CS201878B1 - Method of obtaining thermostable liquids - Google Patents

Abstract

The invention provides a technically simple method for obtaining thermostable liquids, particularly suitable as heat transfer fluids or organic heat transfer media, by isolating and possibly treating secondary intermediates or byproducts of the subsequent petrochemical production of important surfactants.

Description

1 201878

The invention is based on a simple method for obtaining thermostable liquids, suitable for use as heat transfer agents, respectively. The organocolloid heat transfer media, by isolation and possibly further treatment, have resulted in several intermediates or products of subsequent petrochemical reactivations of the production of important proactive substances.

It is known that high-quality thermostable liquids suitable for use as heat carriers, such as heat transfer media, used mainly in power engineering and industry, should have as many use temperature, heat and thermal stability, fire resistance and high explosion resistance as possible, not toxic. However, they should be technically readily accessible and hence hungry and have as low heat consumption or heat loss as possible. the heat carrier includes paraffinic petroleum oils (known under the trade name Humbletherm 500), usable in a range of temperatures from -20.56 to 315 ° C, o-diohlorbenzene (Dowtherm E) for the heat transfer region from -17.7 to 26 ° C, eutectic diphenyl-diphenyl ether (Dowtherm A) mixture for temperature range 12.7 to 398 ° C, di- and triaryl ethers (Dowtherm G) for temperatures from -11 to 343, alkyl aromatic petroleum oil (Mobiltherm 600) for the heat-transfer range from -20.56 up to 315 ° C hydrogenated phenyl (Therminol 66) at temperatures from -3.89 to 343 ° C; polychlorinated diphenyl (Theralin FR-1) for the range from -3.89 to 315 ° C and polyphenylether (Therminol 77) for workup temperature from 15 to 371 ° C [o. L. Golovinski, Chimicheskaya washed. 1975. 2l (31l) J. However, if we do not count water and water vapor to the heatsinks, the eutectic mixture of diphenyl (26.5%) - diphenyloxide (76.5%) is used as a base for the organic heat carriers. £ d. R. Frikken, K. S. Rosenberg: Chem. Eng. 82. No. 12, 86 (1975) J in both liquid and vapor form at a pressure corresponding to temperatures up to 330 ° C. In order to achieve a low freezing temperature, 50% by weight is added to the eutectic mixture eSte. monoisopropyldiphenyl, monoethylbiphenyl or naphthalene [jap. pat. 73-33 879 (1973) J. They are also intentionally produced in addition to diphenyl, diphenyl ether, alkyldiphenyl, terphenyl hydrogenated polyphenyl heat transfer agents [i. D. Dard: V.D.I. Ber. (Ver. Dtsoh.Ing.) 216. 29 (1974)} frano. pat. 2,138,838 (1997) and 2,356,094 (1978) J NSR Pat. 2,038,565 (1976) | me p. pat. 74-36585 (1974)} Chem. Abstr. 81, 93550q, 75-18473 (1975) and patent application no. NSR 2 215 433 (1972)], further chlorinated biphenyls and terphenyls. pat. 150,779 (1973) J, halogenated arylalkyl ethers. pat. 78-018 018 (1978) J, polyarylenes and polymeric compounds (U.S. Pat. No. 3,829,518). Then, indanes (U.S. Pat. No. 4,081,489) and polydimethylsiloxane together with the addition of 0.1-0.5% phenylnaphthylamine as an antioxidant, phenanthrene, diphenoxydicresoxysilane, and the like are also produced as heat carriers. N. Andrianova, A.A. AleksandrovtChim. 3, 178 (1974) J and bis- (dialkyladamantyl) -benzene (U.S. Pat. No. 3,760,020), but also alkylbenzenes and alkylnaphthalenes by alkylation of benzene and naphthalene and by olefins by jap. pat. 78-017 602 (1978) J. However, Ioh's disadvantage is the single-purpose production, the investment and the investment demands, and in some cases the less favorable properties of the heat carriers. Thus, in the case of polyarylenes or halogenated di- to polyphenyls, a disadvantage, despite their high thermostability, is the toxic effect on living organisms, in the case of paraffins, lower thermal stability. Therefore, it is evident from 201878 to obtain thermoheats as simple as possible, which would be physiologically harmless, for example mixtures of alkylbenzenes, indanes and tetralin with pressurized hydrogenation (NSR Pat. 17SA 018) and precursors. This interesting method, however, also requires separate hydrogenation and the need for an effective catalyst, mainly resistant to slim compounds.

Thereafter, the advantages of the known heatsinks are utilized and attained at the same time as production, and the most important sodium alkylarylsulfonates are those of the present invention.

According to the present invention, a method for obtaining a thermostable liquid, preferably a heat carrier, is provided. a heat transfer medium based on alkylbenzenes prepared by the alkylation of benzene with 10 to 18 carbon atoms, preferably catalytic with aluminum and / or aluminum chloride, and / or alkenes with 10 to 16 carbon atoms, preferably C 11 to 13 carbon atoms, with the catalytic action of acids, preferably Lewis acids, by the crude benzene alkylate intermediate of the alkylaryl sulfonates being freed from the unconverted starting materials and the catalyst, in the case of benzene alkylation by the chloroacids also the hydrogen chloride and, usually, after the refining with white clay and separating the impurities with the white clay, the monoalkylbenzenes are separated at a pressure of 0.12 to 40 kPa, preferably 2 to 10 kPa, with a boiling point of 101.3 kPa above 250 ° C. , consisting predominantly of dialkylbenzenes and tri-alkylbenzenes, is isolated or isolated as a thermostable kv apaline, preferably decolorizing and stabilizing against oxidation. The advantage of obtaining the heatsinks according to the invention is not only very good stability, physiological harmlessness, raw and undemanding availability, but also the possibility to produce a valuable product, such as didodeoylbenzenes, in one production plant of the production plant, for example sodium dodoylbenzenesulfonate. with tridodeoylbenzenes and acceptors, practically without investment construction. If we add to this the ability to use catalytic complexes for alkylene benzene or catalysed molecular polymerization of alkenes and dienes, the waste of alkylarylsulfonate (AAS) production can have remarkable significance not only from an ecological point of view, but also from a economical-economical point of view. From the point of view of obtaining heat carriers according to the present invention, it is not important that the di-alkylbenzenes to tetraalkylbenzenes are alkylated by benzene with haloalkanes, most aromatic or alkene or a mixture of alkenes in alkanes (e.g. n-alkanoic dehydrogenate), conventional alkylation and / or Priedel - Crafts Catalysts, especially aluminum chloride, respectively. aluminum together with chloroalkanes as its precursor, aluminum chloride complexes with alkylbenzanes, chlorofluorocarbons, etc., other hydrogen fluoride, phosphorus compounds, boron trifluoride / fluorocarbon mixtures, or hydrochloric acid and the like.

Unconverted feedstocks can be, in addition to benzene and haloalkanes, C10 to C18, also alkenes of Cg, as well as together with alkanes C8 to C16, alkyl aromatics and naphthenes. 3 201078

Refining of crude, alkylates can be done either by whitening or by active clays, activated charcoal and other high-specific solids solids. Similarly, the thermostable liquid itself can be decolorized, i.e., a mixture consisting essentially of dialkylbenzenes and trialkylbenzenes with active clay, activated carbon, powdered silica, aluminosilicates, alumina and other large-scale solids. True, admixtures that color the di- to polyalkylbenzene mixture into dark brown are virtually harmless to thermal stability, so that it is not necessary to remove them from the functional grounds, but only in a dehydrated case for aesthetic reasons. Similar heat carriers according to the present invention are good temperature stable without further modification. However, in the case that they will be applied in the presence of air, it is desirable to stabilize them against oxidation with antioxidants, for example 0.1 to 0.5% by weight. Most preferably, known antioxidants are suitable for stabilizing polyolefins and oils, such as o-substituted butylphenols, e.g. 2,6-di-tero. butyl-4-methylphenol, diphenols with methylone or sulphate moieties such as 4,4'-methylene-bis-2,2'-dimethyl-6,6'-diol. butylphenol and analogous thiobisdialkylphenols as well as a mixture of phenols, organic phosphites and zinc salts of organic acids. Diaryl amines such as phenyl-alpha- and phenyl-beta-naphthylamine, phenylnaphthylamine, alkylated aryl phosphites as well as amine phenols, in particular p-hydroxydiphenylamine, are known. Then also diamines such as N, N'-tetramethyldiaminodiphenylmethane and other available antioxidants, mainly with high heat boiling and thermal stability. Further details of the method of the invention are apparent from the examples. Example 1

With vigorous stirring, the n-alkenes are heated to 90 DEG-95 DEG C. with the effluent feed while continuously evacuating the resulting hydrogen halide and the unconverted fluorine, washing the hydrogen chloride with cold water to form hydrochloric acid, conc. 32 to 33 / " - Substantially mono-alcohols are formed, which in turn are co-produced with benzene in a weight ratio of 4.1 wt. parts of benzene and 3.4 wt. parts of the alkaloid to the alkylator. The alkylation is carried out at 60-75 ° C with the addition of aluminum or aluminum hydroxide granules. From the aluminum granules, the aluminum chloride is "in situ" as the actual alkylation catalyst! CH 3 (CH 2) 10 CH 2 Cl + C 6 H 6 -? -. CH 3 (CH 2) 10 CH 2 C 6 H 5 + HCl; Al + HCl-> A1C13 + 1/2 H2. Hydrogen chloride and hydrogen formed along with the vaporized benzene vaporizer in the alkylatoror formed into the condensers in which benzene vapors were condensed.

The crude alkylate with the catalyst is removed from the cooler to a settling tank, the aluminum chloride and the organic aluminum chloride complexes containing the alkylbenzene in the dense sludge form, which continuously pass through the siphon cap to the buffer. Organic dense sludges (complexes) are carried out either on liquidity, mainly hydrolytic 2D58B5 by cleavage with sodium hydroxide or as an alkylation catalyst, optionally also as an oligomerization and polymerization catalyst (oligomerization and polymerization of alkones to dienes up to C Thereafter, the crude allcylbenzene with alkyls is refined under stirring for 1.5 hours with 1.5% by weight of white clay at a temperature of 40 to 50 ° C. The alkylate is then filtered, the white aluminate and the admixtures adhering to the filter. The benzene is further dried and distilled off from the non-converted benzene and the benzene azeotrope, respectively, and the benzene is further dried and vaporized into the alkylation, and the benzene-depleted alkylate is further fed to the X. vacuum column at a temperature of 130-150 ° C and a pressure of 17 ° C. > 33 kPa, unreacted n-alkanes are distilled off to give the admixtures of alkones and chloroalkanes. The vacuum residue of the first vacuum column is passed as a feed into the second vacuum column, preheating to 220 ° C.

The column heads at 160-180 ° C and pressures of about 4 kPa are vaporized with deoylyl to tridecylbenzene, predominantly with dodoylbenzene. This mixture of monoallcylbenzenes is further condensed to a continuous sulfonation and then to the sodium hydroxide to be neutralized to about 5% by weight. sodium undecylsulfonate, about 86 wt. sodium dodecylsulfonate and 9 wt. sodium trideoyl sulfonate, which is the final product.

The distillation residue from II, the vacuum column consists essentially of dialkylbenzenes and tri-alkylbenzenes with alkyls to monoalkylbenzenes and tetraalkylbenzenes, boiling in the range of 212 to 330 ° c / l, 333 kPa, average molecular weight of 321, density at 20 ° C / d 2 ° / 910 kg · m 2, kinematic viscosity at 20 ° C 53> 7 · 1 · 2 m 2 · e 1 at 60 ° C 11, 0 · 10 · m · ra · s · 1, flash point 200 ° C, melting point 228 ° C, total chlorine content 0.01% w / w. This dark-brown distillation residue is the second final product of the thermostable liquid, respectively. a heat carrier suitable mainly for heat transfer, it being desirable to stabilize it prior to oxidation with antioxidants, most conveniently commercially available and used to stabilize oils and polyolefins. Example 2

Distillation residue II. The vacuum column, as specified in Example 1, is further distilled by differential vacuum distillation at 13 mm Hg to reduce coloration. Of 1000 g of distillation residues, the boiling range is 212 to 318 ° C / l, 333 kPa

- O is distilled off 910 g of product having a density of 906 kg.m. Color evaluation is done by measuring light transmittance at 500 nm. While still the distillation residue II. vacuum distillation of a mixture of monoalkyl- to trialkylbenzenes with alkyls, as specified in Example 1 (batch for differential vacuum distillation), having a light transmittance of 4.5 'ft, the light transmittance of the distilled product is up to 86% (permeability of light distilled water is 100 l) ). This distilled mixture of dialkylbenzenes, especially dodoylbenzenes with a smaller amount of trialkylbenzenes, is also a suitable heat transfer medium, with a service life of 0.1 to 0.5% by weight. antioxidants. 5 201878 Example 3

Diluted " II " of the vacuum column, which is exemplified in Example 1, refined by adding activated carbon to a temperature of 25 [deg.] C. and 210 [deg.] C. and additions of active clay at a temperature of 25 [deg.] C. in%) revealed a wave wave of 500 per oaa and sample water and water, whose eme value was a value of 100. 1.

Table 1

Rafináoia deat. nvydku ektlvaym uhlím Rafináoia deat. mvydkn aktlný hlinka Temperature Quantity act. Coal Permeate Temperature Amount Act. coal 'Priepuatnoet * avetla <° c> fjt mass J (st) Co) fit mass *, w> 25 5 26,1 25 1 12,0 130 3 39,1 25 5 27,2 130 5 43,5 25 10 48.1 210 5 38.5 25 20 61.8 Example 4

Deatllataý avytok II. vacuum de-ethoxylation of monoalkylthio trialkylbenzates as intermediates and of the AAS production intermediates, exemplified in Example 1, and the single and stabilized by addition of an anti-oxidant to the alkylaryl arylfoafite (antioxidant A06) in a quantity of 0.1% by weight. aa subjecting the heat exchanger to a temperature of 250 ° and 260 ° C and following the formation of the subsoil of CSV 66 6255 depending on the eapoal time.

Temperature stress, resp. the time of expiration of the period of application of the reagent is 0.1% by weight and 0.1% by weight. AO 6 30 0.018 0.010 60 0.024 0.013 '90 0.035 0.015 120 0.048 0.017 150 0.066 0.020 180 0.082 0.022 200 0.095 0.025

Claims (1)

Example 5 Under similar conditions as in Example 1 aa to alkylaium, dhaloalkanes are used to give C ^ gg. Unreacted n-alkenes and, after separation of the catalyst and benzene, isolate the de-acetyl pressure at a pressure of 1.6 kPa, whereby the separation by fractional de-ketil of the boiling point in the range of 118 DEG to 100 DEG C. is carried out by a monoalkylbenzene and by separation with a pressure of 0.8 kPa. The temperature of the column is from 210 to 285 ° C. The temperature of the boiling point and the boiling point above 372 ° C at a pressure of 101.3 kPa can be used as a topping agent, roep. tazmoatable fluid. The object of the invention is a method for absorbing thermostable liquids, preferably heat carriers, roep. poplar-bearing media, alkylbenzene-based alkylation of benzene with 10 to 18 carbon atoms, preferably 11 to 13 carbon atoms, under the catalytic action of aluminum and / or aluminum chloride, and / or alkali of 10 to 16 carbon atoms, and preferably and 11 to 13 carbon atoms, under the catalytic action of acids, and preferably Levia acids, characterized in that the crude benzene alkylate, as an intermediate for the production of alkylaryl sulfonates, and the unconverted starting materials and catalyst, are also hydrogen chloride and others, usually after refining with white clay and separating the impurities and white clay and separating the monoalline benzene at a pressure of 0.12 to 40 kPa, and preferably 2 to 10 kPa, with a de-oxidation residue and a boiling point of 101.3 kPa above 250 ° C, predominantly from dialkylbenzenes and trialkylbenzenes and and ool, or isolates it as a thermoa tabillary, wherein aa and preferably discolorate and stabilize oxidase.