DE1138392B - Device for sulfonating petroleum distillates which can be sulfonated or partially sulfonated with sulfur trioxide - Google Patents

Description

The invention relates to a device for sulfonating petroleum distillates containing sulfur trioxide are sulfonatable.

Hydrocarbon oil fractions, such as petroleum distillates, undergo refining treatment with sulfur trioxide subjected to, for example, white oil for medicinal purposes and / or sulfonates or To manufacture sulfonic acids.

In a method known to the inventor, a petroleum fraction is partially sulfonated by treating the oil with a gas containing anhydrous SO ₃ . Even if so much SO ₃ is used that theoretically complete sulfonation of the sulfonatable hydrocarbons present in the oil could take place, the sulfonatable oils are always only partially sulfonated. Usually ₃ may be contained in the gas up to 10% SO, but is usually in the SO ₃ content in the gas between 8 and 8.5 ° / _0th

Although this treatment with anhydrous SO _{3 has} certain advantages over the treatment with concentrated sulfuric acid or fuming sulfuric acid, it is also associated with certain disadvantages and difficulties. For example, the oil must be repeatedly treated with fresh gas containing sulfur trioxide in order to achieve proper sulfonation, or the partially sulfonated oil must be recycled or often treated in several separate stages. Furthermore, a relatively large _{amount of SO 3 is} required and a relatively large amount of sludge tends to be formed.

The implementation of the sulfonation has already been attempted in a wide variety of devices that are known in the chemical industry for treating liquids with gases and vice versa, e.g. B. in columns, packed towers, spray rooms or with cascade trays. However, even using the most efficient known apparatus, large quantities of oil must be recirculated, e.g. B. up to 16 parts by volume of circulating oil per part by volume of fresh use. Furthermore, the SO ₃ consumption is relatively high. In addition, there is a strong build-up of sludge, which is difficult to handle and remove. The installation and maintenance costs of these devices are relatively high, and with some petroleum distillates a washing device must be switched on to avoid excessive contamination of the atmosphere.

The aforementioned difficulties are eliminated by the device according to the invention. This takes place the treatment of the oil to be sulfonated with the gas containing sulfur trioxide all at once Device for sulfonation

of sulfonatable with sulfur trioxide

or partially sulfonated petroleum distillates

Applicant:

Sonneborn Chemical and Refining

Corporation,
New York, NY (V. St. A.)

Representative: Dr.-Ing. A. v. Kreisler,

Dr.-Ing. K. Schönwald and Dr.-Ing. Th. Meyer,

Patent attorneys, Cologne 1, Deichmannhaus

Claimed priority:
V. St. v. America 9 Jan 1958 (No. 707 941)

Engelo Bevevino, Petrolia, Pa. (V. St. A.),
has been named as the inventor

Passage with less acid consumption and less sludge formation.

The invention is described with reference to the drawings.

Fig. 1 shows schematically a vertical section through an embodiment of the device for Carrying out the sulfonation;

Fig. 2 shows schematically a cross section through the device shown in Fig. 1;

Fig. 3 shows a plan view of an embodiment a perforated disc for the device according to the invention, which is provided with a non-perforated disc or a non-perforated part with a smaller diameter and is suitable for operation with lower liquid level is suitable;

Fig. 4 shows schematically a plan view of a further embodiment of one with a heating or Perforated disc with cooling coil for the device according to the invention;

FIGS. 5 to 9 show further embodiments of the rotating internals for the device according to FIG Invention.

According to the invention, the oil is treated with the SO ₃ -containing gas in that the latter is passed through a plurality of rotating, perforated disks which are partly immersed in the oil and which are themselves

209 678/344

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cover with a film of oil. Preferably meant for the passage of the gas. If the treatment is carried out in an essentially horizontal position of the disks, any other open contact zone can be used, through which the oil is passed through and in which a certain oil level is exposed that this overall a round transverse is maintained . Have a multitude of parallel cuts and the liquid, e.g. B. the oil, in mutually arranged disks rotating in the zone form of a film that can accommodate the gas in contact about a substantially horizontal axis, which is brought. The openings in the lower parts of the disks are immersed in the oil and the _{gas containing SO 3} as well as the total area of the openings in comparison to the closed part must be so large that rotating disks with the oil film adhering to them produce the desired gas- or the amount of steam is passed through. can. Suitable internals are, for example, the device in which the treatment is carried out rings, ring segments, spokes, impellers, propellers, men, consists of an essentially horizontal cylinder or cylinder segments, the radial or right-hand liquid trough with a multitude of parallel in one a certain angle on the axial shaft of perforated disks arranged one against the other, which are brought to 15. The individual internals can be connected to one another on a substantially horizontal rotatable shaft of various parts, are fastened and protrude with their lower part into the trough or one part can form the continuation of the other. The upper part of the panes is expediently enclosed by a housing each opening in the panes, the inner wall of which is close to an area of 1.3 to 13 cm ² , preferably 1.3 to the outer edges of the panes. There are devices 2 ° 5.2 cm ² . The total area of the openings is 10 lines in order to set the disks in rotation up to 90%> preferably 53 to 58% of the total area, the oil to be sulfonated through the trough to the internals. Expediently, per meter of cylinder ducts and the gas containing sulfur trioxide are provided through at least thirteen disks in length, but the housing or through the perforated disks is preferably used to lead a larger number. The trough and the housing are preferably designed in the longitudinal direction as a lying cylindrical container, the inner diameter of which, lying one behind the other or in a helical line, corresponds roughly to the outer diameter of the scraper strips arranged rigidly or movably on disks. The disks are preferably attached, which rotate with the disks and slide along an inner wall of the cylindrical container that is guided axially through the center of the container, and is attached to the rotatable shaft. On the outer edges of the 30 For the bottoms are on the shaft 7 radial scraper disks can be attached, strips attached, which extend to the circumference of the disks on the inner wall of the cylindrical container. At one end, a gas inlet 10 can slide along. The container is surrounded by a heating or cooling jacket as seen and by the upper part of the bottom 2. The discs or anyone else leads. At the opposite end is a gas outlet part inside the container can be provided with heating or 35, which can be provided through the upper part of the bottom 3 cooling devices. is led. The gas inlet 10 can also be used as a gas outlet

The cylindrical shell 1 forms with the bottoms 2 occurs and the gas outlet 11 serves as a gas inlet, and 3 a lying cylindrical container, the gas through the bottom 2 is laterally above the middle and is liquid-tight and a liquid inlet pipe 12 is guided as a pressure vessel from the point. in the can be formed. It is provided with a jacket, bottom 3 is a liquid through laterally from the center the a heating or cooling agent are run drain pipe 13 attached in the form of an overflow can. The agent enters at 5 and exits at 6 or (Fig. 2). The tube 12 entering through the inlet vice versa. Liquid flows axially through the center of the container from the drain pipe 13 when it runs a rotatable shaft 7, the gas and liquid has reached the height of this drain pipe. The liquid-tight and preferably pressure-tight through the floors 2 45 keitsstand is maintained at the level of the drain, ahead and. 3 is performed. For this purpose, suitable ones are set so that the incoming amount is not larger Stuffing boxes are provided which do not restrict the rotation than the amount draining through the opening 13. the prevent and at the same time a liquid, gas and drain opening 13 is preferably kept larger, Form a pressure-tight seal. A large number in parallel than is required for the amount flowing out. perforated 50 arranged at a distance from one another. The oil to be sulfonated is passed through the inlet 12 Discs 8 are mounted on the shaft 7 and are inserted. It fills the lower part of the cylindrical rotated by this. The disks 8 have a container, which is to be regarded as a trough, up to the height of the the same or a slightly smaller diameter drain 13. The shaft 7 and those attached to it than the inner diameter of the shell 1, so that they are disks 8 by means of a motor-driven regulating device the rotation, the inner surface of the cylindrical 55 bares reduction gear set in rotation. A Touch the container or at a short distance from it usual, sulfur trioxide-containing gas is then slide by. The exact design of the discs is introduced through the inlet 10. It flows through that and the shape of the perforation are insignificant, openings in the panes and can go through the length of the hole the disk while rotating a film occurs 11 to be discharged. The desired sulfonic acid Liquid, e.g. B. the oil, and the gas 60 tion temperature can be adjusted by a can pass through the openings. The disc can e.g. B. heat exchange medium, ζ. Β. cold water through which be designed as a circular sieve or grid, and inlet 5 introduced into the jacket 4 and through Ausdie Openings can be of any shape and size. occurs 6 is discharged.

For example, they can be square, rectangular, during the rotation of the disks 8 that come with their

If you dip the lower half in the oil in a polygonal, round, slit-shaped or irregular shape, they cover each other

be shaped. Under the term »perforated with a thin film of oil that coincides with the through the

Disk "is any disk or disk-like upper part of the cylindrical container and the opening

Formations with a multitude of openings or passages in the internals flowing sulfur trioxide

containing gas is brought into contact. In this way, a very large oil-coated area is the Exposed to the action of the gas, so that an extremely effective treatment is achieved.

By appropriately setting the number of revolutions of the shaft 7 and the amount of through the inlet 12 entering and exiting through the drain pipe 13 oil can this up to the desired degree be sulfonated. The amount of gas flowing between the gas inlet 10 and the gas outlet 11 can adjusted so that the most efficient utilization of the sulfonation gas is achieved. By the great specific area of the oil exposed to the sulfonation gas and the possibility of an exact

amount can with much higher throughput speeds, much smaller devices, and much less Labor and energy expenditure than previously sulfonated

A major advantage over the known method is that the oil in one-time Passage can be completely sulfonated, while repeated in the known processes Treatment and circulation are required.

The device enables the sulfur trioxide to be used so effectively that _{residual gases practically free of SO 3} can be obtained.

The rotation of the perforated discs through the liquid results in a self-cleaning effect, which prevents clogging or obstruction of the openings.

The possibility of sulfonation of the oil in

Regulation of quantities and speeds can be 15 single pass, it is unnecessary to use the oil in a single pass through the device large amounts for dilution, and the same oil can be completely sulfonated, so that a
There is no need to recycle the oil or treat it again.

The device can be used to sulfonate all petroleum products.

distillates or other oil fractions are used. The cylindrical container is, as in the

those, which are usually shown with a sulfur trioxide ent- figures, preferably exactly horizontally holding gas are sulfonated. Any arrangement is suitable. Of course, he can also use an inclined position of gas, which is usually available for this purpose, but the inclination must not be so strong that it is used, e.g. B. Air containing about 8.35% SO ₃ . 25 that there is no liquid in the lower part into which the

lower part of the perforated disks dips during rotation, can jam. This situation where a certain liquid level is still maintained is referred to here as "essentially horizontal".

Furthermore, the cross-section of the device need not be uniform. He can be changed in every way provided that the internals rotating in each part are as close to the inside of the designed as a housing run along the upper part that most of the gas flow through openings Avird of the discs and cannot flow around the discs without sticking to the disc Touching oil.

The device can optionally be pressurized

detachable, closed partial disks 14 4 ° or vacuum as well as countercurrent or cocurrent are provided, which are shown in FIG. Be operated at this. Precise regulation of the temperature arrangement, the gas only flows through the meshed part of the panes, which can be carried out with the aid of the cooling or heating jacket, so that a higher degree of efficiency is achieved. If the liquid was lower, the individual perforated disks can be provided with a heating level without the closed part of the disks 45 or cooling elements. As worked for example or without separate cover plates,
some of the gas would flow through the middle part of the disks that is not wetted with oil, so that
this part of the gas would not be used for the sulfonation.

Both the acquisition costs and the operating costs of the device are proportionate low. The rotation of the discs through the oil causes the oil to move well so that it is in the in most cases, no sludge will accumulate in the device. If you work under conditions that the Promote the formation of large amounts of sludge, then the device is cleared by the scraper bars 9 held by mud deposits, so that they last for longer

Time can be operated without it for cleaning 60 net. In the form shown, the cylinders are permanently stopped must become. formed and consist of a wire mesh, however

All the reaction conditions for sulfonation, such as temperature and pressure, are the same as in usual procedures. Only the way of working is different.

Instead of the overflow opening 13, a suitable pump can of course be used to discharge the oil will. Furthermore, instead of cocurrent treatment, countercurrent treatment can be carried out by, for example, introducing the sulfonation gas at 11 and removing it at 10.

If the oil level is to be kept lower than halfway up the cylindrical container, it is preferred the middle part of the disks 8 is not provided with openings up to the liquid level, or As shown in Fig. 4, an inlet line 15 and an outlet line 16 for a heat exchange medium guided axially through the shaft 7. A heat exchange coil 17 spirals from the inlet along the surface of the disc to exit 16. In this way, a suitable heating or Coolant passed from inlet 15 through coil 17 and discharged through line 16 will.

FIG. 5 shows an embodiment of the rotating internals which are used in place of the disks 8 can. In this case, there are several cylinders 18 with an increasing diameter, which are attached to the support arms 19 are attached, arranged concentrically around the shaft 7

It is surprising and completely unexpected that the SO ₃ consumption to achieve the same degree of sulfonation is significantly lower than with the usual processes, and the products formed (oil, sulfonate) are just as good or of better quality than they are obtained with the usual devices will.

they can also form a closed surface. The oil film forms in the annular spaces between the Cylinders 18 through which the gas flows.

7 and 8 show a further embodiment of the rotating internals. Here runs from one Middle disk 20, which is fastened on the shaft 7, a plurality of disk segments after radiating

Outside. Each of the disc segments is curved or provided with a slope so that the passages 22 between the segments are formed. The passages 22 cover each other during the rotation of the Discs with an oil film and gas flows through them. Due to the shape of these disc segments a more intensive movement or a promotion of the oil achieved.

In the embodiment shown in FIG. 9, the rotating internals consist of solid disks 23, which are attached to the shaft 7 and of which a plurality of spokes 24 radiate outwards runs. The absorbed oil film adheres to the spokes, through the spaces between which the gas flows.

example 1

A petroleum distillate that has been partially acid-pretreated and has the following properties was sulfonated:

o, ct

Viscosity (Saybolt Universal seconds) 430 at 37.8 ° C

Specific weight at 15.5 ° C ... 0.893

Refractive index at 120 ^a C 1.4860

Iodine number according to Hanus 4.1

Lich sulphonate was only 5.5 percent by volume (as 100% sodium salt).

Example 2

By treatment in the device shown in Fig. 1 at 54 to 66 ° C with 60 g SO ₃ per liter of oil and subsequent neutralization, extraction, drying and filtration in the usual way, the oil prepared according to Example 1 was converted into a medicinal white oil with the following Key figures converted:

Viscosity (Saybolt Universal Seconds) at 37.8 365 ⁰ C.

Specific weight at 15.5 ° C ... 0.8845

Refractive index at 2O ⁰ C 1.4810

Hanus iodine number 0.0

The oil met the requirements of the US Pharmacopeia purity tests.

If, on the other hand, the sulfonation was carried out by the usual method, 102 g SO ₃ per liter of oil were required, while the usual treatment with oleum of 104% H ₂ SO ₄ required 300 g of oleum per liter of oil in three treatment stages.

Example 3

The oil was in that shown in Figs

Device treated. The device had an In the device described and on the im

Length of 1.50 m, a diameter of 0.39 m and example 1 named manner was a petroleum distillate with

was treated with thirty-two metal discs of 37 cm 3 ° following indicators:

Provided diameters, which were fixed at a distance of 13 to 76 mm on the shaft. The area of each opening in the disks was 1.3 cm ² and the total area of the openings was 53 to 58% of the total area of the disks. The shaft to which the disks were attached rotated at 120 rpm.

A stream of air _{containing 8.35% anhydrous SO 3} was introduced through inlet line 10. The residual gases were discharged through outlet 11. The oil was introduced in an amount of 5.7 to 26.5 l / min through the inlet pipe 12 and withdrawn through the drain pipe 13. The treatment temperature was kept ^{between 54 and 66 °} C. with the aid of cooling water, which was introduced at 5 and discharged at 6. The amount of gas carried out was adjusted so that 41 g of SO ₃ were consumed per liter of fresh input. Under the above conditions, the oil leaving 13 was completely sulfonated. After neutralization, purification, i.e. extraction of the oil-soluble sulfonates formed, and drying, it had the following key figures:

Viscosity (Saybolt Universal seconds) 380 at 37.8 ° C

Specific weight at 15.5 ⁰ C ... 0.8863

Hanus iodine number 1.0

Refractive index at 120 ⁰ C 1.4827

Yield of oil-soluble sulfonate in percent by volume (as 100% Na salt) 6.0

55 viscosity (Saybolt Universal Seconds) at 37.8 108 ⁰ C.

Specific gravity at 15.5 ⁰ C ... 0.8827 Flash point (Cleveland open cup) 177 ° C

ASTM pour point -40 ° C

Refractive index at 20 ° C .... 1.4826

Iodine number according to Hanus 8.5

Using 68 g SO ₃ per liter of oil, the starting material was converted into a product with the following key figures:

Viscosity (Saybolt Universal seconds) 100 at 37.8 ° C

Specific weight at 15.5 ° C ... 0.8729

Refractive index at 20 ° C 1.4750

Hanus iodine number 1.0

Yield of oil-soluble sulfonate in percent by volume (100 ° / ₀ sodium sodium salt) 8.4

In contrast, the conventional process 97g SO ₃ per liter of oil were required in application with only 7.9 ° / ₀ oil-soluble sulfonate were obtained.

60

In order to obtain a finished oil with the same properties by treatment according to the usual method, 60.5 liters of fresh input 978 liters of oil per minute had to be circulated. In addition, g SO ₃ per liter of feed material were required. In addition, the oil obtained by the usual process had a much higher iodine number, and the yield of oil-soluble

Claims (4)

PATENT CLAIMS: 1. Device for the sulfonation of sulfur trioxide sulfonable or partially sulfonated petroleum distillates by reaction with sulfur trioxide-containing gases, characterized by an elongated, with inflow and outflow devices for oil and SO ₃ -containing gas, in the lower part more or less filled with the oil to be sulfonated , and in the upper part of the SO ₃ -containing Gas flowed through trough, which is penetrated by a horizontal rotatable shaft, on the perforated Discs that reach close to the wall of the trough are attached. 2. Apparatus according to claim 1, characterized in that the trough of a jacket for Flow is surrounded by cooling or heating means. 3. Apparatus according to claim 1 or 2, characterized in that the perforated discs with 10 a device for cooling or heating are provided. 4. Apparatus according to claim 1 to 3, characterized in that the perforated discs with sliding scrapers are provided on the inner wall of the trough. Considered publications:
German patent specification No. 571 124. 1 sheet of drawings I 209 678/344 10.62