JPS5975904A - Production of hydrogenated petroleum resin - Google Patents

Abstract

PURPOSE:To obtain a hydrogenated petroleum resin at an improved degree of hydrogenation within a shorter reaction time, by filling a reactor with supported Pt or Rh catalyst and downwardly passing a molten petroleum resin together with hydrogen from the top of the reactor. CONSTITUTION:In the hydrogenation of a petroleum resin having aromatic nuclei, a reactor is filled with a fixed bed catalyst carrying ( I ) platinum and/or rhodium, or ( I ) platinum and/or rhodium and (II) at least one metal selected from the group consisting of palladium, ruthenium and rhenium, and a molten petroleum resin together with hydrogen gas are fed concurrently from the top of the reactor, and passed downwardly while the hydrogenation is being carried out continuously. In said catalyst, when at least one metal selected from the group consisting of palladium, ruthenium and rhenium is added to platinum and/or rhodium, the catalyst life can be prolonged by the heat resistance effect resulting from the prevention of sintering of platinum and/or rhodium, though the activity is somewhat lowered as compared with that of platinum and/or rhodium alone.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing hydrogenated petroleum resins. More specifically, in hydrogenating petroleum resins having aromatic nuclei, the present invention relates to a petroleum resin method in which hydrogen gas and molten aromatic nuclei are introduced from the upper part of the reactor under filling of a fixed bed catalyst supporting a specific metal.

The so-called petroleum resin obtained by polymerizing the thermal decomposition product of petroleum naphtha in the presence of a 7-Riedel-Crafts catalyst is mainly used as a tackifier for pressure-sensitive adhesives or adhesives, a modifier for plastic formulations, etc. Resins suitable for these uses usually have a softening point of 60 to 140°0 and a molecular weight of about 600 to 10,000. Among other things,
These hydrogenated petroleum resins improve their weather resistance, color tone,
Stability or rubber, polyolefin or ethylene
Since it has good compatibility with vinyl acetate copolymers and the like, it is particularly suitable as a resin for use in the above-mentioned applications. However, the petroleum resin subjected to the above-mentioned hydrogenation is much less likely to be hydrogenated than its raw material monomer.

The reason for this has not yet been fully elucidated, but in general, hydrogenation becomes more difficult as the degree of polymerization increases. In particular, when converting a benzene ring in a petroleum resin having an aromatic ring to a cyclohexane ring, the hydrogenation reaction is difficult to proceed unless a large amount of catalyst is added and severe conditions such as high temperature, high pressure, and long time are used.

Powdered nickel catalysts or platinum catalysts have been known as catalysts used in the hydrogenation reaction of petroleum resins. As a hydrogenation method, a batch suspension bed system or a flow suspension bubble column system is generally employed.

When hydrogenating by this conventional method, a filtration step is essential to separate the hydrogenated petroleum resin and the trunk catalyst after the hydrogenation. Furthermore, 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 the filtration time is delayed. After diluting the catalyst with an organic solvent such as
Then, by evaporating the solvent from the furnace liquid, the target hydrogenated petroleum resin can be extracted. 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 therefore the catalyst cannot be quantitatively recovered, resulting in a large economic loss. In view of these problems, there is a strong desire to establish a hydrogenation process for petroleum resins using a fixed bed from an industrial and economic standpoint such as resource and energy conservation.

The inventors of the present invention have conducted intensive research to develop a new and extremely streamlined continuous hydrogenation process for petroleum resins that eliminates the filtration and evaporation steps that are problems with conventional technology. By using a reactor filled with a fixed-bed catalyst and adopting a specific flow-down system, we solved all the drawbacks of the prior art and found that the above object could be achieved, leading to the completion of the present invention. .

That is, in hydrogenating a petroleum resin having an aromatic nucleus, the present invention uses (I) platinum and/or rhodium or (1) platinum and/or rhodium and (II)
Continuous In the present invention, a petroleum resin having an aromatic nucleus is an aromatic hydrocarbon having a double bond in its side chain or a fused ring containing a double bond. It refers to a homopolymer of aromatic hydrocarbons or a mixture of aromatic hydrocarbons and other olefins, and the following components are Friedel-Crafts catalysts such as aluminum chloride and boron trifluoride. It can be obtained by polymerization in the presence of

Examples of aromatic hydrocarbons include styrene, α-methylstyrene, vinyltoluene, vinylxylene, propenylbenzene, indene, methylindene, and ethylindene.

Examples of olefins include butene, pentene-hexene-heptene, octene, butadiene, pentadiene, cyclopentadiene, dicyclopentadiene,
Examples include octadiene.

The catalyst used in the present invention needs to be a fixed bed catalyst supporting a specific metal. This is because, as mentioned above, petroleum resins, especially petroleum resins having aromatic nuclei, are difficult to hydrogenate and therefore require a highly active catalyst. On the other hand, the petroleum resin usually has a sulfur content of 100 to 100% as sulfur.
Sooppm is contained, which acts as a catalyst poison and shortens the life of the catalyst. Therefore, a highly active catalyst is not necessarily suitable, and resistance to sulfur poisoning is also an important factor for the catalyst of the present invention.

As a result of examining the above two factors, surprisingly, very satisfactory results were obtained when a fixed bed catalyst carrying platinum and/or rhodium was used. A fixed bed catalyst obtained by combining platinum and/or rhodium with a metal such as palladium, ruthenium or rhenium can also be suitably used. That is, by adding at least one metal selected from the group consisting of palladium, ruthenium, and rhenium to platinum and/or rhodium, the activity is slightly lower than when platinum and/or rhodium are used alone. It is effective in extending the life of the catalyst due to the heat resistance effect based on the prevention of sintering of platinum and rhodium.

Although knowledge regarding catalyst poisoning has not been elucidated in detail, in the present invention, clear differences were confirmed between the case of platinum and/or rhodium catalysts and the case of nickel catalysts. That is, when a nickel catalyst is used, catalyst deterioration occurs due to sulfur being adsorbed onto the catalyst very quickly or reacting with sulfur to produce nickel sulfide. On the other hand, when platinum and/or rhodium catalysts were used, sulfur was hydrogenolyzed to form hydrogen sulfide, which was removed from the catalyst layer along with hydrogen gas, so it was not accumulated on the catalyst.

That is, the catalyst of the present invention contains at least one member selected from the group consisting of (I) platinum and/or rhodium, or (I) platinum and/or rhodium, and (1) palladium, ruthenium, and rhenium. Examples include supported fixed bed catalysts.The amount of platinum and rhodium supported alone or in combination is 0.2 to 10% by weight based on the weight of the carrier.
(hereinafter referred to as %), preferably 0.5 to 5%.

In addition, the amount of the metal (II) supported can be such that the total weight of the supported amount of the metal (I) satisfies the above range with respect to the carrier weight, and it can be used in combination up to the same weight as the metal (I) above. can.

The carrier used is not particularly limited, but alumina, silica, carbon, titania, etc., which are porous and have a large surface area, are preferable.

The shape of the catalyst used may be cylindrical, extrudate, pellet, or spherical, but spherical is particularly preferred.

The size of the catalyst is better as it affects the effective activity of the catalyst, but considering the pressure loss that occurs in the reactor due to catalyst filling, the size of the catalyst should be 0.6 to 8 mm in diameter, preferably 0.6 to 3 mm. It is better to

The production method of the present invention involves causing a liquid phase consisting of a molten petroleum resin to drip downwardly onto the packed bed of the fixed bed catalyst, and forming a thin film of petroleum resin on the catalyst surface. It employs the so-called trickle bed method, which efficiently adds hydrogen in a fluid phase.

Regarding the reaction conditions of the present invention, hydrogenation rate, reaction time,
It will be determined appropriately taking into consideration the reactor specifications, etc.
Usually the reaction pressure is 30 to 300 vQm, preferably 50 to 150 vQm. The amount of hydrogen supplied is 2 to 50 times, preferably 2 to 30 times, the theoretical hydrogen absorption amount of the petroleum resin, and the reaction temperature is 200 to 650 degrees a1, preferably 260 to
It is preferable to set it to 320°a. Also, the supply amount of petroleum resin is W
H8V (Weight Hourly 5 pace V
elocity.

Petroleum resin supply weight/catalyst filling weight per hour) is 0
．． It is good to set it as 0.01-10, preferably 0.05-2.

As mentioned above, according to the production method of the present invention, petroleum resin is melted at high temperature and lowered from the upper part of the reactor to form a thin film of petroleum resin on the catalyst surface, which is then injected with hydrogen as a continuous phase. By efficiently contacting and diffusing gases, the reaction time can be shortened and the hydrogenation rate can be improved compared to conventional batch suspension bed systems or flow suspension bubble column systems.

Next, the present invention will be specifically explained with reference to Examples.

Example 1 A reactor with a length of 2 m, an inner diameter of 16 rnrn, and an internal volume of 11 was used. The outside of the reactor was heated with a cast-in brass heater, and divided into 4 blocks to keep the internal temperature constant. so that the temperature can be adjusted. The upper part of the reactor was filled with a 200 mJ stainless steel packing for preheating.
500 g of a spherical 2% platinum-alumina catalyst (manufactured by Nippon Engelhard Co., Ltd.) with a particle size of 1.50 was fixedly placed at the bottom of the catalyst.

Temperature inside the reactor: 295-305°01 Pressure: 100kg/
am”, hydrogen gas supply 1t15ONz/hr and petroleum resin (“Vetrogin #120”, softening point 120
ocJ1 sulfur content 150ppm, aromatic nucleus content 54%
, manufactured by Mitsui Petrochemical Co., Ltd.) Supply jt 150g/'h
Hydrogenation was carried out by flowing downward from the top of the reactor at r. Then, after separating gas and liquid in a separator, the hydrogenated petroleum resin was taken out of the reaction system.

Note that since the above-mentioned apparatus was a bench scale, hydrogen gas was not circulated. Next, continuous operation was performed to confirm the catalyst activity and catalyst life, and the analysis results of the hydrogenated petroleum resin obtained after each time period are shown in Table 1.

Table 1 As is clear from Table 1, despite 3000 hours of continuous hydrogenation reaction, the catalyst did not deteriorate and maintained a high hydrogenation rate of about 90%.

The hydrogenation rate decreased to 70% over time, and a tendency for catalyst deterioration was observed.

The hydrogenation rate was determined by the following measurement method. That is, the absorbance at 274.5 nm was measured using an ultraviolet spectrometer, and the hydrogenation rate was calculated by the following formula.

-B -X100 (%) (In the formula, A indicates the absorbance of the raw petroleum resin, and B indicates the absorbance of the hydrogenated petroleum resin.) Examples 2 to 5 The platinum catalyst of Example 1 was combined with each catalyst shown in Table 2. Hydrogenation was carried out in the same manner as in Example 1 except that . The analysis results of the obtained hydrogenated petroleum resin are shown in Table 2.

Table 2 As is clear from the results in Table 2, in Examples 2 and 6, the hydrogenation rate decreased after 4000 hours, and a tendency for catalyst deterioration was observed.

On the other hand, when catalysts containing ruthenium or palladium were used in Examples 4 and 5, there was almost no decrease in the hydrogenation rate even after 4,000 hours had passed, clearly showing an effect on extending the life of the catalyst.

Procedural amendment (voluntary) Commissioner of the Japan Patent Office Kazuo Wakasugi 1. Indication of the case 1982 Patent Application No. 186496 2. Name of the invention Process for producing hydrogenated petroleum resin 3. Person making the amendment Relationship to the case Patent applicant Masa Ara Kawa Representative Yoshi Masa Ara Kawa 4 Agent 〒540 5. Subject of amendment (1) 1. Scope of claims in the specification Column 6. Contents of amendment (1) ``Scope of claims'' in the specification The amendment shall be made as shown in the attached "Amended Claims."

7 List of Attached Documents (1) Amended Claims 1 Amended Claims 1. In hydrogenating a petroleum resin having an aromatic nucleus, (I) supporting platinum and/or rhodium Production of hydrogenated petroleum resin characterized by filling a reactor with a fixed-bed catalyst and causing hydrogen gas and molten petroleum resin to flow downward in cocurrent from the top of the reactor to perform hydrogenation continuously. Method.

2. When hydrogenating petroleum resins having aromatic nuclei,
A reactor is filled with a fixed bed catalyst containing (■) platinum and/or rhodium and (II) at least one metal selected from the group consisting of palladium, ruthenium and rhenium, and hydrogen gas is supplied from the top of the reactor. A method for producing a hydrogenated petroleum resin, characterized in that hydrogenation is continuously carried out by flowing downwardly a molten petroleum resin and a molten petroleum resin in parallel flow. ” Written amendment (method) September 2, 1980 1 Indication of case 1988 Patent Application No. 186496 2 Name of invention Process for producing hydrogenated petroleum resin 3 Relationship with the person making the amendment Patent application Person 4 Representative 540 Address Dairy Building 5, 3-60 Kyobashi, Higashi-ku, Osaka
Subject of amendment (1) Application Contents of amendment 6 (1) Add the indication "(Patent application pursuant to the proviso to Article 68 of the Patent Act)" to the right shoulder of the application.

(2) Add the statement "Number of inventions stated in the claims: 2" after line 5 of the application.

that's all (2)

Claims (1)

[Claims] 1. In hydrogenating a petroleum resin having an aromatic nucleus,
(1) A fixed bed catalyst supporting platinum and/or 0 dium is packed into a reactor, and hydrogen gas and molten petroleum resin are allowed to flow downward in cocurrent from the top of the reactor. A method for producing a hydrogenated petroleum resin, characterized by carrying out hydrogenation continuously. 2. When hydrogenating petroleum resins having aromatic nuclei,
A reactor is filled with a fixed bed catalyst containing (■) platinum and/or rhodium and (n) at least one metal selected from the group consisting of palladium, ruthenium and rhenium, and hydrogen gas is supplied from the top of the reactor. A method for producing a hydrogenated petroleum resin, characterized in that hydrogenation is continuously carried out by flowing downwardly a molten petroleum resin and a molten petroleum resin in parallel flow.