JPS5855163B2 - Petroleum resin manufacturing method - Google Patents

Description

[Detailed description of the invention] This invention relates to a method for producing petroleum resin.

In Japanese Patent No. 1109252 (Japanese Patent Publication No. 55-34167), we have described and claimed a method for producing a hydrocarbon feedstock suitable for the production of petroleum resins, as well as a method for producing the resins.

In the production of the above hydrocarbon feedstocks, the C5 hydrocarbon stream distilled from cracked naphtha or cracked gas oil is heated at a temperature of at least 160° C.
It is preheated by heating for a period of time up to an hour.

Suitably the C5 hydrocarbon stream is heated to a temperature range of 60-200°C, and the heating time is preferably 0.05-1.5 hours.

It is likewise described in the above patent application that the preheating of the C5 feedstock is carried out in a continuous or batch process.

The invention is particularly suitable for continuous processes and provides a method for keeping the concentration of monocyclopentadiene in the polymerization feed as low as possible.

The presence of monocyclopentadiene in the polymerization feedstock results in gelatinous precipitates of polycyclopentadiene during polymerization that adhere to plant equipment, often requiring shutdown and cleaning of the equipment. There is a problem that it must be done.

Therefore, it is advantageous in terms of operation to trimerize as much monocyclopentadiene in the raw material as possible to form dicyclopentadiene.

According to the invention, the C5 hydrocarbon stream distilled from cracked naphtha or cracked gas oil is preheated to a temperature of at least 160° C. for up to 5 hours before being converted into resin, and then further heated. The temperature is maintained between 100°C and below 160°C for up to 5 hours.

Preferably the C5 hydrocarbon stream is at a temperature of 160-250°C, especially 1
Preheated to a temperature range of 60-200°C.

Preferably, the C5 hydrocarbon stream is between 100'C and 160'C.
0.05-1 at temperatures below ℃, especially 130-150℃
．． Holds for 5 hours.

Adiabatic conditions are used in which the preferred temperature is maintained isothermally or the temperature can vary within a certain range over a given period of time.

At temperatures between 100°C and less than 160°C, 160°C
At temperatures above, the monocyclopentadiene present trimerizes to dicyclopentadiene.

The C5 hydrocarbon stream is obtained from thermal or steam cracked naphtha or gas oil and typically boils at 10-80°C.

This includes the following hydrocarbons: isoprene, cis-
and trans-piperylene, n-pentane, isopentane, pentene-1, cyclopentadiene, dicyclopentadiene, trans-pentene-2,2-methyl-butene-2, cyclopentene, cyclopenkune and benzene.

Additionally, some C4 hydrocarbons are present as well.

If necessary, this C5 hydrocarbon stream may be further purified prior to use in the process of this invention.

For example, isoprene is removed by distillation and/or
or monocyclopentadiene at 100℃ to 160℃
The trimerization may be carried out by heating at a temperature below 0.degree. C., for example 120.degree. C., preferably for up to 5 hours, especially 0.05-1.5 hours.

Although the monocyclopentadiene content of the C5 stream is reduced by this treatment, subsequent temperature increases above 160° C. tend to convert some dimers to monomers.

If the C5 stream is directly cooled from a temperature above 160°C, the C5 stream will have an increased concentration of monocyclopentadiene, giving an inferior resin.

According to this invention, the monomer concentration is again reduced.

The Soaking stage is preferably carried out continuously and is conveniently carried out in a tubular reactor into which the feedstock is charged through a tube, the residence time being such that a constant Soaking stage is required to take place. It's time to do it.

The vessel is maintained at the desired temperature, ie isothermal, or the system is maintained in an adiabatic state where the heat generated by the reaction is used to obtain a temperature increase or to maintain the desired temperature.

For example, the first step is an adiabatic process with an elevated temperature of 100-180°C, the second step is an isothermal process at 180°C, and the third step is an adiabatic process between 100°C and below 160°C, and the trimerization The heat for maintaining the temperature in this range, for example 130-140°C.

If necessary, cooling treatments may be performed between each step to reach the desired temperature.

When the C5 stream is subjected to pretreatment in accordance with this invention, it is catalytically polymerized to produce resin.

Friedel-Crafts catalysts, such as inorganic halides and inorganic strong acids, are thus suitable, for example.

Inorganic halides are generally preferred and include halides of aluminum, iron, tin, boron, zinc, antimony and titanium used in combination with hydrogen halides such as hydrogen chloride.

For example, treatment with aluminum chloride complexed with hydrogen chloride, preferably in an aromatic solvent such as toluene or xylene, provides a solution from which the resin can be recovered.

Preferably, however, the Friedel-Crafts catalyst is a benzene that is liquid at the polymerization temperature and substituted with at least one secondary or tertiary alkyl group or cycloalkyl group, such as t-butylbenzene. , p-cymene, p-isobutyltoluene, p-ethyl-t-amylbenzene or, in particular, cumene.

Such a catalyst is disclosed in our UK Patent Application No. 5097/
No. 71 (corresponding to Belgian Patent No. 779,454), and complexes of aluminum chloride, cumene and hydrogen chloride are preferred.

Polymerization of the C5 feedstock is carried out under atmospheric pressure or, for example, at 70°C.
0p, s.

0.05-5 weight φ of C5 stream under pressure up to 10 g,
Preferably a catalyst concentration of 0.5-1.5 weight φ is used, preferably -100 to +200°C, more preferably +5
It is carried out at concentrations between 0 and +100°C.

The catalyst is finally destroyed and removed from the polymer by treatment with, for example, alcoholic ammonia, aqueous alkali or aqueous alcohol, followed by one or more washings with water and optionally removing residual monomers. It is steam distilled.

Suitable alcohols are alkanols having 1 to 4 carbon atoms, such as isopropanol, and suitable alkalis are alkali metal hydroxides, such as sodium hydroxide.

The polymerization is preferably carried out continuously, more preferably by passing through a plurality of alternating polymerization zones and cooling zones in which catalyst is added to each polymerization zone.

Since the polymerization is exothermic, the temperature rises adiabatically in each polymerization zone and falls only in the cooling zone, which is a preparatory step for the next polymerization in a subsequent polymerization zone.

In practice, however, the cooling zone is cooled with water.

The polymerization zone and the cooling zone may consist of any vessel capable of carrying out the desired treatment, but tubular reactors are particularly suitable.

In this case, the preheated C5 feedstock is charged into the tube along with the catalyst.

The residence time of the C5 feedstock in the tube is predetermined and its passage through the tube increases the temperature due to the heat of polymerization.

The next tube is cooled and the residence time of the hydrocarbon is such that the required temperature drop occurs while the hydrocarbon passes through the tube.

The next tubular reactor in the series is the polymerization zone and additional catalyst is introduced into the hydrocarbon feed.

There are preferably 2-8 pairs of such polymerization and cooling zones,
In particular, there are 3-5 pairs.

The amount of catalyst added overall is allocated to reach approximately the same temperature rise and therefore the same conversion in each zone.

The removal of the catalyst and the final washing of the polymer are likewise carried out continuously, for example in a series of stirrers and settlers.

The polymer is finally stripped of the remaining C5 stream hydrocarbons, for example by steam distillation, and then made available for use.

The invention will be further described with reference to the accompanying diagrammatic drawings.

Isoprene, cis- and trans-piperylene, n-
Pentane, isopenkune, pentene-1, cyclopentadiene, dicyclopentadiene, trans-pentene-
A C5 hydrocarbon stream consisting of 2,2-methylbutene-2, cyclopentene, cyclopenkune and benzene is stored in storage tank 1.

From this it is continuously fed into three tubular reactors 2, 3 and 4 in sequence.

In the first reactor the temperature of the C5 stream rises adiabatically to 120-180 DEG C. as exothermic trimerization of the cyclopentadiene takes place and then maintains this temperature in the second reactor.

After leaving the second reactor, the temperature of the stream is reduced to 135° C. and maintained at this temperature in the third reactor.

The residence time of the C6 stream in each reactor is 5 and 20, respectively.
and lead content.

After passing through the third reactor, the hydrocarbon stream is cooled to 60° C. in water cooler 5 and then in between each water cooler 10.
, 11, 12 and 13 are successively introduced into a series of tubular polymerization reactors 6, 7, 8 and 9.

Catalyst is supplied from storage tank 14 to each polymerization reactor.

The catalyst is a liquid complex consisting of aluminum chloride, hydrogen chloride and cumene and is fed to the four polymerization reactors in such amounts as to give the same temperature rise in each reactor.

The temperature of the hydrocarbon stream is 90=100° C. in each reactor and then reduced to 60° C. in each subsequent cooler.

The residence time in each reactor is approximately 3 minutes.

After leaving the last cooler 13, the polymerization product passes through the mixer 16
It is mixed therein with 10 weight φ of a 1:l mixture of water-improper tool from tube 15 and then settled in settler 17.

The isopropanol/water/aluminum chloride is removed from the settler by line 18 for isopropanol recovery, while the polymer solution is fed to mixer 19 and settler 20 for repeating the isopropanol/water wash process. Re, Improper Tools / Mizuha! The consumed cleaning liquid supplied from '21 is removed from pipe 22.

A third washing with only water takes place in mixer 23 and settler 24, water being supplied via line 25 and removed via line 26.

The washed polymer solution is stored in a storage tank 27;
From there, the resin is supplied to the final steam distillation device 28, where the molten resin is recovered from the bottom of the device and solidified into, for example, a tablet shape.

Meanwhile, the distillate consisting of water and unreacted hydrocarbons is transferred for recovery.

Example 1 A C5 hydrocarbon stream containing 13.6% monocyclopentadiene was passed continuously through a tube heated to 175° C. with a residence time of 20 minutes.

The monocyclopentadiene content of the stream leaving the reactor was 18%.

This stream was then passed through a second tube heated to 145°C with a residence time of 40 minutes.

The cyclopentadiene content of the stream leaving this tube is 0.8%
Met.

The pressure for the entire operation was 35.2 Ky/c in both tubular reactors.
1. Gauge (500p, s, i, g,).

Examples 2-7 The operation according to Example 1 was repeated in Examples 2-7 using C5 streams with different monocyclopentadiene contents.

The results are as follows: Example 8 A C5 hydrocarbon stream of 2.5 Ky was heated to 180° C. in a 5t autoclave and held at this temperature for 25 minutes.

Next, the temperature in the autoclave was lowered to 150°C and maintained at this temperature for an additional 40 minutes.

As a result, this became a feedstock for polymerization consisting of the following composition: ni-3-methylbutene-1 (0.4% by weight), pentene-1<2. s wt%), 2-methylbutene-1 (
5,1 weight φ), pentene-2 (1.7 weight %), isoprene (12,9ii weight %), 2-methylbutene-2 (
2.8 wt φ), trans-piperylene (5.6 wt%
), cis-piperylene (3,3 wt φ), cyclohentene (3,1 wt%), dicyclopentadiene (13,3
% by weight), a mixed dimer of isoprene, piperylene and cyclopentadiene (5.7% by weight).

The internal temperature of the autoclave was adjusted to 60°C, and the catalyst 28
Added rnl.

The catalyst consisted of an aluminum chloride/hydrogen chloride/cumene complex and contained 8 g of aluminum chloride.

After catalyst addition, the temperature rose and when it reached 85°C (2 minutes), the temperature was lowered to 60°C using cooling water.

Then 10 mA of catalyst was added and the temperature rose to 107°C.

The reaction mixture was cooled again to 60°C and 10M of catalyst was added again.

After further cooling to 60° C., the final catalyst 20 r
nl was introduced and after 2 minutes of reaction the mixture was cooled to room temperature.

A total of 68 parts of the catalyst complex were added, containing a total amount of aluminum chloride of 19.89.

The resin solution obtained by the polymerization was gently stirred with 300 ml of a 1:1 volume mixture of Improper Tool and water to cause sedimentation.

The resin layer was separated and the process was repeated.

Finally, the resin solution was washed with two portions of water each consisting of 300 ml.

In order to remove the unpolymerized components of the C5 hydrocarbon stream, the boiler temperature was initially increased to 180°C at atmospheric pressure and finally to 50°C.
The resin was isolated by distillation using a retort at mm pressure and boiler temperature of 200°C.

The yield of resin was 38 wt. per weight of C5 hydrocarbon stream used, Gardner color 11 (50% solution in toluene), softening point (balls and links → 108°C and melt viscosity 4.1 poise (200°C)). and 78.4 poise (1
30°C).

Additional relations This invention is disclosed in Japanese Patent No. 1109252 (Japanese Patent Publication No. 55341)
No. 67) An invention that is an addition to the invention, which is 1 in the original invention.
Whereas a C6 hydrocarbon stream preheated to 60°C or above is directly cooled to polymerize into a resin, after the above preheating, the C5 stream is further heat soaked to below 100°C to 160°C prior to polymerization. This is an improvement on the method of the original invention.

[Brief explanation of drawings]

The accompanying drawings are diagrams showing one embodiment of the invention. The main things shown in the figure are as follows. 1...
... C5 hydrocarbon stream storage tank, 14 ... Catalyst storage tank, 27 ... Polymer storage tank, 2゜3.4 ... Preheating reactor, 6 ,7,8,9・
...Polymerization reactor, 5, 10, 11, 12.13.
...Cooler, 16,19.21...Mixer, 17,20°24...Settler, 28...
・・・・Steam distillation unit.

Claims (1)

[Claims] 1 C5 hydrocarbon stream obtained by distillation from cracked naphtha or cracked gas oil at a temperature of at least 160°C.
First heat for up to an hour, then Friedel
In a process for the production of petroleum resins polymerized by treatment with a Krafun catalyst, the C5 hydrocarbon stream contains residual cyclopentadiene after said heating at at least 160° C., and the residual cyclopentadiene content is determined in the polymerization step. The C5 hydrocarbon stream was heated to 100'C to 160°C before
A process for producing the above-mentioned petroleum resin, characterized in that it is substantially reduced by holding at a temperature below °C for a period of 0.05 to 5 hours.