charged into a stainless steel pressure vessel together with a catalyst which is prepared by carrying Ni, at least one of metals in group IIb of the periodic table such as Cu, Ag, Au or at least one of metals in group IIa such as Mg, Ca, sr or Ba on a support such as diatomaceous earth. The inside space of the vessel is replaced with nitrogen gas, then hydrogen, pressurized to effect the hydrogenation at 10kg/cm<2> hydrogen pressure and at 290 deg.C for 4 hours. Thus, inexpensive and high-quality hydrogenated petroleum resin is obtained by using a catalyst of high activity having prolonged catalyst life and improved sintering resistance and sulfur resistance.

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, which uses 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]

2. Description of the Related Art Spent fractions of C4 to C6 aliphatic olefins obtained by thermal cracking of petroleum naphtha or catalytic cracking using a catalyst and C having olefinic unsaturated bonds
Of the aromatic hydrocarbon spent spent fractions, resins obtained by subjecting one or more compounds contained in those fractions to homo- or copolymerization 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 6
It is about 00 to 10,000 and is widely used mainly as an adhesive or a plastic modifier. 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,
There is a drawback that the working environment deteriorates. Therefore, so-called hydrogenated petroleum resins have been developed in which these petroleum resins are hydrogenated in the presence of a catalyst to solve the above-mentioned drawbacks. This hydrogenated petroleum resin is usually transparent to white, has no odor, and has excellent heat stability and weather resistance. Further, since it has excellent compatibility with various plastics such as rubber, polyolefin, and ethylene-vinyl acetate copolymer, 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
According to the line, 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 various spent fractions as a raw material, the sulfur compounds contained in the raw material monomer are 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 technology. In addition, Japanese Examined Japanese Patent Publication No.
No. 01 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. An object of the present invention is to provide a method for producing a hydrogenated petroleum resin excellent in quality by solving the above-mentioned conventional problems in hydrogenating a petroleum resin having an aromatic nucleus and / or an olefinic unsaturated bond. is there.

[0007]

Means for Solving the Problems 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 olefinic unsaturated bond, at least one selected from Ni and a metal of Group Ib 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 is deteriorated, the metal particle size is increased, and the catalytic activity is decreased.

Metals of Group Ib of the periodic table are Cu, Ag,
Au, and of these, Cu is preferable. These may be inorganic elements such as halides, oxides, hydroxides and nitric oxides as the metal element itself.
By adding these group Ib, the hydrogenation activity of Ni can be increased and maintained. That is, it is possible to suppress the growth (sintering) of Ni particles due to heat, and to suppress the poisoning due to the sulfur derived from the raw material petroleum resin.

In the present invention, in addition to at least one metal selected from Group Ib of the Periodic Table, IIa
It is also possible to use a Ni catalyst in which at least one selected from the group metals is supported on a carrier. In this case, the suppression of sintering and the suppression of sulfur poisoning are further improved, and the hydrogenation activity of Ni can be increased and maintained. Metals of Group IIa of the Periodic Table are Be, Mg, Ca, Sr, B
a and Ra, and of these, Mg and C are preferable.
a, Sr, and Ba. These elements have no hydrogenation activity by themselves, 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. Periodic Table Ib, IIa
The amount of the group metal carried is in the range of 0.1 to 100% by weight, preferably 1 to 25% by weight, based on the Ni metal.

As a method of supporting Ni and a metal of Group Ib or IIa of the periodic table on a carrier, a usual method for preparing a carrier-supported catalyst may be used. For example, Ni in which a carrier is dipped or Periodic Table I
The desired catalyst can be obtained by dropping a precipitant into an aqueous solution of a b, IIa metal salt and collecting and collecting the resulting solid by filtration, washing with water, drying, calcination and hydrogen reduction. 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 may be powder, extrusion molding, spray molding,
Any shape such as a sphere-forming product or a tablet-molded product can be used. The catalyst thus obtained can be used for hydrogenation of petroleum resins. The amount used is preferably in the range of 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, based on the petroleum resin.

The petroleum resins having an aromatic nucleus and / or an olefinically unsaturated bond according to the present invention are C obtained by thermal decomposition of petroleum naphtha or catalytic cracking using a catalyst.
Among the spent fractions of 4 to C6 aliphatic olefins and the spent fractions of C8 or more aromatic hydrocarbons having an olefinic unsaturated bond, one or more compounds contained in those fractions are used. Freeder-Crafts type catalysts such as aluminum chloride and boron trifluoride, and C5 series, C9 series and C5 to C obtained by heat or homopolymerization
It is a 9-based 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 compounds contained in the spent fraction of aromatic hydrocarbons having C8 or more include styrene, α- and β-methylstyrene, vinyltoluene, vinylxylene, propenylbenzene, indene, methylindene, ethylindene and the like. Can be mentioned.

The petroleum resins referred to in the present invention include not only a polymer of a spent fraction produced by thermal decomposition or catalytic cracking of petroleum naphtha, but also butene, pentene, hexene, heptene, butadiene, pentadiene, cyclopentadiene, diene. 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 which do not affect the catalyst 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, and cycloparaffins such as cyclopentane and cyclohexane, but the types of these solvents are 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 type of hydrogenation reaction 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. At 350 ° C. or higher, decomposition of petroleum resins occurs, 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 . Three
00 kg / cm ² or more is not practical in terms of equipment and economy. For these, appropriate conditions described above can be selected depending on the type of reaction.

[0019]

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-Cu / 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.
Diatomaceous earth 100g then heated to to 60 ° C. and mixed to this, the addition of 2N-Cu (NO _{3) 2} aqueous solution 79ml was prepared in advance, is reacted by dropwise addition of aqueous sodium hydroxide as a precipitating agent while stirring . 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 precipitate obtained is suction filtered and then 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 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 (Preparation of Ni-Cu-Mg / diatomaceous earth catalyst) 2N-Cu
Simultaneously with 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) In Reference Example 1, Cu
A Ni / diatomaceous earth catalyst was prepared by performing the same operation except that the (NO ₃ ) ₂ aqueous solution was not used.

Example 1 Commercially available petroleum resin ("Petcole 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 placed in a pressure-resistant stainless steel container having an inner volume of 200 ml equipped with a stirrer and a heater, and the atmosphere was replaced with nitrogen and then hydrogen, and then pressurized with hydrogen. 10
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.

Then, 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 diameter of Ni metal in the catalyst.

The catalyst of this example maintained a high hydrogenation rate of about 96%, even though it was repeatedly used four times, 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 was suppressed.

In the present example, the hydrogenation rate was determined by the following formula 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. Where K is a constant, λ is the wavelength of X-rays, and Δ (2
θ) indicates the diffraction line width, and θ ₀ indicates the diffraction angle.

Kλ / Δ (2θ) cos θ ₀ Example 2 In Example 1, a Ni-Cu / diatomaceous earth catalyst was used as Reference Example 2.
The hydrogenation reaction was carried out in the same manner as in Example 1 except that the Ni-Cu-Mg / diatomaceous earth catalyst prepared in step 1 was used. Table 2 shows the analysis results of the obtained hydrogenated petroleum resin and the crystallite diameter of Ni metal.

In this example, the catalyst did not deteriorate despite being repeatedly used four times, the high hydrogenation rate of about 97% was maintained, and the sustained catalytic activity was observed. In addition, the growth rate of the Ni metal crystallite diameter in the catalyst was small, sintering hardly occurred, and it was higher than in Example 1.

Comparative Example In Example 1, the Ni-Cu / 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.

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

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

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 (5)

[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 Ib 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. A catalyst in which at least one selected from Ni and a metal of Group Ib of the periodic table and at least one selected from a metal of Group IIa of the periodic table are supported on a carrier as a catalyst. The method according to 1. 3. The method according to claim 2, wherein at least one selected from the group IIa metals 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.
4. The method according to claim 3, wherein 5. The method according to claim 1, wherein at least one selected from metals of Group Ib of the periodic table is Cu.