CS256164B3 - Thermally and thermooxidised liquid - Google Patents

Abstract

Thermally and thermo-oxidatively stabilized liquid according to AO No. 238 506 based on hydrocarbons containing 1 to 50% of at least one organic stabilizer, from the group of aromatic amines and their derivatives, and/or phenol and their derivatives, especially their condensates, the organic stabilizer component of which is alkaline earth metal sulfonate, such as calcium metal sulfonate, and the derivatives of phenol and their condensates with oxy- ■nyl]phosphite, tris(4-cumylphenyl)phosphite, bis(2,4- nylethyl)phenyl]phosphite, tris(2,4-di-tert-butyl)phosphoric chloride, phosphorus trichloride and pentaerythritol include tris[2,4-(1-fe- -di-tert-butylphenyl)-pentaerythritol diphosphite, bis(4-cumylphenyl)pentaerythritol diphosphite and bis- [ 2,4-(1-phenylethyl)phenyl]pentaerythritol diphosphite. It is used as a heat transfer agent medium in the energy, chemical and wood industries, metallurgy, construction, for its excellent electrical, oxidation and other physical and physicochemical properties, also in the electrical industry.

Description

The invention relates to thermally and thermo-oxidatively stabilized liquids, suitable in particular as heat transfer medium, but also dielectric insulating liquids, formulated using technically readily available stabilizers.

High-quality thermally and thermo-oxidatively stabilized liquids based on alkanic, isoalkanic, cycloalkanic, aromatic and alkylaromatic hydrocarbons, suitable especially as heat carriers or heat transfer media, used mainly in power engineering, chemical, metallurgical, mechanical engineering and timber industries, should have the highest possible working temperature and heat capacity, chemical and thermal stability, fire resistance and the highest explosion resistance, the lowest freezing point should not be toxic, but technically readily available. In particular, the thermal and thermo-oxidative stability of liquids and thus the possibility of long-term application of such liquids is excellent, in addition to other valuable physical and physico-chemical properties, such as excellent dielectric, viscosity and coloristic parameters of said liquids and the like.

Thus, until recently, expanded thermostable liquids, respectively. heat carrier, usable in the working temperature range from -3.6 ° to 316 ° C, respectively. 16 to 371 ^C , include polychlorinated diphenyl, or chlorinated biphenyls and terphenyls, respectively. polyphenylether [Golovinskij GL: Chim. Think. 1976, 21 (311); MS. pat. 150 779], However, in addition to the obvious advantages, but also the drawbacks, such as the relatively high freezing point, the considerable difficulty of their use in the winter season, the problem of their toxicity has increased more and more. Also noteworthy are heat carriers based on polyarylenes and polymer-aromatic compounds (U.S. Pat. No. 3,829,518) as well as indanes (U.S. Pat. No. 4,031,489) and polydimethylsiloxane, phenanthrene, diphenoxydicresoxysilane (Andrianova, Aleksandrov: Chim. Promysl. 1974, 178), as well as bis (dialkyladamantyl) -benzenes [U.S. Pat. No. 3,760,020; Japanese Pat. No. 78-017 602 (1978)], but many have a high pour point, are both raw and technically demanding. Alkylbenzenes (cf. author's certificate 201 878) Although technically and raw materials are relatively readily available, are harmless to health, they also have very low pour points (below -40 ^° C), but also only about 325 ° C, which limits their safe application limit to about 260 ° C. However, this application and other hydrocarbon liquids can be significantly increased by adding 1 to 50% of at least one organic stabilizer from the group of aromatic amines and their derivatives and / or al. or phenol, phenol derivatives and their condensates and / or diphenyl to terphenyl and derivatives thereof, according to U.S. Pat. of the author's certificate no. 238 506. It is also an extension of the functional capability of thermally and thermo-oxidatively stabilized liquids under difficult conditions, which is achieved by further modification of their formulation.

According to the present invention, it is a thermally and thermo-oxidatively stabilized liquid, suitable in particular as a heat transfer medium, mainly based on alkali, isoalkane, cycloalkane, aromatic and alkylaromatic hydrocarbons according to U.S. Pat. 238 506, so that an optional component of the organic stabilizer is also an alkaline earth petrosulfonate, preferably calcium petrosulfonate, and the phenol derivatives and their condensates include tris [2,4- (1-phenylethyl) phenyl] phosphite, trls- ( 2,4-di-tert-butylphenyl] phosphite, tris- (4-cumylphenyl) phosphite, bis- (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (4-cumylphenyl) pentaerythritol diphosphite and bis [2,4- ( 1-phenylethyl) phenyl] pentaerythritol diphosphite.

The advantages of the thermally and thermo-oxidatively stabilized liquids of the present invention are the synergism of their organic stabilizers as components, their wide application possibilities even under severe conditions and the technical and raw material availability, not least the biocidal, mainly bactericidal and fungicidal effect of most defined organic stabilizers.

According to the invention, a suitable component of the stabilized liquids is also an alkaline earth petrosulfonate such as magnesium petrosulfonate, in particular a readily available calcium petrosulfonate which is based on calcium salt obtained by neutralizing oil-soluble organic sulfoacids resulting from sulfonation of aromatic-naphthenic petroleum distillate hydrocarbons. It is mainly a detergent additive to a stabilized liquid, which also prevents the deposition of higher molecular weight and other sludge components on the walls of equipment formed during long-term application. Even thermally and thermo-oxidatively stabilized liquids, which together with other positive effects · Liquids.

The organic stabilizer of the above-mentioned liquids is, among other substances having an antioxidant effect, mainly phenol derivatives, such as mono- to trialkylphenols, aralkylphenols, aralkylphenols and their condensates, whether with phosphorus oxychloride or phosphorus trichloride, pentaerythritol or trimethylolpropane.

Further details of the formulations of the liquids of the present invention as well as their other advantages are apparent from the examples.

Example 1

Distillation residue from II. The vacuum column from the production of monoalkylbenzenes with C 1 -C 13 alkyls, consists mainly of dialkylbenzenes and trialkylbenzenes with C 1 -C 18 alkyls, with admixtures of monoalkylbenzenes, tetraalkylbenzenes, diphenylalkanes and other, unidentified hydrocarbon admixtures. At least 90% of the total amount has a boiling point in the range of 212-330 ^{and a} C / 1.3 kPa, an average molecular weight of 321, a density at 20 ^° C (yields ²⁰ ) of 910 kg. m ^-3 , kinematic viscosity at 20 ° C 5.37.10 ^-5 m ² .

. s ^-1 and at 60 ° C 1,10.10 ^-5 m ² .s ^-1 . The flash point is 208 ° C (determined according to ČSN 65 6212), the combustion temperature 222 ° C (determined according to ČSN 65 6212) and the ignition temperature 348 ^C C (determined according to ČSN 650 321). The freezing point of this heat carrier is -46 ° C.

Addition of anioxidants and calcium petroleum sulfonate (calcium salt of the aromatic-naphthenic hydrocarbon petroleum distillates, containing 53% w / w calcium sulphonaphthenate, molecular weight 940 and kinematic viscosity at 100 ° C 34 mm ²⁾ are added to this distillation residue ^{. 1} ), and subjected to a tempering temperature of 290 ° to 305 ° C, with an interruption of 10 hours, the effective time counting only the time during which the thermo-oxidatively stabilized liquid is exposed to the said high temperature and air ingress. The results of the dependence of acid number (mg KOH / g) and sludge formation (% / w / w) on time in individual experiments are shown in FIG.

1. FIG. 1, curve 1 shows the effect on the acid number and 1 'on the sludge content of the distillation residue with the additive and 0.2% by weight. % tris [2,4- (11 ^- phenylethyl) phenyl] phosphite (AO 6); calcium petrosulfonate.

Curve 2 and 2 ‘show the course of the acid number and the sludge content of the thermo-oxidized stabilized liquid consisting of said distillation residue with the addition of 5% by weight. calcium petrosulfonate, 0.5% w / w; tris [2,4- (Tphenylethyl] phenyl] -phosphite (AO 6) and 1% by weight of α-tert-butylated p-cumylphenol (AO 301) and curve No 3 and 3 'containing said distillation residue, 1 wt% tris- [2,4- (1'-phenylethyl) phenyl] phosphite and 1 wt% 2,6-di-tert-butyl-4-methylphenol (AO 4 K).

Example 2

For the removal of the heat of reaction from the tempered tubular reactor in which the heterogeneous catalyst undergoes a strong exothermic oxidation reaction at a temperature of 240 to 250 ° C, a substantially isodecane fraction is used as the heat-removable liquid, having a "life" of 1% by weight. tris [2,4- (1-phenylethyl) phenyl] phosphite is increased by 68% and in addition with the addition of 1.5% by weight of calcium petrosulfonate by 96%. For the combination of organic stabilizers in the amount of 0.5% tris- ( 4-cumylphenyl) phosphite, 0.85% bis [2,4- (1-phenylethylphenyl) pentaerythritol diphosphite increases the service life by 79% and in addition with the addition of 2% calcium petrosulfonate by 102%.

Claims (2)

256 5 l of boiling in the range of 212 to 330aC / l, 33 kPa, average molecular weight of 321, density at 20 cc (d20) 910 kg. m-3, cinematic viscosity at 20 ° C 5.37.10 -5 m 2. . s-1 and 1,10.10-5 m2.s-1 at 60 ° C. The temperature of the flame is 208 ° C (determined according to ČSN65 6212), the burning temperature 222 ° C (determined according to ČSN 65 6212) and the ignition temperature348 CC (determined according to ČSN 650 321). The freezing point of this heat carrier is -46 ° C. Further to this distillation residue are added calcium anoxidants and petrolsulfonates (calcium salt of sulfo-aromatic-naphthenic hydrocarbons of petroleum oil distillates, with calcium sulfo-naphthenate content of 53 °, molecular weight 940 and kinematic viscosity at 100 ° C of 34 mm 2 s). -1), and subjected to a temperature of 290 ° C to 305 ° C, interrupted after 10 hours, while the time during which the thermo-oxidising fluid is exposed to said high temperature and air access is counted in effective time. The results of acid number dependence (mgKOH / g) and sludge (%) on the individual experiments are shown in FIG. 1. In Figure 1, curve 1 shows the effect of acidity number and 1 'on the sludge content of the distillation residue with addition and 0.2% by weight of tris [2,4- (11-phenylethylphenyl] phosphite (AO 6) and 6% calcium petrosulfonate 64. Curve 2 and 2 'show the course of the acid number and sludge content of the thermo-oxidatively stabilized liquid, consisting of said distillation residue with the addition of 5% calcium petrosulfonate, 0.5%. Tris [2,4- (1'-phenylethyl) phenyl] phosphate (AO 6) and 1% by weight of α-tert-butylatedhophexylphenol (AO 301) and curve 3 and 3's of said distillation residue, 1% by weight of tris- [2,4- (1'-phenylethyl) phenyl] phosphite and 1% by wt. 2,6-di-tert-butyl-4-methylphenol (AO 4 K). EXAMPLE 2 A substantially isodecane fraction with a 1% by weight addition of heat is used as a heat-transfer fluid for the removal of the heat of reaction from a tempered vortex reactor in which a halo-thermal oxidation reaction takes place on a heterogeneous catalyst at 240-250 ° C. Tris [2,4- (1-phenylethylphenyl] -phosphite is increased by 68% and, with the addition of 1.5% by weight calcium phosphosulfonate by 96%), with the combination of organic stabilizers at 0.5%. % of tris- (4-cumylphenyl) phosphate, 0.85% of bis [2,4- (1-phenylethyl) phenyl] pentaerythritol diphosphite increases lifetime by 79% and higher with addition of 2% petrosulfonate; SUBSTITUTE THERMAL AND THERMOOXIDOUS STABILIZED LIQUID, IN ACCORDANCE WITH ARTICLE 2 50 506, characterized in that the organic stabilizer components are also alkaline earth petro sulphonate, preferably calcium pentosulphonate and condensate phenol derivatives. include tris [2,4- (1-phenyl-N-ethyl) phenyl] phosphite, tris- (2,4-di-tert-butylphenyl) phosphite, tris- (4-cumylphenyl) ) -phosphite, bis- (2,4-di-tert-butylphenyl) pentaerythritol di-phosphite, bis (4-cumylphenyl) pentaerythritol-phosphite and bis [2,4- (1-phenylethyl) phenyl] penta-erythritol diphosphite . 1 sheet of drawings