CS265526B1 - A method for removing an aluminum chloride or boron trifluoride catalyst from a petroleum resin manufacturing process - Google Patents

Abstract

The solution relates to a method of removing a catalyst based on aluminum chloride or boron trifluoride in the process of producing petroleum resins. The essence of the solution is that the reaction mixture containing petroleum resin dissolved in a mixture of hydrocarbons is treated in one to three stages with hydrochloric acid in the form of an aqueous solution of such a concentration that the acidity expressed in pH values is less than 3 and after separation of the aqueous solution, it is subsequently washed with water in one to three stages, the amount of these solutions to the amount of organic material being in a weight ratio of 2 to 0.05:1 and the weight ratio of acids in the form of an aqueous solution to the amount of water used for washing is 5 to 0.1:1, the entire washing process being carried out at such a temperature that the difference in the densities of the hydrocarbon and aqueous phases at a temperature of 20 °C is at least 90 kg.m". The solution can be used in the petrochemical industry.

Description

265526 2

The present invention relates to a process for the removal of a catalyst based on aluminum chloride and boron trifluoride in the process of producing petroleum resins.

Typically, for the production of petroleum resins, carbon monoxide and Cg are formed as raw materials for the pyrolysis of gasoline and kerosene. However, there are other olefinic sources, either monomers or fractions that are polymerizable to resins and are still most commonly used as flammable. Depending on the type of monomers and the molecular structure, the aliphatic, aromatic, aliphatic-aromatic and resins are polymerized. cyclanic. Aliphaticropic Resins are formed by polymerization and fractions, aromatic from Cg fractions and aliphatic-aromatic polymerization of Cg and C ^ and C ^, respectively. C ^ fractions. Cyclanic resins are prepared by hydrogenation of aromatic resins. The polymerization can be carried out thermally, in the presence of radical initiators, or with the presence of acidic or acidic initiators. basic catalysts. Cationic polymerization occurs most often in the presence of Friedel-Crafts catalysts based on aluminum or boron complexes. a large number of such catalysts are described in the patent literature (Jap. patent 78- 146 792; Jap. patent 75-7,560; Jap. patent 78-10678; Jap. patent 79-163,988; NSR patent 2,924,164; Jap. 80-149,309) which influence the course of the polymerization process. By choosing a catalytic system, it is possible to prepare resins with defined utility properties, especially the soaking temperature, color, adhesion properties, molar mass, compatibility with other polymeric substances and the like. To catalyze the polymerization reactions, the ionic catalysts are added in an amount of 0.1 to 5% by weight based on the olefinic feedstock. In order not to detract from the useful properties of the obtained petroleum resins after their reaction, it is necessary to remove the reaction mixture. Inadequate removal of the catalyst from the polymerization reactor effluent results in a deterioration of the resin color, a reduction in its clarity and solubility in organic solvents.

Typically, the catalysts are decomposed and removed with water or an aqueous alkaline solution.

According to some methods, the catalyst is removed by trace amounts of water or alkaline species, the acid catalyst being converted into an insoluble hydroxide or a base complex which precipitates and is removed by filtration. Importantly, the catalyst is precipitated in a readily filterable form. The particles are concentrated by the addition of alkali metal carbonate or alkaline earth metal carbonate (U.S. Pat. solid adsorbents (Jap. patent 74-99 587), such as activated carbon, so that filtration is facilitated. According to another method (Jap. Patent 74-99588), the reactor effluent (in the case of BF2 polymerization) is contacted with hydrogen in the presence of a hydrogenation catalyst. Thus, the hydrogenation and the removal of the catalyst are carried out simultaneously, and the remainder of the BF2 catalyst is removed by filtration. In the case of anhydrous catalyst removal, it is necessary to provide treatment and treatment of solid waste. Separation of the catalyst with the use of aqueous solutions often leads to the formation of emulsions. This can sometimes be avoided by the addition of hydrocarbon to the oil layer, which has a higher boiling point than water (Jap. Patent 74-109,482), or by the addition of polyethylene, respectively. polypropylene glycol monophenyl ether during washing with water (Jap. patent 79-152,093). According to Japanese Patent 76-148,789, the polymerization is washed with methanol. If the polymerization is carried out in the presence of a highly active-active catalyst, which is at extremely low concentrations, similar to the production of a catalyst, which is at extremely low concentrations, similar to the production of polyethylene or polypropylene, the process of producing petroleum resins will be simplified, since the catalyst does not need to be removed from the reaction mixture. However, the drawback of such high-activity catalysts is that they are readily inactivated by traces of impurities, moisture, and especially catalytic poisons, which are always found in the base materials for the production of petroleum resins. A more complex catalyst removal situation occurs as petroleum resins are prepared with hydrophilic properties, for example, by copolymerizing unsaturated petroleum fractions with alpha, beta unsaturated acids or anhydrides. In such cases, it is very easy to form an emulsion, since the aluminum or other carboxylic acid salts bound to the hydrocarbon skeleton of the petroleum resin act as emulsifiers and it is difficult to separate the aqueous and hydrocarbon phases and remove the polymerization catalyst.

These drawbacks are avoided by removing the aluminum chloride or boron trifluoride catalyst from the petroleum bitumen process of the present invention, wherein the reaction mixture containing the petroleum resin dissolved in the hydrocarbon mixture is treated in one 265526 to three steps with hydrochloric acid. in the form of an aqueous solution at a concentration such that the acid, expressed in pH, is less than 3 and, after separation of the aqueous solution, is washed with water in one to three steps, wherein the amount of these solutions is in a weight ratio of 2 to 0.05: 1; the weight ratio of the acids in the aqueous solution to the amount of water used for the washing is 5 to 0.1: 1, the entire washing process being carried out at a temperature such that the difference in hydrocarbon and aqueous phase densities is at least 90 kg.m washing and polishing in the case of hydrochloric acid, a further solvent not mixed with water may be added in such a way that the density of the resulting solution at 20 ° C is not more than 910 kg.m \ t

After polymerization of unsaturated hydrocarbon fractions, optionally in combination with other olefins or polar monomers in the presence of Friedela-Crafts type catalysts, satento is deactivated first. According to the invention, water and / or aqueous solutions containing hydrochloric acid and / or hydrobromic acid are used for this purpose. These convert catalytically complexes into compounds containing water molecules or hydroxyl groups as metal ligands, whereby the metal complexes lose activity. Depending on the pH value of the aqueous solution used for deactivation and also the amount thereof, the catalyst results in compounds which are dissolved or almost insoluble in water or aqueous solutions. In order to avoid the formation of insoluble compounds in the catalyst deactivation process, so that the process of removing the catalyst from the organic phase of the petroleum resin hydrocarbon solutions is reduced, it is necessary to maintain the pH of the aqueous catalyst removal solutions at a value lower than 3. they provide hydrogen halides in an amount such that the aqueous solution reaches a pH of less than 2. If desired, aqueous solutions of hydrogen halides, especially hydrochloric acids, can be used directly for washing. In order to better remove the aluminum and / or boron salts from the organic phase, it is preferable to use a larger amount of acidic aqueous solutions, but at the same time there are problems with their processing prior to canning. Therefore, it is preferred to wash the organic phase several times with smaller amounts of acidic aqueous solutions. Usually this is done in 2 to 4 sections, which consist either of stirred vessels or columns filled with, for example, sieves, thus ensuring intensive contact of the aqueous and organic phases. In order to reduce the amount of water required for washing, a countercurrent connection is preferred, i.e. the washing solution, for example, from the third section, is used for washing in the second section and the solution from the second section is used for the first section. In this connection, only deionized water is fed to the third section, since the polymerization mixtures prepared in the absence of polar monomers, for example unsaturated acids and alcohols, phenolic, and deionized water can contain some basic substances to remove trace amounts of halide ionions . The first wash aqueous solution containing the highest concentrations of dissolved salt of the deactivated catalyst results in further processing prior to sewage, somewhere to remove salts, entrained and water-dissolved organic materials. For efficient removal of the catalyst from the organic phase, it is preferred to use aqueous solutions in the individual sections with a pH of less than 3 in a weight ratio of 2 to 0.05: 1, preferably 0.8 to 0.2: 1, based on the amount of organic phase, wherein the weight ratio of acidic aqueous The solutions and water used for washing are 5 to 0.1: 1. In order to achieve a good and especially rapid separation of the organic and aqueous phases, the entire process of washing and removing the catalyst is required to be such that the densities of the two phases are not very close. That is to say, the polymerization reaction of unsaturated hydrocarbons results in petroleum resins having a density of about 1,000 kg. That is, depending on the degree of conversion, that is to say the amount of emerging bitumen resins, the density of the organic phase increases after polymerization and approaches the density phase. This promotes the formation of emulsions and slows down the phase separation process. Akosme found that the phase separation is fast enough if the density difference between the two phases is more than 90 kg.m at 20 ° C. This can be achieved by increasing the phase separation temperature, or by diluting the polymerization mixture with a solvent that does not mix with water and / or aqueous solutions, this being added to the polymerization mixture in such a quantity that the density of the resulting solution is at a maximum of 910 kg / m 3 at 20 ° C, such solvents are benzene, toluene, xylenes and other hydrocarbons that dissolve well oil resin. Temperatures at which a good breakdown of the distribution phase and the organic phase occurs. they are 40 to 120 ° C. The advantages of removing the catalyst of the present invention can be seen from the following examples. Přikladl

To a 50 L reactor equipped with a heating and cooling coil, stirrer and feed feed and catalyst feed, 30 kg of pyrolysis gasoline fraction were boiled in a temperature range of 130-190 ° C with a density at 20 ° C of 890 kg.m 3 containing 34.6% by weight. unsaturated hydrocarbons. After heating the reactor to 65 ° C, 540 g of a liquid complex catalyst containing 507 mg of AlCl 3 in 1 cm of complex was gradually added over 25 minutes.

After 1.5 hours of polymerization at 65 ± 5 ° C, the density of the reaction mixture, measured at 20 ° C to 937 kg / m 3, was increased. By adding 4.5 dm 3 of deionized water, the polymerization was stopped, the temperature of the resulting mixture was adjusted to 70 ° C and the whole mixture was left without stirring for 30 minutes. During this time, phase separation occurred, with 87.3 wt. the catalyst (calculated on the Al ion content) has gone into an aqueous phase whose pH has dropped below 1 and the density of this phase, measured at 20 ° C, increased to 1,018 kg.m After separation of the phases, 12 dm of an aqueous solution was added to the organic phase HCl pH 2, the whole mixture was heated to 70 ° C, stirred well and left to stand for 40 minutes at that temperature. 10.9 wt. the amount of catalyst used for the polymerization. 12 dm 3 of water was added to the organic phase once more, the mixture was heated to 70 ° C, stirred for 45 minutes, the organic phase was separated and subjected to distillation. Distillation at normal pressure distilled water and hydrocarbons boiling to 150 ° C. It was further distilled under a vacuum of 1.3 kPa and simultaneously supplying dried nitrogen to the liquid. The distillation was complete when the temperature of the liquid in the cooking pot reached 150 ° C. The crude oil obtained contained 0.005 wt. aluminum; the presence of chloride ions was not detected. Example 2

Polymerization conditions as in Example 1, but 1.5 kgmaleic anhydride was added to the olefinic feedstock and the amount of catalyst was increased to 590g. The polymerization was stopped in 2.5 hours (reaction mixture density at 20 ° C, 920 kg.m 3) by addition of 12 dm 3 of an aqueous 80 ° C solution containing 0.28 wt. Al + 3 ions and 0.66 wt. HCl. The pH of this solution was less than 1 density at 20 ° C, 1026 kg · m 3. After 15 minutes of standing, the organic phase was separated from the aqueous phase and 12 dm 3 of an aqueous solution containing 0.03% by weight was added. Al + 3 ions and 0.07 wt. HCl with a pH of less than 1. After being brought to 80 ° C and well mixed with each other, after 10 minutes of standing, the aqueous and hydrocarbon phases are separated. The hydrocarbon phase was washed again with 12 DM of water at 80 ° C and separated after 10 minutes from the aqueous phase. This phase was further processed as in Example 1 and the resulting hydrophilic petroleum resin contained 0.03% by weight. of aluminum and did not contain chloride ions. Example 3

Following the procedure of Example 2, a series of 5 polymerizations was carried out, with the removal catalyst being such that for the first and second stages of each wash the aqueous solution from the second and third washes of the previous experiment was used. Only deionized water was used for the third wash. The aqueous solution from the first wash was sewn after treatment. The countercurrent arrangement of each of the five polymerizations yielded an oil resin of 36-38% by weight. with substantially the same content of aluminum ions, which ranged from 0.027 to 0.035% by weight. Example 4

The reaction mixture was prepared by polymerizing 100 parts of pyrolysis gasoline fraction from 190 to 240 ° C, density 948 kg.m-3 at 20 ° C containing 14.8% by weight. naphthalene. As a catalyst

Claims (1)

5,255,526 tor were used 1.4 parts of BF, -etherate. The polymerization was carried out at 90 ° C for 1 hour. The resulting reaction mixture had a density of 986 kg.m. The reaction was quenched by the addition of 50 parts of deionized water, but the emulsion was stable for several days at 20 ° C. The phase separation was not achieved either by heating the mixture to 80 ° C. However, by adding 60 parts of xylene fraction, the density of the polymerized mixture measured at 20 ° C to 908 kg.m 3 was reduced, indicating that the aqueous and organic phases were separated at 45 ° C over 45 minutes. 40 parts of water were used in the further washing and 30 parts of water in the third stage. After distilling off the solvent and unreacted hydrocarbons, the resulting petroleum resin (57% yield) did not contain bromide ions. DISCLOSURE OF THE INVENTION A method for removing an aluminum chloride or boron trifluoride catalyst from a petroleum resin process, characterized in that the reactant containing the ropnd resin dissolved in the hydrocarbon mixture is treated in one to three steps with hydrochloric acid in the form of an aqueous solution of the same concentration. that the acidity expressed in pH values is less than 3 and after separation of the aqueous solution it is washed with one to three steps in subsequent water, wherein the amount of these solutions is washed in one to three steps, the amount of these solutions being in weight ratio 2 to 0.05: 1 and the weight ratio of the aqueous solution to the water used for washing is 5 to 0.1: 1, the entire washing process being carried out at a temperature such that the difference in hydrocarbon density at 20 ° C was at least 90 where the hydrocarbon-containing solvent is not added to the petroleum resin dissolved in the mixture prior to hydrochloric acid processes and washing, in such a quantity that the density of the 20 ° C solution is not more than 910 kg.m