CS242183B1 - Hydrophilic petroleum bitumen's stable aqueous emulsion preparation method - Google Patents

Abstract

The invention solves the process of preparing a stable one emulsion of hydrophilic petroleum resin. The essence of the solution lies in the homogenisation blends consisting of hydrophilic petroleum bitumen with an acid number of 10 to 140 mg KOH.g "* 1, an emulsifier with an HLB value of 11 to 17, monoethanolamine and / or hydroxide alkali metals in weight ratio 100: 3 to 30: 3 to 40. After mixing the mixture water is added at 50-130 ° C in an amount of 0.1 to 40 wt. relative to the amount of hydrophilic petroleum resin; forming an oil-in-water emulsion was diluted to the desired concentration by others water up to 49 ° C. Emulsions of hydrophilic petroleum resin may be used in the paper industry for refining paper.

Description

The invention relates to a process for preparing a stable aqueous emulsion of a hydrophilic petroleum resin containing, for example, carboxyl groups.

Hydrophilic petroleum resins used in emulsifying organic substances or as synthetic petroleum sizing agents are used in the form of an aqueous emulsion to the user. Various auxiliary emulsifiers are used to prepare synthetic petroleum resin emulsions. They may be rosin, tall oil or fatty acid. The alkaline component is most often sodium and potassium hydroxide. Pozyrev. S. A. et al. in Bumaž prom. 3, 17, 1976 disclose that a rosin is used to emulsify the Pyroplast petroleum resin, which is heated to 120-150 ° C with the resin to form a milky emulsion when the aqueous sodium hydroxide solution is homogenized. Similarly, the preparation of an emulsion is described in Japanese Patent 32,762. As emulsifiers, they use tall oil alone or in combination with a rosin. In Japanese patent no. No. 11,446, U.S. Pat. 986 616, Austrian patent no. 347 679, the alkali component being sodium hydroxide or potassium. U.S. Pat. 978 291, the petroleum resin is melted together with the solid fatty acid and then saponified with an aqueous alkali solution.

For the preparation of emulsions of petroleum products such as mineral oils, paraffin, asphalts, etc. a wide variety of emulsifying agents and excipients are used, such as various soaps, nonionic surfactants, cationically active emulsifiers, sulfated fatty alcohols, and others. In most of the processes described above, the emulsified substance is heated with the emulsifier while warming and the resulting mixture is treated with an aqueous solution of the basic component. The emulsion thus prepared, usually of low stability, is passed through a colloid mill, ultrasonic, jet or other homogenizer, thereby clearly increasing its stability. However, such an increase in stability always involves the consumption of a relatively large amount of energy. However, even multiple homogenization does not prolong the substantial stability of the oil product emulsion.

These shortcomings are eliminated! The method of the invention is characterized in that a stable hydrophilic petroleum resin emulsion is prepared from a hydrophilic petroleum resin having an acid number of 10 to 150 mg KOH.g ^-1 . From an emulsifier having an HLB of 11 to 17 monoethanolamine and / or a concentrated aqueous solution of alkali metal hydroxide in a weight ratio of 100: 3 to 30: 3 to 40 at a temperature of 60 to 130 ° C. The amount of the components used for the preparation depends on the properties of the hydrophilic resin, the type of emulsifier, the basic component and the desired properties of the final product. After homogenization, water at a temperature of 50 to 130 ° C is added in an amount of 0.1 to 40% by weight. based on the weight of the hydrophilic petroleum resin and after formation of the oil-in-water emulsion, it is diluted to the desired concentration with an additional amount of water at a temperature of up to 49 ^° C. The hydrophilic petroleum resin used for the preparation may be dark or light in color. the weight ranges from 1,000 to 1,100 kg.m ^-3 and the average molar mass does not exceed 2,000 kg. .mol ^-1 . To some extent, these properties also affect the melting point of the resin, which should not be higher than 140 ° C. The melting point of the resin is determined by the temperature at which all components are mixed. It is important that this mixing is sufficiently homogeneous, in particular before and during the addition of water, which is achieved by using mechanical stirrers, homogenizers of different designs, possibly by ultrasound. Various ionogenic or non-ionic types are used as auxiliary emulsifiers, for example tall oil, fatty acids, ethoxylated fatty acids or rosin, either alone or in a mixture thereof. In their use, however, it is important that the HLB value of the auxiliary emulsifier or mixtures thereof used is in the range of 11-17. In the case that such emulsifiers contain carboxylic or other acidic functionalities, these emulsifiers may first be mixed with monoethanolamine and / or a concentrated aqueous alkali metal hydroxide solution and then mixed with the molten, hydrophilic resin. The hydrophilic petroleum resin concentrate, which contains no water or only a small amount (below 20% by weight), can be diluted with water at a temperature of about 60 to 100 ° C immediately after preparation or after several months. Upon dilution, the abbot was warmed to approximately the temperature at which it was prepared.When diluting and vigorously stirring, a water-in-oil emulsion was formed first, which gradually turned into an oil-in-water emulsion. The aqueous emulsions of hydrophilic petroleum resins prepared according to the process of the invention are stable for several months to years and are not sensitive to low temperatures down to -25 ° C. The emulsions solidify when cooled to temperatures below 0 ° C , but after warming to ambient temperature and stirring, they are homogeneous and stable exemplified by the following examples:

Example 1

K 50 wt. 5 parts by weight of synthetic hydrophilic resin having an acid number of 40 mg KOH.g ^-1 , a softening temperature of 35 ° C, a specific gravity of 1050 kg.m ^-3 and a mean molecular weight of 550 kg.mol ^-1 are added. parts of an emulsifier based on polyethylene glycol and olein (Slovasol O) (HLB = 16). The mixture is heated to 80-100 ° C and homogenized by gentle stirring. Of 6 wt. parts by weight of potassium hydroxide and 6 wt. A portion of water is prepared and added to the mixture of the molten resin and emulsifier with stirring while stirring. The mixture is stirred at 80 to 100 ° C until a homogeneous V / O emulsion is formed. The concentrate thus prepared can be converted into an O / V emulsion by successively adding 100 wt. parts of water at a temperature of 60 to 80 ° C and gentle stirring. By adding an additional amount of 400 wt. parts of cold water t = 11 to 15 ° C to form an emulsion stable for at least 6 months.

Example 2

K 50 wt. by weight of the same resin as in Example 1, 5 wt. parts by weight of an emulsifier based on olein and polyethylene glycol (Slovasol 6018) HLB = 15, 10 wt. parts by weight of potassium hydroxide, 10 wt. parts of water. The mixture is stirred at 80-100 ° C until a homogeneous V / O emulsion is formed. The concentrate thus prepared can be converted into an O / V emulsion by adding 100 wt. parts of water at a temperature of 60 to 100 ° C. After the addition of another 150 wt. parts of water at a temperature of 10 to 15 ° C to form an emulsion stable for more than 3 years.

Example 3

The procedure was as in Example 1, but instead of potassium hydroxide, 6 wt. parts of sodium hydroxide. The resulting emulsion is stable for 3 months and after one year of standing 5% of the petroleum resin used is separated.

Example 4

The procedure is the same as in Example 1, but 10 wt. parts of an emulsifier based on tall oil and polyethylene glycol (an emulsifier Tj having an HLB value of 14. The stability of the resulting emulsion is more than 6 months.

Example 5

K 50 wt. 3 parts by weight of hydrophilic resin having an acid number of 63.2 mg KOH.g ^-1 and a specific gravity of 1074 kg / m @ ³ are added. parts of an emulsion based on olein and polyethylene glycol (Slovasol 6018) having an HLB value of 15, 16 wt. parts of a 50% potassium hydroxide solution. The mixture is homogenized by gentle agitation at a temperature of 90 to 90 ° C

120 [deg.] C. 80 wt. of water at 75 ° C to convert the flood type I / O emulsion into an O / V type emulsion. After the addition of an additional 500 wt. parts of cold water to form an emulsion stable for at least a month.

Example 6

The procedure was as in Example 5, but instead of Slovasol 6018 a mixture of an olein-based emulsifier and polyethylene glycol was used by mixing from 2.5 wt. parts of Slovasol O (HLB = 16) and 2.5 parts by weight of Slovasol 2530 (HLB = 18). A stable emulsion is formed.

Example 7

At 100 DEG-130 DEG C., 4 wt. parts of tall oil with an acid number of 178 mg KOH.g ^-1 and 16 wt. parts of monoethanolamine. To this solution was added 100 wt. parts of molten petroleum resin having an acid number of 23.5 mg KOH.g ^-1 , a specific gravity of 1,027 kg.m ^-3 and an average molecular weight of 496 kg.mol ^-1 . The mixture is maintained at a temperature of 100 to 130 ° C during the addition of the resin.

The resulting homogeneous mixture is divided into two equal portions. To one portion, 100 wt. parts of water at a temperature of 80 to 90 ° C with constant stirring. Stirring is intensified when the flood type I / O emulsion is being converted to type O / V. By adding an additional 300 wt. parts of cold water to form an emulsion stable for at least 6 months.

The second portion of the mixture, after being carefully heated to 90-120 ° C, can be processed to a stable emulsion by the same procedure as the first portion within 6 months of its preparation.

Example 8

At a temperature of 80 to 110 ° C, a homogeneous mixture consisting of 50 wt. parts by weight of petroleum resin with an acid number of 32.3 mg KOH.g ^-1 , 10 wt. parts of rosin with an acid number of 170 mg KOH.g ^-1 and 10 wt. parts of monoethanolamine. Then, with stirring, 100 wt. parts of water at a temperature of 60 to 80 ° C and 500 wt. parts of cold water. An emulsion with high stability is obtained.

The hydrophilic petroleum resin emulsions described are used e.g. in the paper industry for paper refining or for the refining of various organic products.

Claims (2)

SUBJECT Process for the preparation of a stable hydrophilic petroleum resin emulsion, characterized in that a mixture consisting of a hydrophilic petroleum resin having an acid number of 10 to 150 mg KOH.g ^-1 , an emulsifier having an HLB value of 11 to 17, is homogenized at 60-130 ° C. , monoethanolamine and / or alkali metal hydroxide in a weight ratio of 100: 3 to 30: 3 to 40 after homogenization under stirring, water at a temperature of 50 to 130 ° C in an amount of 0.1 is added. Up to 40 wt. based on the amount of hydrophilic petroleum resin and after formation of the oil-in-water emulsion, it is diluted to the desired concentration with an additional amount of water at a temperature of up to 49 ° C. 2. A process for the preparation of an emulsion according to claim 1, characterized in that a mixture of at least two emulsifiers is used in a ratio such that the resulting HLB value is in the range of 11 to 17.