DE2138637A1 - Dispersant with low foamability - prepd by pyrolysis of petroleum fractions or coal, and sulphonation - Google Patents

Abstract

A method for producing dispersing agent having improved properties of less foamability and high dispersibility, which comprises: (a) heat-treating raw material hydrocarbons of petroleum and coal types at 700 degrees C to 2,000 degrees C for a time instant of from 0.0001 second to 0.5 second; (b) cooling condensed polycyclic aromatic compound resulting from the heat-treatment; (c) subjecting the condensed polyclic aromatic hydrocarbon compound to sulfonation; and (d) neutralizing the sulfonated substance to produce a sulfonic salt thereof.

Description

Process for the production of hydrocarbon sulfonates and their Use as dispersants "Dispersants are often used for dispersing used by oil and fine solid particles in water. Most known However, when used, dispersants cause the mass in question is kept in motion, a strong foam formation or an air lock. the In some cases a foaming effect is even desired, but it often causes it big problem. Due to the foam layer on the surface of the liquid, the Shielded from the atmosphere and observing the state of the liquid The surface of the liquid is made more difficult. Another disadvantage of the foaming effect occurs in ceramic technology, in slurries or Crowds used by dispersing finely powdered solids in water can be obtained. Obstruct the foam layers generated on the liquid surface the pressing therefore slurries or masses. Those in the dispersion by air entrapment Foams produced also lead to Pxesslinge with high porosity and therefore finally molded parts with low mechanical strength are obtained. It there is therefore interest in improved, highly effective dispersants with reduced Foaming effect The object of the invention was to provide a process for the production of new, can be used in a wide variety of technical fields with dispersants reduced foaming effect and excellent dispersing effect are available too place. This object is achieved by the invention.

The invention thus provides a method for producing Hydrocarbon sulfonates, which is characterized in that one hydrocarbon mixtures petroleum-based or coal-based foal hydrocarbon mixtures 0.0001 to Heated for 0.5 seconds to temperatures of 700 to 20000C, the product mixture obtained cools down, the resulting aromatic-rich tar or pitch fraction or one of them heavier fraction obtained by thermal treatment or separation per se sulfonated in a known manner and the sulfonic acid mixture obtained in itself in a known way converted into a salted milk.

As hydrocarbon mixtures based on petroleum are used in the process the Invention of crude oil or petroleum distillation products such as gas oil, kerosene, heavy fuel, Heavy oil or bitumen.

The starting hydrocarbon mixtures can be used in the process of the invention regardless of their different composition due to their different origins or the different distillation processes involved in their production to form mixtures converted from hydrocarbons with the desired high aromatic content. When heated, the Koglenwasserstoffe obtained in the starting mixtures are in subject to a high degree of implementation, the nature of which is not fully understood. There is mainly a pyrolysis of the hydrocarbons and a polycondensation the pyrolysis products instead. This creates a liquid void or solid pitch extremely high aromatic content, but no aliphatic hydrocarbons. It is Surprisingly, that in the process of the invention from a wide variety of starting mixtures by suitably setting the conditions for heating, products are always rich in aromatics with extremely similar properties can be obtained.

In the method of the invention, the starting mixtures are vorzugsauf 0.005 to 0.1 seconds / temperatures of about 900 to 1500 ° C. The subsequent Cooling is carried out in any way. When using made from coal Starting mixtures can the process of the invention at the same temperatures -as when using petroleum-based hydrocarbon mixtures. However, a longer heating time is required.

The product mixtures resulting from heating consist of gases, such as hydrogen, olefins or acetylene, and oil-like products. The oily products can further into light fractions, such as benzene or toluene, as well as cere fractions, like tars, are separated. These tears turn out to be due to different analytical methods such as chromatography, nuclear magnetic resonance spectroscopy and IR spectroscopy as mixtures of different condensed polycyclic aromatics with different Molecular weight. The mixtures not only contain no aliphatic hydrocarbons, but the aromatics also have only a small amount of aliphatic side chains on.

The aromatic-rich mixtures can be sulfonated as such. It can however, fractions obtained from the samples are also sulfonated.

mix e.g. by distillation or solvent extraction / man the mixtures can also be heated to temperatures of Convert 350 to 1000C into heavier hydrocarbon mixtures.

Any conventional method can be used for the sulfonation will. The sulphonating agent used is e.g. concentrated or fuming sulfuric acid, Sulfur trioxide or chlorosulfonic acid is used. By setting the reaction conditions During the sulfonation, the degree of sulfonation can be regulated.

The mixed hydrocarbon sulfonic acids obtained in the sulfonation will neutralized with an inorganic or organic base to form salts. as lint is preferred ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, Sodium phosphate, triethanolamine or mor) holin.

The invention also relates to the use of the aforementioned Process produced hydrocarbon sulfonates as dispersants, in particular for concrete The sulfonates obtained by the process of the invention of the condensed Polycyclic aromatics can be mixed with the neutralization as by-products other salts may be used. If necessary, add the sulfonates however, separated from the remaining salts before use. You can use the invention produced sulfonates also together with auxiliaries, such as other salts or surfactants.

The hydrocarbon sulfonates made by the process of the invention can be used as dispersants in a wide variety of technical fields, If you use them in the manufacture of heat-resistant materials, the clay masses or slurries or casting compounds, they not only make handling easier because they do not Have a foaming effect, but with their help can also compact molded parts can be obtained with increased mechanical strength. Analog results can can be achieved by pressing clay-hound carbon stones. According to the invention manufactured Hydrocarbon sulfonates are also suitable as dispersants for drilling fluid in oil well drilling or for making slurries for the mud circulation process in construction engineering. When the sulfonates are used as dispersants for concrete no air is trapped in the fresh concrete. According to the advice the concrete therefore has the required mechanical strength. According to the invention Hydrocarbon sulmonates produced are therefore particularly suitable as dispersants in the production of concrete with high mechanical strength in the hardened state.

The sulfonates prepared according to the invention have when used a low foaming effect as a dispersant. In the case of fresh concrete it is however, it is sometimes desirable to entrap air bubbles in the wet for the sake of machinability of the hardened concrete and its resistance to freezing and increasing melting water. For this purpose, concrete is used in certain Air entraining agents added at intervals. If the invention produced sulfonates as dispersants together with such air entrained substances are used, the effects of the two additives complement each other the base material in such a way that an overall air entrapment effect is achieved will.

The examples illustrate the invention.

B e i s p i e 1 1 Heavy fuel 0.04 e is used. in one from within heated reactor to 1100 ° C. After cooling, it becomes ethylene and acetylene obtained as a gaseous product and a tar as a liquid product. Gate tar is at. Distilled 5 torr at temperatures up to 25,000. That as a residue The pitch obtained turns out to be a mixture on the basis of various analytical methods of various condensed polycyclic aromatics.

30 g of the pitch are then concentrated for 3 hours at 80 ° O with 40 g Sulfuric acid sulfonated. The sulfonic acid mixture obtained is then with Calcium hydroxide neutralized. The precipitated sulfonates are filtered off, pus thickened and dried. 80 g of sulfonates are obtained in the form of a dark brown Powder. This powder is used in various proportions to make a concrete of the table 1 apparent composition added.

Table 1 Composition of the concrete Components proportions, kg "Asano" type cement (Nippon Cement Co., Ltd.) 1 5, 0 Gravel (grain diameter above 10 mn) 41.2 Gravel (grain diameter up to 10 mm) 13.8 Sand (grain diameter above 0.6 mm) 23.3 Sand (grain diameter up to 0.6 mm) 15.7 Mixing water quantity 9.2 Table II shows the properties of the concrete obtained with the addition of certain proportions of the aforementioned sulfonate dispersant.

T able II Disper- Reduction in- Spreading- Pressure-resistant search for greedy- the connection- closed area, speed, kg / cm² -No. proportion,% water volume, air volume, cm ***) *)% **)% ***) ***) after after 7 days 28 days gene 1 - - 2.1 18.1 127 247 2 0.1 3.8 2.0 17.7 133 258 3 0.3 7.2 2.0 18.1 139 276 4 0.5 10.9 1.9 17.9 145 284 *) Percentage by weight, based on the concrete.

**) Based on the amount of mixing water for the non-dispersant Concrete (= 100%).

***) Determined according to Japanese industrial standards (JIS A-1128-1960 and JIS A-1108-1963).

The results of Table II show that the amount of mixing water to be used the lower and thus the higher the mechanical strength of the hardened concrete the higher the proportion of dispersant.

-B e i s p i e l 2 30 g of the sulfonated pitch from Example 1 neutralized with sodium hydroxide. 76 g of a sulfonate mixture in Obtained in the form of a dark brown powder.

This powder is used as a dispersant in various proportions added to a concrete of the composition shown in Table III. In the Concrete should contain air bubbles.

T ab el 1 e III Composition of the concrete Components proportions, kg Portland cement (Onoda Cement Co.) 15.0 Gravel (grain diameter above 10 m) 44.1 Gravel (grain diameter up to 10 mm) 14.7 Sand (grain diameter above 0.6 mm) 22.3 Sand (torna diameter up to 0.6 mm) 15.0 Mixing water quantity 8.3 Table IV shows the properties of the concrete obtained with the addition of certain proportions of the aforementioned dispersant and an air-entrained substance.

Table IV Disper- Air- Reduce- Compressive strength, such greed- pore- closed wide- kg / cm² -No. medium, the amount of air in the air, area, kg / cm² % share mach-%% after % water- 7 days 28 days *) lot, % 1 - - - 1.5 7.2 179 335 2 0.25 - 4.2 1.2 7.3 221 368 3 0.35 0.006 15.7 5.3 7.5 246 394 4 # 0.25 0.005 13.3 5.2 @ - 8.3 231 381 5 0.15 0.004 10.8 4.2 8.3 233 397 *) Non-ionic surfactant ("Hi-Foam"; Onoda Unilon Co., Japan); The proportion of air entrained substances relates to the entire concrete.

The values given in Table IV show that when using the Sulphonate mixtures produced according to the invention have excellent air storage is achieved and that the required amount of mixing water is reduced.

Be i s p i. e 1 3 Kuwait raw oil is preheated to 3000C and then superheated in flowing at a rate of 5 kg hour Water vapor sprayed in. Water vapor is used in a heat storage heater heated to about 20000C using zirconia heat stones.

The crude oil is 0.06 seconds at temperatures from 1100 to 1200 ° C brought into contact with the superheated steam and cooled the product mixture. Be there get 700 liters of gases and 4-50 g of a tar per hour. The tar is at 5 torr Distilled up to a temperature of 2000C. This gives you the residue per Hour 230 g of pitch, which is based on the analysis carried out according to Example 1 proves to be a mixture of various condensed polycyclic aromatics.

The pitch is sulfonated according to Example 1. The sulfonic acids are neutralized with sodium hydroxide. The sodium sulfonate mixture thus obtained is added to an aluminum oxide casting compound. The mass consists of aluminum oxide cement (10 percent by weight, based on the surcharge) and fireclay sand as a surcharge as well a certain amount of mixing water. The properties of the additive-free or sulfonate-containing Table V shows the dimensions.

Tab 1 1 e V no addition + 0.2 weight- percent of bad luck derived Sulfonates Mixing water quantity, ß 16.5 13.0 Porosity, £?, I 32.4 29.3 Compressive Strength, kg / cm after hardening *) 170 300 after drying **) 160 180 after firing ***) 240 310 *) Hardening: 24 hours at room temperature **) Drying: 10 hours at 105 ° C *** -) Firing: at 1400 ° C.

The results of Table V indicate that, as a dispersant the amount of mixing water used. in making the concrete as well reduces the porosity of the poured concrete and its mechanical strength increase.

Example 4 The sodium sulfonate mixture from Example 3 is used as Dispersants in the manufacture of clay-bonded carbon stone-graphite base nen on / inserted. Table VI shows the properties of additive-free stones as well as stones to which a certain amount of the sodium sulfonate mixture has been added became.

T l 'abe 1 1 e VI + + 0.2 percent by weight Sodium sulfonate no additional mix Mixing water volume,% 17.1 16.6 Porosity,% 25 23.7 Shrinkage on drying,% 3.82 3.75 Compressive strength after Drying, kg / cm2 295 354

Claims (4)

13 a t e h t a n s p r ü c h e 1. Process for the production of hydrocarbon sulfonates, d u r c h e k e n n n z e i c h n e t that one hydrocarbon mixtures on Petroleum-based or coal-based hydrocarbon mixtures 0.0001 to 0.5 Seconds heated to temperatures of 700 to 20000r, the product mixture obtained cools, the resulting aromatic tar or pitch fraction or a heavier fraction obtained therefrom by thermal treatment or separation in sulfonated in a manner known per se and the Sttlfonsäuregemisch obtained in converted into a salt mixture in a manner known per se. 2. The method according to claim 1, characterized in that the Hydrocarbon mixtures 0.005 to 0.1 seconds at temperatures from 900 to 150,000 heated. 3. The method according to claim 1 or 2, characterized in that one for salt formation ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium phosphate, Triethanolamine or morpholine is used. 4. Use of the prepared according to Verrahren of claims 1 to 3 Hydrocarbon sulfonates as dispersants, tel, especially for concrete.