CS239392B1 - A method of preparing oil-soluble sulfoacids and white oil to form a low-viscosity acid slurry - Google Patents

Abstract

The invention relates to an improved method for the preparation of oil-soluble sulfonic acids and white oils from mineral oils and their raffinates by sulfonation with contact gas or gaseous sulfur dioxide diluted with an inert gas containing 2 to 30 parts by volume of sulfur trioxide, while sulfuric acid or oleum with a total sulfur trioxide content of 40.0 to 87.2% by weight is added to the sulfonated oil, in an amount of 0.1 to 8.0% by weight, calculated as one hundred percent sulfuric acid on the starting oil, preferably 90 to 98 percent sulfuric acid in an amount of 1.0 to 1.5% by weight, thereby ensuring the necessary low viscosity, good fluidity and manipulability of the acid sludges formed.

Description

239392 3 4

The present invention relates to the improvement of the preparation of oil-soluble sulfoacids of white oils of mineral oils and of Irafinates by sulfonation of single-stage or multi-stage, feed or continuous sulfur trioxide in the form of a contact gas with sulfur trioxide content. 5 to 9% by volume, or sulfur dioxide dilute inert gas, with a sulfur dioxide content of 2 to 30% by volume, to provide the desired low viscosity waste product sludge product required for its and transporting the production equipment by adding a small amount of sulfuric acid or olea to the sulfonated oil.

In the sulphonation of mineral oils used mainly in the form of selective raffinates, hydrogenated, or hydrogenated selective raffinates, a very fine mixture of reaction products is formed, which is divided into two mainly groups. One group consists of hydrocarbyl-soluble sulfoacids, also called mahogany acids. The species form a sulphoacid-insoluble in hydrocarbon oil, which also abolishes green acids. The green acids are collected in an acid sludge which is separated from the sulfonated oil as a lower layer by more specific gravity by sedimentation or by means of a centrifuge. The oil-soluble petroleum sulfoacids are monosulfoacids whose sulfo group is bound to either the hydrocarbon radicals consisting of the aromatic-naphthenic nucleus to which a relatively long paraffinic chain is attached and the acid type corresponding to the quality, pure mahogany acid, or the sulfo group being bound an oxygenated residue derived from the aforementioned radicals. The insoluble voluminous sulfoacids include, on the one hand, the monosulfoacids which the sulfo group is linked to the radical consisting of aromatic-naphthenic nuclei by short paraffinic chains (hydrocarbon sulfoacids), or to the oxygen compound derived from the last-named radical ( sulfoacids of resins), or a radical consisting of oxygenated polymers of higher molecular weight, asphaltenic sulfoacids), and disulfoacids in which sulfo groups are attached to the aromatic-naphthenic nucleus with short side-paraffinic chains (less aromatic disulfonic acids) or to the highly aromatic nucleus without paraffinic chains (highly aromatic disulfoacids), or oxygenated and polymeric compounds derived from the latter types of hydrocarbons (bitumen and asphaltenic disulphuric acid) and higher polysulfoacids.

The acid sludge contains, in addition to the oil-insoluble sulfoacids, still entrained mahogany acid, entrained unsaturated oil and a small amount of sulfuric acid.

In addition to the composition of the starting hydrocarbon oil, the selectivity of the sulfonation with the maximum formation of oil-soluble monosulfoacids is mainly due to the following: the composition of the sulfonating agent and the monomeric ratio to the sulfonable oil compounds, the reaction temperature and the closest possible constituents of the reactants given by the type-sulfonating reactor.

The ratio of the sulfonating agent to the sulfonated hydrocarbon oil has a stoichiometric ratio needed to convert the monosulfoacids. In a multi-stage sulfonation, the sulfonation ratio of the rails in the first sulfonation steps is smaller (for example, in the first sulfonation step of 0.4 to 0.5 at three sulfonation stages) and at the last sulfonation stage at a higher quality grade. In this connection, it is very important to have a high-efficiency mixing of the reaction mixture when it is a heterogeneous reaction in order to achieve the closest possible contact of the reactants with the exclusion of a local excess of the sulfonating agent in order to prevent the oil from being presulphonated. The excess of the sulfonating agent, especially in conjunction with the higher reaction temperature, promotes the formation of disulfoacids, possibly higher polysulfoacids.

The reaction temperatures for the sulfonation of mineral oils with reaction times of several tens of minutes, or even several hours, are generally 20 to 60 ° C, 45 to 55 ° C for white oils, and up to 80 for high viscosity oils. ° C. However, when the reaction mixture is subjected to very large shear forces, the contact time of the reactants is only a few seconds to a fraction of a second to completely react the sulfonation mixture, it is possible, or even preferable, to use higher reaction temperatures of up to 100-150 ° C, depending on viscosity and the contact time of the reactants.

In order to create the optimum reaction conditions in the sulfonation process, allowing the formation of mono-sulfoacids to a maximum extent, the type of sulphonating reactor, its construction, which determines the physical parameters of the sulphonation process, is essential. The sulfonator must allow for a very rapid formation of a very fine dispersant sulfonating agent in the sulfone liquid material (ideally molecular dispersion), adequate dissipation of the heat of reaction, which is relatively large to avoid deposition of presulfonating and complete reaction of the reactants with a relatively short duration. . A number of types of sulfonators are proposed in the patent literature, many of which satisfy these requirements in a satisfactory manner.

For the uninterrupted process of the production process, especially continuous, it is important that the acid sludge has a sufficiently low viscosity, necessary for its movement in the production plant, transport via pipeline and further handling. The acid slurries from sulphonating processes using sulfur trioxide as the sulphonating agent are substantially more viscous to solid than from oleate sulphonation. The viscosity of the acid sludge depends on the degree of a sulfonated oil composition.

In the known processes, viscosity is reduced and, in part, reduced formation of acidic sludge during sulphonation of the oil by sulfuric acid gas supports the addition of non-sulphonated organic diluents to the sulphonated mixtures. As diluents, U.S. Pat. No. 2,769,736 nitro- and chloro-nuclear-hydrocarbons are proposed; USA2 802 026 toluene or xylene fraction; UK 680 613 low molecular weight low molecular weight hydrocarbon; and V. Brtan 79S 763 non-sulfonable motor oil, gas oil and white oil. The disadvantage of the present invention is the need for the addition of a large amount of diluent and its costly desulfurization from the reaction product.

In the sulphonation of mineral oils with sulfuric acid and / or contact gas, the viscosity of the acid quencher increases with the viscosity of the starting oil and with the depth of the oil refining with the selective solvent and hydrogenation. acid slurries are obtained in the first sulfonation step, which often solidifies rapidly. For example, in a three-stage sulphonation of selectively furfuran-refined oil and a hydrotreated aromatic hydrocarbon content of not more than 7% by ndM, such highly viscous and rapid-setting acidic resins were obtained in the first sulphonate step to prevent the oil from being processed into petroleum white oils. oil-soluble sulfonates on continuously operating equipment. Therefore, a process has been chosen in the production that high-refined oils providing high yields of white oils and a high proportion of desirable solubilized sulfo acids over the undesired oil-insoluble sulfoacids are mixed with the lower quality refined oils in order to achieve the desired fluidity. However, at the cost of reducing the yields of the desired products and impairing the economics of production.

It has now been found that in the sulfonation by contact gas or gaseous sulfur-dioxide diluted inert gas of mineral oils and their raffinates, providing unacceptable high-viscosity to solid acid slurries, the viscosity of acidic sludge can be reduced to a satisfactory sulfuric acid or oleate value , with a content of 40.0 and 87.2% by weight of total sulfur trioxide, in an amount of 0.1 to 9.0% by weight, calculated as 100% sulfuric acid per starting oil, preferably by addition of 0.8 to 1% by weight of sulfuric acid. 6% by weight 90 to 98% o sulfuric acid, calculated as the starting oil. In view of the operational handling of acid sludge, it is desirable that its viscosity be below 100,000 Pa. s / 30 ° C maximum 180,000 Pa. s / 30 ° C. Acid viscosity of the sludge below 100,000 Pa. with / 30 ° C, 90 to 98% by weight, calculated on the starting oil, is already added by adding 1.0 to 1.5% by weight sulfuric acid. Sulfuric acid or oleum is added to the sulfonated olefin with stirring during sulfonation, or immediately prior to sulfonation, or after sulfonation is complete before the acid sludge is separated off by gravity sedimentation, or by centrifugation and is continuously added during continuous sulfonation. sulfonation. Sulfuric acid used, which has already been used for the purification of white oil, may also be used.

In the multi-stage sulfonation of the oil with a contact gas or sulfur trioxide with inert inert gas, which is usually a three-stage, four-stage, it is usually sufficient to add sulfuric acid or sulfonated oil only in the first sulfonic step. The method of preparing the oil-soluble sulfoacids and white oil with the formation of a viscous acid sludge by the addition of a small amount of sulfuric acid or olea to the sulfonated oil has the following advantages: a) it also allows the processing of deeply refined mineral oils, resulting in an increase in the yield of white oil; which is difficult and costly for the environment to be disposed of, - increasing the capacity of the production facility; b) allowing the production of higher viscous white oils; c) completely eliminating the difficulties which in the manufacturing process cause high-viscosity and rigid acid pitch according to known processes. Illustrative examples are non-limiting examples. Example 1

For the sulfonation, a mineral oil produced from paraffinic oil, refined with furfural, and hydrogenated with a kinetic viscosity of 66.02 mm 2 was used. S-1 at 20 ° C, VI 104, flash point (PMj 202 ° C. Sulfonations were performed in a glass laboratory apparatus equipped with a stirrer with a rotational speed of 3,200 rpm, at 50-55 ° C. 5% by weight sulfuric acid and 92.5% by volume of nitrogen The sulfonation depth corresponded to about one sulfonation step of three-stage operation sulfonation at about 40 to 55% by weight in the first stage, and 30 to 30% by weight in the second stage. a) Sulfonation of oil without addition of acid sludge diluent: oil deposition bound SO3 acid sludge acid slurry viscosity Acid sludge composition: mineral oil sulfuric acid water sulfo acid acid number b) Sulfonation of oil with addition of feed oil bound SO3 acid slurry viscosity of acid sludge Acid sludge composition: mineral oil sulfuric acid sulfo acid water acid value 2000 g 7.3 wt.%, calculated on oil

19.7% wt. calculated on the oil of 3242 psig. s / 30 ° C 26.4% wt. 19.2 wt. 7.5% wt. 46.9% wt. 206.7 mg KOH / g, 3% wt. sulfuric acid 92%: 2000 g 7.25% by weight, calculated on oil

17.25 wt.%, Calculated on oil 47.217 Pa. s / 30 ° C 28.9% wt. 26.8% wt. 10.9% lim. 30.8% wt. 272.2 mg KOH / g. The results show a decrease in the viscosity of the acid sludge during the sulfonation of the oil with the addition of sulfuric acid diluent (method b) to one-seventh compared to the viscosity of the sulfonation without the addition of sulfuric acid (method a). the process a) is unsuitable for the manufacturing process. Example 2

A very highly refined mineral oil having a kinematic viscosity of 53.7 mm 2 was used for sulfonation under the conditions as in Example 1. s' 1 at 20 ° C (16.48 mm 2. s_1 at 50 ° C), VI 129, flash point (PM) 218 ° C. a) Sulfonation of oil without addition of acid sludge diluent: oil feed bound SO3 acid oil acid slurry viscosity of acid slurry Acid oil products: alcoholic soaps sodiumneutral oilSalic sludge composition: mineral oil acid sulphide acid acid number bj Sulfonation of oil with addition of 1.5 oil-bound SO3 acid slurry viscosity acidic kieselguhr oil

Acid Oil Products: Alcoholic Soap Soap Neutral Oil 2,000g 9.5% by weight, calculated on an oil feed of 95.0% by weight, calculated on an oil shaft of 14.5% by weight, calculated on an oil shaft of 711.651 Pa. s / 30 ° C. 38.7 ° / o wt., Calculated on an oil shaft of 80.7% by weight, calculated on the oil shaft. 14.0% wt. 33.9% wt. 10.0% wt. 42.0% wt. 449.4 mg KOH / g. % wt. sulfuric acid 93%: 2 000 g 9.5% by weight, calculated on an oil feed 15.2% by weight, calculated on the oil feed

41,789 Pa. s / 30 CC 94.3 wt.%, calculated on an oil shaft of 34.3 wt.%, calculated on an oil shaft of 81.0 wt.%, calculated on the oil shaft.

Claims (1)

Process for preparing oil-soluble sulfoacids and white oil with the formation of low-viscosity acid sludge by one or more stage, batch or continuous sulphonation of mineral oils and their raffinates with contact gas or sulfur trioxide diluted with inert gas containing 2 to 30% by volume sulfuric acid Sulfonated oil adds with stirring during sulfonation, or immediately prior to sulfonation or after sulfonation, but before separating the acid sludge from the acid oil, sulfuric acid or oleate having a total sulfuric acid content of 40.0 to 87.2% by weight in the amount of 0, 1 to 8.0 wt.%, Calculated as 100% sulfuric acid on the starting oil.