JPH01190704A - Production of hydrogenated petroleum resin - Google Patents

Abstract

PURPOSE:To obtain the title resin economically in a high degree of hydrogenation by facilitating reaction control, by passing a molten aromatic ring- containing petroleum resin and hydrogen gas through a reactor packed with a specified fixed bed catalyst. CONSTITUTION:A mixture of at least 50wt.% aromatic unsaturated hydrocarbon with, optionally, other olefins is polymerized in the presence of a Friedel-Crafts catalyst to obtain an aromatic nucleus-containing petroleum resin (A). Molten component A and a hydrogen gas in an amount 2-50 times larger than the theoretical hydrogen up-take of component A are passed through a reactor packed with a fixed bed catalyst composed of Pd supported on a carrier, preferably, alumina at a space velocity (the volume of the feed of the petroleum resin per hr/the volume of the catalyst packed) of 0.01-10hr<-1> and hydrogenated at 200-350 deg.C under a pressure of 10-300kg/cm<2> to a degree of hydrogenation of the aromatic nuclei of component A of at least 50%, preferably 50-70%.

Description

[Detailed description of the invention] upper profit The present invention relates to a method for producing hydrogenated petroleum resin.

The so-called petroleum resin, which is obtained by polymerizing the thermal decomposition product of Hongdae Wuhan Petroleum Naphtha in the presence of a free-solat fluorocarbon, is mainly used as a tackifier for adhesives or adhesives, and as a modifier for compounding plastics. Resins suitable for these uses usually have a softening point of 80 to 140°C and a molecular weight of about 800 to 10,000. Above all, these hydrogenated petroleum resins have good weather resistance, color tone, stability, etc., and are also good in compatibility with rubber, polyolefin, ethylene-vinyl acetate copolymer, etc., so they are suitable for the above uses. It is particularly excellent as a resin to be used. However, petroleum resins are much more difficult to hydrogenate than resins due to their raw materials. Although the reason for this has not yet been fully elucidated, it is generally known from experience that as the degree of polymerization increases, hydrogenation becomes more difficult. In particular, when replacing the benzene ring of a petroleum resin with an aromatic ring with a cyclohexane ring, a large amount of catalyst is added and the hydrogenation reaction is difficult to proceed unless severe conditions such as high temperature, high pressure, and long time are used.

Conventionally, as a method for producing hydrogenated petroleum resins, a batch suspension bed system or a flow suspension bubble column system using a powdered nickel catalyst or platinum catalyst has generally been adopted. However, when this conventional method is employed, a filtration step is essential to separate the hydrogenated petroleum resin from the powdered catalyst after hydrogenation. Moreover, among the above-mentioned petroleum resins, those with a high softening point, that is, those with high viscosity, are difficult to filter in a molten state, and filtration is delayed, so xylene,
Hydrogenated petroleum resin can only be obtained by diluting the catalyst with an organic solvent such as toluene, filtering the catalyst, and then evaporating the solvent from the filtrate. Therefore, the production process is extremely complicated, and it also leads to an increase in product cost, which is undesirable. In particular, when a platinum catalyst is used as the catalyst in the conventional method, the catalyst is very expensive and cannot be quantitatively recovered, resulting in a large economic loss.

In view of the above problems, a method for producing hydrogenated petroleum resin using a fixed bed of platinum or rhodium catalyst (Japanese Unexamined Patent Publication No. 59-75
No. 904 and Japanese Patent Application Laid-open No. 59-13Ei312), and according to this method, the complexity of the production process can be sufficiently solved. However, noble metal catalysts such as platinum and rhodium are very expensive and have a high production cost, which has not been solved yet.

Usually, hydrogenated petroleum resin has a hydrogenation rate of aromatic nuclei of 50 to 70.
%, the compatibility with ethylene-vinyl acetate copolymer etc. is best. However, hydrogenation catalysts such as nickel, platinum, and rhodium have a very high ability to hydrogenate aromatic nuclei.
Most of the aromatic nuclei can be easily hydrogenated. Therefore, when a noble metal catalyst such as nickel, platinum, or rhodium is used, it also has the disadvantage that it is difficult to control the hydrogenation reaction so that the hydrogenation rate of aromatic nuclei is in the range of about 50 to 70%.

While the hydrogenation is about to occur, the present invention aims at producing a simple and economical hydrogenated petroleum resin in which the hydrogenation reaction can be easily controlled despite the hydrogenation rate of aromatic nuclei being as high as 50% or more. The purpose was to provide a method.

□ 1. To Ru - Wood The inventors have conducted extensive studies focusing on hydrogenation catalysts in view of the above technical and economic backgrounds, and have found that when a palladium catalyst is used and a specific reaction method is adopted. They found a way to solve all of the above problems and completed the present invention.

That is, in hydrogenating a petroleum resin having an aromatic nucleus, the present invention involves filling a reactor with a fixed bed catalyst in which palladium is supported on a carrier, and supplying hydrogen gas and molten petroleum resin to the reactor-h section or the lower part of the reactor. The present invention relates to a method for producing a hydrogenated petroleum resin, characterized in that hydrogenation is carried out continuously by flowing downward or upward in a cocurrent flow to hydrogenate 50% or more of the aromatic nuclei.

In the present invention, petroleum resins having aromatic nuclei refer to aromatic unsaturated hydrocarbons or mixtures with other olefins containing at least 50% by weight of aromatic unsaturated hydrocarbons, such as aluminum chloride and boron trifluoride. It refers to a polymer obtained by polymerization in the presence of a Friedel-Krauch catalyst.

Here, aromatic unsaturated hydrocarbons refer to those with a boiling point of 100 to 280°C among those obtained by decomposition of petroleum, and specifically, styrene, α-methylstyrene,
Examples include vinyltoluene, propenylbenzene, vinylxylene, indene, methylindene, and ethylindene. Other olefins include butene, pentene, hexene, heptene, octene, butadiene,
Examples include pentadiene, cyclopentadiene, dicyclopentadiene, and octadiene.

In the present invention, it is essential to use a catalyst in which palladium is supported on a carrier. This is because, in light of the above-mentioned objectives of the present invention, the catalyst of the present invention is relatively inexpensive, and the hydrogenation ability of the aromatic nuclei of petroleum resins is smaller than that of platinum, rhodium, etc., despite the high hydrogenation rate. This is because a hydrogenation catalyst that can easily control the hydrogenation reaction is required. In addition, the petroleum resin usually has a sulfur content of 100% as sulfur.
Since the content is ~500 ppm, it must have good resistance to sulfur poisoning, and it must also have good resistance to sulfur heat, taking into account the large amount of reaction heat generated by hydrogenation of aromatic nuclei.

As a result of examining various factors on V, surprisingly, palladium was supported on the phase. Very satisfactory results were obtained using fixed bed catalysts.

Further, the carrier supporting palladium is not particularly limited, but a porous carrier having a large surface area, such as alumina, silica, carbon, titania, etc., may be used. Among these, alumina is particularly preferred. It is not clear why alumina is particularly preferable as a carrier, but the reason is that palladium, which is a supported metal, tends to be highly dispersed compared to other carriers, and that hydrogen dissociated on palladium migrates as a spillover (phase). This is thought to be due to the fact that it is easy to do.

The amount of palladium supported on the carrier is also not particularly limited, but is usually about 0.2 to 10% by weight based on the weight of the carrier.
Preferably it is 0.5 to 5% by weight.

The shape of the catalyst obtained as described above may be cylindrical, extrudate, pellet, or spherical, but spherical is particularly preferred. Further, since the size of the catalyst affects the effective activity of the catalyst, it is preferable to use the smallest possible catalyst. More specifically, the catalyst is loaded into a reactor,
In consideration of the pressure loss that occurs in the reactor when fluid is flowed, it is preferable to use a spherical shape with a diameter of about 0.3 to 8 square centimeters, preferably 0.6 to 3 square centimeters.

The production method of the present invention involves dripping a liquid layer of molten petroleum resin downwards on the packed bed of the fixed bed catalyst to form a thin film of petroleum resin on the catalyst surface. There is a so-called trickle or bed method that efficiently hydrogenates in the downward wave phase, or a liquid layer made of molten petroleum resin is introduced from below into the packed bed of the fixed bed catalyst, and hydrogen gas is made into fine bubbles and flows through the catalyst. Any of the so-called gas-liquid upward cocurrent flow systems that efficiently hydrogenate on the surface may be adopted.

The reaction conditions are decolorization state, hydrogenation rate of aromatic nucleus, reaction time,
It is determined as appropriate, taking into consideration the reactor specifications, etc. Usually, the reaction pressure is 10-300 kg/cm', preferably 50-150 kg/cm'. The hydrogen supply speed is 2 to 50 times, preferably 5 to 30 times, the theoretical hydrogen absorption amount of the petroleum resin, and the reaction temperature is about 200 to 350°C, preferably 230 to 320°C. The supply amount is Wt(SV (Weight Hourly
5pace velocity (amount of petroleum resin fed candy/hourly filler capacity) is preferably 0.01 to 1 ohr, preferably 0.1 to 2 hr.

The hydrogenation rate of aromatic nuclei of the hydrogenated petroleum resin thus obtained is 50% or more, preferably 50 to 70%.

If the hydrogenation rate is less than 50%, the compatibility with ethylene-vinyl acetate copolymer etc. tends to deteriorate. Further, the color tone is a Gardner color number of 1 or less, preferably a Hazen color number of 200 or less, and more preferably a Hazen color number of 100 or less. The softening point is preferably about 80 to 120°C.

EXAMPLES The present invention will be explained in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these examples.

Example 1 A reactor with a length of 5 m, an inner diameter of 27 mm, and a content of 2.8 fl was used, and the temperature could be adjusted by flowing a heat medium outside the reactor. 200 m above the reactor for preheating
M alumina spheres with a particle size of 4 to 8 mm were filled, and a spherical 2χ palladium-alumina catalyst (manufactured by Nippon Engelhardt Co., Ltd.) 15002 with a particle size of 1.5 mm was fixed and placed below the alumina spheres. Temperature 280°C 1 pressure inside the reactor? O
kg/cm', hydrogen gas supply amount 1.5Nr
rf/hr and petroleum resin (manufactured by Mitsui Petrochemical Industries, Ltd. Part name Vetrogin #120 Softening point 120°C) Supply amount 4
A hydrogenation reaction was carried out by flowing downward from 11 parts of the reactor at a rate of 00 g/hr. After gas and liquid were separated in a separator, the hydrogenated petroleum resin was taken out of the reaction system.

After the reaction was stabilized, the hydrogenation rate of aromatic nuclei, color tone, softening point, and compatibility of the obtained hydrogenated petroleum resin were measured according to the following test method.

The results are shown in Table 1. The catalyst, reaction temperature, and reaction method used as reaction conditions are also shown in Table 1.

Test method (measurement of hydrogenation rate of aromatic nucleus) The number of protons of the aromatic nucleus of the obtained hydrogenated petroleum resin was measured by H-NMR, and the hydrogenation rate was calculated using the following formula.

A: Number of protons in the aromatic nucleus of raw petroleum resin B, Number of protons in the aromatic nucleus of hydrogenated petroleum resin (measurement of color tone) Hydrogenated petroleum resin obtained according to the method specified in ASTM (I) 1888) The Hazen color number was measured. The smaller the color number, the better the decolorization.

(Measurement of softening point) According to the ring and ball method specified in JIS-253+,
The softening point of the obtained hydrogenated petroleum resin was measured.

(Compatibility) 2 g of ethylene-vinyl acetate copolymer (manufactured by Mitsui Polychemical Co., Ltd., Ko/'-Flex 220) and 2 g of hydrogenated petroleum resin were placed in a test tube and heated in a silicone oil path for 16 hours.
When the temperature reached 0°C, stir with a glass rod, further heat the oil bath to 200°C, and then let it cool. At this time, the inside of the test tube was observed to become cloudy, and the temperature was 10
If it was less than 0'O, it was marked as ○, and if it was more than 100'O, it was marked as ×.

Example 2 Temperature inside the reactor: 300°C1 Pressure: 100kg/c
The operation was exactly the same as in Example 1 except that rri' was replaced.

After the reaction stabilized, the properties of the obtained hydrogenated petroleum resin were measured in the same manner as in Example 1. The results and reaction conditions are shown in Table 1.

Example 3 The lower part of the reactor of Example 1 was filled with alumina spheres having a particle size of 4 to 6 mm for preheating, and the upper part was filled with 1500 g of the same palladium catalyst as in Example 1. Temperature inside the reactor is 300°
C1 was maintained at a hydrogen pressure of too kg/crrf, a hydrogen gas supply rate of 2ONrn'/hr, and a petroleum resin (manufactured by Mitsui Petrochemical Industries, Ltd., trade name Vetrogin #120, softening point 120°C) supply rate of 300 m into the reactor. The hydrogenation reaction was carried out by flowing upward from the bottom. Then, after separating gas and liquid using a separator, the produced resin was taken out of the reaction system. After the reaction stabilized, the properties of the obtained hydrogenated petroleum resin were measured in the same manner as in Example 1. The results and reaction conditions are shown in Table 1.

Comparative Example 1 The catalyst was a 2z platinum-alumina catalyst (Nippon Engelhardt).
The same procedure as in Example 1 was carried out except that the material was replaced with (manufactured by Co., Ltd.).

Then, after separating gas and liquid using a separator, the produced resin was taken out of the reaction system. After the reaction stabilized, the properties of the obtained hydrogenated petroleum resin were measured in the same manner as in Example 1. The results and reaction conditions are shown in Table 1.

[Blank below] According to the present invention, the cost of the catalyst can be lowered by using an inexpensive palladium catalyst, and the hydrogenation rate of aromatic nuclei can be increased because the hydrogenation reaction is easy to control. Hydrogenated petroleum resins of 50% or more, particularly 50 to 70%, can be easily produced.

Claims (1)

[Claims] 1. In hydrogenating petroleum resins having aromatic nuclei, a fixed bed catalyst with palladium supported on a carrier is filled in a reactor, and hydrogen gas and molten petroleum resin are poured into the upper part or lower part of the reactor. A method for producing a hydrogenated petroleum resin, characterized by hydrogenating 50% or more of aromatic nuclei by flowing downward or upward in a cocurrent flow and hydrogenating continuously. 2. The method for producing a hydrogenated petroleum resin according to claim 1, wherein the hydrogenation rate of aromatic nuclei is 50% or more and 70% or less.