HU202906B - Process for obtaining petroleum sulfonates - Google Patents

Abstract

Petroleum-sulphonates are extracted from acid resin free, acid contg. oils. The oils are neutralised at 40-70 deg.C by 5-15 vol.% sodium hydroxide soln. and mixed at 50-80 deg.C with 1-20 vol.% of an ethanol-water soln. contg. these components in a 1.3:0.7 and 0.7:1.3 vol. ratio. The mixt. is allowed to settle and the phases are sepd. The sulphonate-free phase is rejected. Ethanol is distilled off from the first aq.-ethanolic sulphonate soln. and the water content of the remainder is set to 35-60 vol.%. 85 vol.% iso-butanol is added in a proportion that iso-butanol to water wt. ratio should be 1-1.9 and that the solvent to petroleumsulphonate should be at least 3. The mixt. is agitated at 40-60 deg.C, while pH is set to 8-9 with conc. sulphuric acid. The mixt. is allowed to settle and the phases are sepd. - The lower phase contg. inorganic salts i-butanol and hydrophilic sulphonates is removed. To the upper phase contg. an aq. i-butanol sulphonate soln., 0.5-2 vol. of a filter aid is added. The soln. is filtered. The oil content of the filtrate is adjusted and the filtrate is neutralised.

Description

The present invention relates to a process for recovering petroleum sulfonate from acidic oil formed during the refining and sulfonation of petroleum fractions with oleum or sulfur trioxide (for example in the production of white oil).

Petroleum sulfonates are salts of alkyl-aromatic sulfonic acids (Ullmanns Encyclopedia dér technischen Chemie 4, Aufl., Band 18.1).

As a result of the increasing demand, instead of the nature of older by-products, a growing proportion is now being produced as a target product. Of particular interest are the salts of the oil-soluble sulfonic acids - mahogany acids - which are widely used in motor oil additives, drilling and petroleum auxiliaries, flotating agents, metalworking oils, degreasing agents, corrosion inhibitors, leather and textile finishing agents. emulsifiers.

The mahogany sulfonic acids formed as a result of sulfonation are soluble in the unreacted oil phase and can be recovered therefrom. In the phase known as acid resin, the main weight of sulfuric acid introduced into the sulfonating agent and / or formed during the sulfonation, in the case of poorly oleophilic sulfonic acids - usually polysulfonated products - and resinous substances, contaminating it.

The recovery of the mahogany sulfonic acids can be carried out in the acidic state or after salt formation. Recovery essentially involves isolation from neutral oil, and in some cases from inorganic acids or salts.

The phenomenon of varying degrees of separation between oleophilic and hydrophilic solvents is generally utilized in the literature, but insoluble salts are also formed to reduce the content of inorganic salts.

U.S. Patent No. 4,321,215 discloses the addition of acidic oils to an aqueous solution of C1-C4 alcohols and neutralization after removal of the separated neutral oil. Treatment with a polar solvent (water, alcohol) before neutralization creates very corrosive conditions.

U.S. Patent No. 4,269,789 discloses the addition of C5-C10 alkane hydrocarbons, water, and C1-C4 alcohol to the neutralized acid oil to give a reduced oil and salt product from the middle phase after settling. Dilution of the oil phase with hydrocarbons makes the further processing of the oil more expensive and difficult.

U.S. Pat. No. 4,087,456 discloses an oleophilic alcohol, an alkylphenol, an aldehyde for the separation of a brine phase which is not removed or recovered in the process, and its residues also contaminate the sulfonate and sometimes the neutral oil.

According to Dutch Patent No. 6602619, the sulfuric acid content of sulfonic acids is removed as a calcium salt in a hydrocarbon solution. The precipitation of sulfuric acid in the form of CaSCU always entails the possibility of simultaneous formation of calcium sulfonate. The properties of the latter are significantly different from the desired sodium sulfonates.

Japanese Patent No. 7378127 relates to the implementation of sulfonation in a tubular reactor. The neutralization in the presence of the isopropyl alcohol mentioned in the example is intended only to aid in the separation of the nautical oil and the sulfonate;

The Hungarian Patent No. 177232 refers to the enrichment and / or evaporation of the sulfonate obtained by the process described without giving any conditions. The aqueous isopropyl alcohol treatment used in the example is intended only to isolate the major weight of the neutral oil and the sulfonate composition prepared contains all the inorganic salts formed during the process. The sulfonate thus obtained is well suited for specific purposes, such as high efficiency extraction of petroleum, but for many applications such as motor oil additive, corrosion inhibitor, etc. cannot be used, a high purity sulfonate formulation is suitable for these purposes.

We have sought a sulfonate recovery method which overcomes the above disadvantages and thus ensures easy processing of the recovered oil phase on white oils and low inorganic salt content of the sulfonate produced.

In our experimental work, it has been found that the use of two low molecular weight alcohols, ethanol and isobutanol separately, as an extraction medium can meet the stated requirements. After neutralization, the acid product of the sulfonation is treated with aqueous ethanol to isolate the neutral oil, which in this case contains only a small amount of ethanol and water as foreign matter, and can thus be easily and economically processed even to the final white pharmaceutical oil. after lowering the ethanol, mixed with isobutanol and adjusted to a pH of 8-9, an aqueous solution containing a small amount of isobutanol can be separated as the lower phase containing most of the inorganic salts.

It has also been found that by filtering the isobutanolic sulfonate solution with a filter aid, "veil-like" and any floating impurities present on the phase boundary can be removed to ensure a uniform purity of the recovered sulfonate.

The invention thus provides a fertilizer process for recovering petroleum sulfonate from an acid resin separated from an acidic resin obtained from oleic or sulfur trioxide sulfonation at a temperature of 10 to 80 mnT / sec at 40 ° C, wherein the acid oil is 5-15% by weight with It is neutralized at 40-70 ° C, preferably 5060 ° C, in an amount of 10-20% by weight, preferably 16-17% by weight, of ethanol: water in a volume ratio of 1.3: 0.70.7: 1.3, preferably 1 The mixture is separated by settling, the upper, essentially sulfonate-free oil phase is separated off, the ethanol is removed from the lower aqueous ethanol sulfonate solution and isobutanol

HU 202 906 Β

preferably at a concentration of 85% by weight, and if necessary water is added such that the weight ratio of isobutanol to water, based on the petroleum sulfonate and water content, is from 1 to 1.9, preferably from 1.5 to 1.9, the solvent / petroleum sulfonate. weight ratio of at least 3 in the mixture, stirring at 40-60 ° C, adjusting the pH to 8-9, settling the phases, settling, removing the lower aqueous solution containing most of the inorganic salts, a small amount of isobutanol and a relatively hydrophilic sulfonate the upper aqueous isobutanolic sulfonate solution is mixed with 0.5 to 2% by weight of filtration aid, filtered, and the filtrate, after adjusting the oil content (up to 50% by weight) to improve handling of the finished product if necessary, is degassed in a known manner.

Example 1

1000 parts by weight of acidic oil obtained by sulphonation of an oil having a viscosity of 18 mm ² / s at 40 ° C is neutralized with 200 parts by weight of 10.2% sodium hydroxide solution at 56 ° C and 170 parts by weight at 65 ° C. It is mixed with a 1: 1 by volume mixture of ethanolic water and settles for 2 hours. The sulfonate-free neutral oil which forms the upper phase is removed and the aqueous-ethanol lower phase containing 395 parts by weight of the petroleum sulfonate is evaporated to ethanol-free. To the concentrate was added 203 parts by weight, petroleum sulfonate content 38.6% by weight, water content 53.2% by weight, 306 parts by weight 85% by weight of isobutanol (this is 1.7% by weight of isobutanol / water, 5.3% by weight of solvent / petroleum sulfonate). and at pH 45, with stirring, by adding concentrated sulfuric acid to pH 8. After two hours of sedimentation, the separated lower phase is removed, and 5 parts of Perfil K-340 aluminum silicate-based filtration aid are added to the upper portion 465 parts, mixed and filtered. To the 439 parts by weight of the filtrate was added 68 parts by weight of spindle oil and evaporated. The finished product contains 157 parts by weight of commercial grade kerosene sulphonate having the following characteristics:

sulfonate content 50.1% oil content 48.8% inorganic salt content 0.3%

Example 2

1000 parts by weight of an acid oil obtained by sulfurization of oil at 40 ° C with an oil of 18 mm ² / s in oleum was neutralized with 200 parts by weight of 10.2% by weight of sodium hydroxide at 56 ° C at 220 ° C. 60 parts by weight of isopropanol (0.5 parts by weight of isopropanol / water and 5.1 parts by weight of solvent / petroleum sulphonate) are added and the mixture is settled for 2 hours. The sulfonate-free neutral oil which forms the upper phase is removed and the lower phase of the petroleum sulfonate containing 500 parts by weight of water-isopropanol is adjusted to pH 8 with conc. Sulfuric acid, 53 parts by weight of spindle oil are added and concentrated. The 160 parts by weight of the finished product have the following characteristics:

sulfonate content 48.7% by weight oil content 47.8% by weight.

inorganic salt content 3.0% by weight

Because of the high inorganic salt content of the resulting petroleum sulfonate, it does not meet the specifications for commercial grade petroleum sulfonate.

The sulfonate recovery process of the present invention provides up to 50% neutral oil and up to 0.5% inorganic salt content of the product. It allows for a simple and economical processing of neutral oil, since the neutral oil, in addition to the extraction flow water, only comes into contact with ethanol. It uses two solvents that are highly recoverable, recoverable at 96% and 85% respectively. The process can be performed in either batch mode or continuous mode.

Claims (2)

PATIENT INDIVIDUAL POINTS 1. A process for recovering petroleum sulphonate by extraction and evaporation at 40 ° C from 10 to 80 mNr / sec of acidic acid separated from the resin by oleum or sulfur trioxide sulphonation, characterized in that the acid oil is 5-15% by weight of sodium. hydroxide solution, 40-70 ° C, preferably 50-60 ° C, neutralized with 1020% by weight, preferably 16-17% by weight of ethanol in water: 1.3: 0.7-0.7: 1.3 by volume - preferably with a 1: 1 by volume mixture at 50-80 ° C, preferably 65-70 ° C, the layers are separated after pelleting, the upper virtually sulphonate-free oil phase is separated and ethanol is removed from the lower aqueous ethanol sulfonate solution. and adding to the concentrate as much isobutanol, preferably at a concentration of 85% by weight, and adding water, if necessary, to an amount such that the concentration of petroleum sulphonate and water in the concentrate is reduced. ve isobutanol / water weight ratio 1-1.9 - preferably 1.5-1.9 -, the solvent / petroleum sulphonate weight ratio is at least 3 in the mixture, mixed at 40-60 ° C, with a pH of 8-9. after settling, the phases are separated, the lower aqueous solution of the lower inorganic salts, a small amount of isobutanol and a relatively hydrophilic sulfonate is removed, the upper aqueous isobutanol sulfonate solution is mixed with 0.5-2% by weight of filter aid, filtered, and the filtrate is filtered off. the oil content of up to 50% by weight of the finished product can be adjusted by oil dewatering, if necessary, in a manner known per se. 2. A process according to claim 1 wherein the filter aid is an aluminum silicate type excipient.