CS238506B1 - Thermally and thermooxidised liquid - Google Patents

Abstract

Thermally and thermo-oxidatively stabilized liquid, particularly suitable as a heat transfer medium, a liquid with an increased ignition temperature, based on hydrocarbons, but also their derivatives, containing 1 to 50% of at least one organic stabilizer, which significantly increases the ignition temperature. Such stabilizers include aromatic amines and their derivatives /diphenylamine, N-phenyl-N'-isopropyl-p-phenylenediamine, distillation residues from its production and intermediate products, naphthylamine, aminodiphenyl, N-phenylnaphthylamines, phenothiazine and phenoxazine/, phenol, phenol derivatives /cumylphenol, monoalkyl- to trialkylated cumylphenol, alkyl to trialkylphenols, benzylphenol, benzylmethylphenol and dibenzylmethylphenol/, diphenyl and terphenyl and their derivatives.

Description

1,238,506

BACKGROUND OF THE INVENTION The present invention relates to a simple process for the preparation of tenao-stable liquids, mainly with elevated temperature, suitable for use as hydrocarbon-based or derivative-based heat carriers using other technically available compounds.

It is known that high-quality thermostable liquids, suitable as heat carriers, or heat transfer media, used mainly in power engineering, in chemical, mechanical and woodworking applications, should have the highest possible heat and heat capacity, chemical and thermal stability, bridging into the bridge and as explosion-proof as possible, it is not toxic but should be technically easy to access · So, to the most common thermostable liquids, respectively. heat transfer agents include paraffin oils usable at temperature limits t -20 to 315 ° C, o-di-chlorobenzone for operating temperatures from -17 to 7 ° to 260 ° C, eutectic mixture of diphenyl with di-phenylether for the hot 12 , 7 to 395 ° C, di- to tri-aryl ethers for temperatures ranging from -20 to 316 ° C, hydrogenated terphenyls at temperatures from -3 to 6 to 3 ° C; 3 ° C. Then the polychlorinated diphenyl for the range of temperature in the range of -3 »6 to 316 ° C and the polyphenyl ether for the area of the working temperature from 16 to 371 ° C JjGolovinskij G» L: Chim · thought through. Their disadvantage, however, is a relatively high solidification temperature, which makes problems especially in the shutdown of equipment with the application of such heatsinks in the winter as well as the toxicity of several of the known heatsinks. Suitable for particularly high temperature chlorinated bifehyls and terphenyls (U.S. Pat. No. 130,779) and halogenated arylalkyl ethers. Pat., 78-1018018 (1978) J. Their disadvantage, however, is the relatively high toxicity and the demanding disposal of heat carriers based on them. Also noteworthy are the heat carriers based on polyarylenes and polymeromatic compounds (U.S. Pat. No. 3,829,318), such as ajindans (U.S. Pat. No. 031,489) and polydimethylsiloxane , phenylenetrene, diphenoxydicresoxysilane ^ Andrian TM, Aleksandrov A · A: Chim. thought. 178] and bis (di-alkyladimethyl) benzenes, as well as alkylbenzones and alkylnaphthalenes. $ 3 760 020 jap. pat · 78 - 017,602 (i978) J. Their disadvantage is either the high freezing point or, in the case of several technically and raw materials, the demanding production and in the case of alkylbenzenes, the relatively low use temperature. The low temperature of use up to 250 ° C also limits the use of otherwise easy-to-use paraffinic heat carrier dialkyl to trialkylbenzenes with alkyls (MS Author's Certificate 201 878). This is the reason that their ignition temperature is only slightly above 30 ° C. The ignition temperature is important for the maximum application temperature of the vel'rai. The temperature, ignition of the respective substance is the lowest temperature-sensitive surface at which the substance in admixture with the air-borne material results from contact with this hot surface under the pre-written (ČSN 65 0Jl1) test subfamilies A just at the bottom. of the present invention, by means of additives, further increase the ignition temperature of thermostable liquids or heat carriers.

According to the present invention, the thermally and thermo-oxidatively stabilized liquid, suitable in particular as a heat transfer medium for hydrocarbon and / or derivative hydrocarbons, mainly based on 238,506 alkane, isocyanic, cycloalkane, aromatic and alkylaromatic hydrocarbons, contains 1 to 50 wt. . at least one organic stabilizer from the group of aromatic amines and their derivatives and / or phenol, derivatives of phenol and their condensates with phosphorous oxychloride and / or diphenyl to terphenyl and derivatives thereof. The advantage of thermally and thermo-oxidatively stabilized liquid with an increased ignition temperature, particularly suitable as a heat carrier, is the possibility to prepare not only new thermostable liquids, such as carriers, but to increase the ignition temperature and hence their usability at even higher temperatures of the manufactured and commercially available heatsinks. A further advantage is the synergistic effect of most of the added organic stabilizers in thermostable liquids. In addition to increasing the application temperature, they also increase their overall stability, especially the thermo-oxidative and thus overall lifetime of the heatsinks, in the series of advantages, the fact that by adding an organic stabilizer, the low freezing temperatures of the starting thermostable liquids are increased, allowing the heat carriers to be applied to the prepared bed. of the present invention over a wide range of temperatures. The organic stabilizer or mixture of organic stabilizers is usually added to the thermostable liquid to be added during its primary production or additionally, immediately prior to the application of the heat transfer medium.

The organic stabilizer of the aromatic amine derivatives of this invention is predominantly di-phenylamine, alkyldiphenylamine, di-phenylaroin, N-phenyl-N-isopropyl-p-phenylenediamine, and intermediate products thereof, as well as distillation residues. from its production, naphthylamines, aminophenols, aminodiphenyls, N-phenylnaphthylamines, phenothiazine and phenoxazine, further phenol derivatives, to which phenol, dian, cumylphenol and its mono-trialkyl derivatives, mono- to tri-alkylphenols, benzylmethylphenol isomers 4 238 506 and dibenzylmethylphenol, their products include condensation with phosphorus chlorides, in particular phosphorous oxychloride, diphenyl-terphenyl derivatives are mainly their alkyl derivatives and polyalkyl derivatives,

The details of the preparation process and the advantages of the stable liquids of the present invention are evident from the examples. Example 1

The distillation residue II, the vacuum column from the production of the predominant dodecylbenzene, consisting mainly of dialkylbenzenes and trialkylbenzenes with alkyls to C14, with direct monoalkylbenzenes and tetraalkylbenzenes, has a boiling point in the range of 212 to 330 ° C / 1.33 kPa, average molecular weight of 321, density at 20 ° C / d / 910 kg.m "', kinematical viscosity at 20 ° C 5.37.lo" ms "and at 60 ° C 1.1.ΙΟ" 5 m2s "1, Flash point i 208 ° C / set according to ČSN 65 6212 /, burning temperature 222 ° C / set according to ČSN 65 6212 / and ignition temperature 348 ° C / determined according to ČSN 65 0321 /, freezing point of this carrier is -46 ° C, to which Various amounts of diphenylamine or diphenyl (biphenyl), as well as a mixture of diphenyl with terphenyl (37% tert-phenyl), are added to the mixture by distillation residue, resulting in a change in the above mentioned parameters, but a substantial increase in the ignition temperature, such as that obtained by the thermostable liquid results. on 1. 5

Table 1,238,508

Thermostable Liquid Composition Properties Component Temperature Temperature Temperature Type Quantity Type Flammability Formation Mass (% w / w / w / w / C) Mixture of dialkyl and trialkylbenzenes with Cn to C13 alkyls dest, residue / 100 «» 208 222 348 Mixed dialkyl-99 di phenyl-1 208 222 359 and trialkylbene amine zens with alkyl-C__ and? C 98 diphenyl-2 207 221 369 11 13 amine / dist, residue / 95 diphenyl amine 5 204 220 388 90 diphenyl-amphetamate 10 186 208 401 dialkyl / trialkylbene 95 diphenyl / biphenyl (5,196,206,363) with alkyl C 1 to C 13 50 diphenyl / biphenyl (50 211 220 388) dist. residue / 90 mixture of diphenylphenylphenol 10 200 210 372 - 6 - 238 SQ6 The solidification temperature of the heat carrier and 5% of diphenyl amine is -45 ° C to 5 ° C and 10 ° C of diphenylamine -45 ° C. 5 Jo diphenyl (biphenyl) is -47 ° C. Example 2

The distillation residue from the production of the alkylbenzene and the alkylsulfonate, consisting mainly of dialkylbenzenes and tri-alkylbenzenes, is refined with bleaching earth and stabilized by the addition of 0.2% by weight. an alkylated aryl antioxidant-based antioxidant and can be applied as a thermostable liquid or a heat carrier for indirect heating. Its flame temperature is 188 ° C, the flame is 194 ° C and the flash point is 318 ° C. 1 wt. N-phenyl-Ν -isopropyl-β-phenylenediamine (CD antioxidant) has a flash point of 344 ° C and 5% by weight additive. -phenyl-Ν-isopropyl-β-phenylenediamine at 378 ° C.

By using diphenylaraine additives instead of N-phenyl-isopropyl-p-phenylenediamine, a thermostable liquid of 5 wt. diphenylamine, flash point 188 ° C, 200 ° C, and 378 ° C flash point. With 10% by weight of diphenylamine it has a flash point of 184 ° C, a melting point of 198 ° C and a flash point of 390 ° C. So on 5 Jo Mass. of diphenylamine, the ignition temperature of the heat carrier is 50 ° C and 10 µl. diphenylamine additions of 62 ° c Example 3

The commercial dibenzyl-dibenzyltoluene-based heat carrier has an open crucible temperature of 210 ° C, a melting point of 236 ° C and a flash point of 465 ° C. diphenylamine, its ignition temperature increases to 477 ° C. Example 4 238 506 To refined distillation residues from the production of alkylbenzene with alkyls of cn to C13 'Specified in Example 2, 5, 10 and 20 ub masses of a mixture of tris-isopropylphenoyl phosphates are added, consisting mainly of monoisopropylphenyldiphenylphosphate, of bis-monoisopropylphenyl diphenylphosphate and bis-monoisopropylphenylphosphate, as well as small amounts of tris-monoisopropylphosphate and tris-phenylphosphate (Re-tar 13l), prepared by condensing isopropylphenols and phenol with phosphorous oxychloride. Flash point of ter-stable fluids from 188 ° C (without additive) to 190 ° C at 5% w / w, 191 ° C at 10% and 194 ° C of 20 Jb of Retaru 131 · Burning temperature of 194 ° C ° C at 5 wt.% Retar 131 212 ° C at 10 wt. and 2 18 ° C at 20 wt. Ignition temperature from 328 ° C (no additive) to 337 ° C at 5%, 342 ° C at 10wt and 355 ° C at 20wt% Retaru 131 · Re-tar 131 alone has a flash point of 240 ° C , burning temperature ó20 ° C and ignition temperature 550 ° C. Example 5

The procedure is similar to Example 2, but 2% of diphenylamine and 3% of distillation residues from the production of N-phenyl-N'-isopropyl-p-phenylenediamine containing other nitrogenous organic compounds are added to the distilled residue. N-phenyl-N ' -isopropyl-propylenediamine compound 48. The ignition temperature of the thermostable liquid thus obtained is 374 ° C. EXAMPLE 6 238,506 Mechanical impurities are separated from the distillation residues from the production of cumene (isopropylbenzene) by alkylation of bonzene propylene on polyphosphate catalysts and distillation is carried out at a temperature of 205-212 ° C / 100 kPa, consisting essentially of the isomers of diisopropylbenzene. This fraction has a flashpoint of 78 ° C; burning point 80 ° Cj non-safety class III. and ignition temperature 388 ° C, ignition group = B. diphenylaraine in this fraction © has a heat carrier prepared to have a flash point of 80 ° Cf burn point 80 ° C hazard class III. and ignition temperature up to 441 ° C (53 ° C rise); distillation residues, the so-called "sm6MM (after separation of the oil-insoluble fraction) from the production of N-phenyl-N'-isopropyl-p-phenylndiamine (antioxidant CD) instead of diphenyl ignition temperature reaches 437 ° C. Example 7

Commercial heat carrier consisting of a mixture of paraffinic hydrogen (average Cgj) has an average molecular weight of 320 g.mol Its flash point is 200 ° C and 222 ° C and a flash point of 322 ° C. To this is added 10 wt. of an intermediate from the production of phenolic antioxidant, consisting of 64 wt. % of 1-phenyl-1 (2-hydroxyphenyl) tartrate with 1-phenyl-1 (4-hydroxyphenyl) ethane, 14 wt. phenoxyphenol, 7 µl mixtures of dibonzylraethylphenol isomers and 14 wt. phenol.

The ignition temperature remains 196 ° Cj the burning point is 218 ° C $ hazard class = TVj the ignition temperature rises to 336 ° C. Adding 10 wt. of a mixture of 4-cumylphenol with a 2-cumylphenol instead of an intermediate phenolic antioxidant, the ignition temperature rises to 30 ° C. Example 8 238 506

A high-quality commercial heat carrier consisting essentially of a mixture of dibenzyltoluene isomers of raster mass of 270 g »mol applicable at temperatures of 350 to 370 ° C, with a freezing point of -35 ° C, has a flash point of 210 ° C and a melting point of 236 ° C and a ignition temperature (point) of 450 ° C. The addition of 9% diphenylamine further aggravated the rate of ignition to 483 ° C. Example 9

Commercial heat transfer medium (Slovtherm) based on hydrotreated dewaxed selective raffinate 936 has a freezing point of -12 ° C, kinematic viscosity at 100 ° C 6.3 µm 2 with a flashpoint of 220 ° C, a point of elevation of 246 ° C and ignition temperature 324 ° c. Adding 6 wt. diphenylamine increases the ignition temperature to 359 ° C (flash point = 206 ° C and burning point 224 ° C). 10 - Example 10 238,506 To the distillation residue As specified in Example 1, 1.5% by weight of phenothiazine and 0.5% by weight of diphenylamine are added, while the flash point of the thus obtained thermally and thermooxidised liquid is 207 ° C and the temperature of ignition 370 ° C. Example 11 1% diphenylamine, 3% phenyl-6-naphthylamine (N-phenyl-2-naphthyl-amine) and 2.5% by weight diphenyl are added to the distillation residue specified in Example 1. The ignition temperature is as follows Example 12 To the distillation residue Specified in Example 1, 2% by weight of phenoxazine and 5% by weight of diphenyl are added, with the resultant thermally and oxidatively stabilized liquid having a temperature of 372. EXAMPLE 13 To the fraction of the distillation residue from the production of isopropylbenzene specified in Example 6 by the addition of 3% by weight of o-naphthylamine (lnf-ylamine) and 2% by weight of diphenylamine to the degree of ignition of degree o 49 DEG C. EXAMPLE 14 5% of diphenylamine, 4% of o-aminodiphenyl (2, biphenylamine, 2-aminobiphenyl) and 5% of diphenyl containing terphenyl are added to the heat transfer medium specified in Example 9, and the heat transfer media thus obtained the medium has a flash point of 368 ° C. EXAMPLE 15 238 506 35% by weight is added to the fraction of the isopropylbenzene bottoms product. mixtures of isomers of benzylmethylphenols and dibenzylmethylphenols produced by arylalkylation of phenol with styene or methylphenylcarbinol.

Claims (3)

OBJECT OF THE INVENTION 238 506 1. A thermally and thermo-oxidatively stabilized liquid, suitable in particular as a heat transfer medium, based on hydrocarbons and / or light derivatives, in particular based on Slavonic, isoalkane, cycloalkane, aromatic and alkylaromatic hydrocarbons, characterized in that it contains 1 to 50% by weight, at least one organic stabllisator from the group of aromatic amines and their derivatives and / or phenol, phenol derivatives and their condensates with phosphorus oxychloride and / or diphanyl to terphanyl and their derivatives · 2. A thermally and thermo-oxidatively stabilized liquid according to claim 1, characterized in that the aromatic amines and their derivatives include phenylamine, N-phenyl-N-isopropyl-p-phenylenediamine, de-distillation residues from diphenylamine production, distillation residues from N-phenyl production - N-isopropyl-p-phanylenediamine and madreducts from the production of N-phenyl-N-isopropyl-p-phenylenediamine, naphthylamine, aminodipanyl, N-phenyl-2-naphthylamine, phenothiazine and phenoxazine, 3. The thermally and thermo-oxidatively stabilized liquid according to claim 1 or 2, wherein the phenol derivatives include cumylphenol, monoalkylated to trialkylated cumylphenol, monoalkylphenol to trialkylfanol, benzylphenol, benzylmethylphenol and dibenzylmethylphenol.