CS259576B1 - Method of synthetic lubricant and/or component production - Google Patents

Abstract

A method of producing a synthetic lubricant and / or a lubricating oil component, in particular ester oils based on a mixture of oxygenates organic compounds are carried out by esterification, by transesterification and / or polyesterification by-product of oxidation cyclohexane with an aliphatic monovalent alcohol Ce to C24 or binary to with a hexavalent alcohol at 60 to 280 [deg.] C. with subsequent treatment of the product the by-product is isolated from the acidic the waters obtained by washing the crude oxidate, % containing 30 to 90 wt. water concentrating by distilling off the water a crystallization. Obtained concentrate concentrate the product has a water content of 0.5 to 25 ° / o mass, acid value 400 to 800 mg KOH / g, bromine number 0 to 5 g Br / 100 g, at least two dicarboxylic acids wherein the acid adipic forms 35 to 80%. Concentrate sa leads to esterification and polyesterification.

Description

The invention relates to a process for the production of a synthetic lubricant, in particular a lubricating oil or component, in particular a synthetic ester oil, based on a by-product from the petrochemical process as well as traditional raw materials.

Known (Štěpina V., Veselý V .: Lubricants and Special Oils. Veda, Bratislava 1980; Vilenkin AV et al: Chim. I technolog, heating and butter, No 9, 31/1980 / j production of ester oils based on dialkyl esters of dicarboxylic acids acids, as well as acyl esters of C8-C9 monocarboxylic acids and polyhydric alcohols such as ethylene glycol, 1,4-butanediol, trimethylolpropane and pentaerythritol, but there are also limited raw material resources, which also hinder wider application of ester and polyester oils. with polyhydric primary alcohols having 2 to 20 carbon atoms per molecule and branched monoalcohols having 3 to 18 carbon atoms as alcoholic components and mixtures of butyric, valeric and caproic acids resulting from the oxidation of 6 to 12 carbon atoms of cycloalkanes having pat. and US Pat. No. 561,519 does not utilize hydroxycarboxylic acids, esters, lactones and lower carboxylic acids. elines, which are also formed by oxidation of cycloalkanes.

In this respect, technical progress is the process for the production of a synthetic lubricant and / or lubricating oil component, a lubricant based on oxygenated organic compounds, by catalyzed or non-catalysed esterification, transesterification and / or polyesterification of a by-product from cyclohexane oxidation by at least one aliphatic monovalent alcohol C6 to C24; / or a divalent to quaternary alcohol at 80 to 280 ° C according to US. of the author's certificate no. In this case, a mixture consisting of 60 to 98 wt. esters, hydroxyls and carboxylic acids. The viscous product thus obtained is subjected to a physico-chemical treatment as a result of the adsorbents with subsequent removal. selective inhibition, additivation and / or separation. as a rule under reduced pressure, preferably by film or molecular distillation for two to four fractions.

However, even this method does not exhaust the new possibilities of use to achieve an industrially separate uninsulated by-product, respectively. of an intermediate - a dilute aqueous solution of oxygenated organic compounds. generated in the process of oxidizing c-hexane to c-hexanone and / or cyclohexanol. And, as has been shown, the extract and quality of the lubricant or ester oils has an impact on both the esterification, the transesterification or the semi -ification, as well as the bromine number of the by-product, which should be as low as possible.

According to the present invention, a process for the production of a synthetic lubricant and / or a component of lubricating oils, lubricants, based on a mixture of oxygenated organic compounds, catalysed or non-catalysed esterification, transesterification and / or polyesterification of by-product from oxidation of cyclohexane to cyclohexanol and cyclohexanone , wt. carboxylic acids, semi-esters, esters and hydroxy compounds, with at least one C 6 to C 24 aliphatic monovalent alcohol and / or a bivalent to six mono alcohol at a temperature of 60 to 280 ° C, the product thus obtained is physically chemically treated as adsorbents with subsequent removal %, by selective hydrogenation, additivation and / or divided into two to four fractions, carried out by isolating the by-product from the acidic water obtained by scrubbing the crude oxidate containing 30 to 9.0% by weight of the product. water, having an acid number of 70 to 200 mg KOH / g, a mixture of at least two dicarboxylic acids C4 to Ce and at least two monocarboxylic acids C1 to Ce and / or hydroxycarboxylic acids Cs to Ce with a hydroxycaproic acid content of 1 to 16% by weight, of polyesters, esters and unsaturated organic compounds, which is concentrated by distilling off water and crystallizing, the by-product concentrate obtained having a water content of 0.5 to 25% by weight, having an acid number of 400 to 800 mg KOH / g, a bromine number of 0 to 5 g Br / 100 g, containing at least two dicarboxylic acids, of which adipic acid constitutes 35 to 85%, leads to esterification, transesterification and / or polyesterification.

An advantage of the process of the present invention is the technical evaluation of a low-component mixture substantially free of unsaturated, water-soluble, organic by-products from the catalytic oxidation of cyclohexane, reducing the color and antioxidant stability of the final product to high-quality ester oils with low pour point. Absence of bituminous, respectively. polymeric admixtures in the feedstock, on the one hand, particularly the use of the C8 to C6 hydroxycyclic acids, saturated monocarboxylic and dicarboxylic acids, caprolactone and other esters for esterification and polyester with monovalent to hexavalent alcohols, on the other, provides better, lighter ester oils , more oxidatively and thermally stable. Moreover, by conducting the reaction in two stages, the first being applied diol to polvol, the latter reacts quantitatively and in the second stage the reaction with monovalent alcohol is no longer dependent on the degree of reaction to the extracts and the quality of the lubricants, respectively. ester oils.

The oxygenated organic by-product from the oxidation of cyclohexane to cyclohexanone and / or cyclohexanol exits the process

259578

oxidation - as a dilute aqueous solution obtained by scrubbing a crude oxidate frame containing organic compounds, predominantly carboxylic acids, most often in the range of 20 to 35%, and in exceptional cases their concentration may also be outside this range. The organic component of the aqueous solution consists primarily of the aliphatic mono-carboxylic acids C2 to C6 as well as the hydroxycarboxylic acids, in particular ε-hydroxycaproic acid, respectively. 6-hydroxyhexanoic acid and 5-hydroxypentanoic acid, dicarboxylic acids, in particular glutaric acid and -adipic acid. Hydroxy acids form lactones depending on the reaction conditions. In addition, minute amounts of cyclohexanol, cyclohexanone and other, unidentified additives are present. Such a dilute aqueous solution must be freed from at least a substantial part of the water by conventional means, such as by distillation or rectification, in particular by condensation, by azeotropic distillation, crystallization, optionally by recrystallization and the like before being used for esterification, pre-esterification and polyesterification.

The by-product concentrate thus prepared is obtained by isolating from an aqueous solution of the oxygen-containing organic intermediate from the produced oxidation of cyclohexane to cyclohexanone and cyclohexanol (withdrawn from the DK-109 production column), distillation or rectification, notably under reduced pressure, crystallization and separation of the crystalline fraction, filtration, sedimentation and in particular centrifugation. Depending on the composition of the starting aqueous solution of the mixture of organic substances, the efficiency of water separation, concentration and crystallization, as well as the efficiency of crystallization, the by-product concentrate usually has the following composition: water - 0.5 to 25% by weight; acid number = 400 to 800 mg KOH / g; bromine number = - 0.1 to 5 g Br / 100 g; adiic acid content ~ 35 to 80% by weight; glutaric acid = 0.5 to 3.0 wt%; propionic acid ~ 0.01-0.3% by weight; % valeric acid ~ 0.01 to 1 wt. The remainder consists of 5-hydroxyvaleric acid, 6-hydroxycaproic acid, condensation products such as esters, oligomers and other unidentified oxygenated organic compounds.

When calculating the quantities of the by-product concentrate, the dry matter weight or the dry matter weight is taken into account. of anhydrous concentrate. However, it is also practically applied with water admixtures. However, this amount, in addition to the concentrate, in addition to the reaction water produced, should also be taken into account when determining the amount of "discharger".

The manufacturing process is most often carried out continuously, but it can also be carried out semi-continuously and continuously.

Further data on carrying out the production process of the present invention as well as other advantages are apparent from the examples.

Example 1

Of the 1,246, -0 acidic by-products, respectively. 'Intermediate' of cyclohexane oxidation by-product - apparatus DK-109 with a water content of 66,6% by weight, an acid number of 140,6 mg KOH / g, a bromine value of 2,9 g Br / 100 g and an ester number

25.3 mg KOH / g (propionic acid = 0.2 wt%; n-butyric acid = 0.6 wt%; n-valeric acid = 0.3 wt%; n-caproic acid = 0.6 2-methylvaleric acid = 0.7% by weight 6-hydroxycaproic acid = 9.6% by weight succinic acid = 0.8% by weight glutaric acid = 1.2% by weight adipic acid = 4.2% by weight cyclohexanol = 2.4% by weight (cyclohexanone = 1.1% by weight) by distilling off water at 2.67 kPa to give 526 g of a concentrate having an acid number of 321.6 mg KOH / g; ester number 86.2 mg KOH / g; bromine number 1.1 g Br / 100 g; % and a water content of 20.9 wt.

The concentrate contains mainly (in% by weight):

0,3% propionic acid,

1,0% n-butyric acid,

0,5% n-valeric acid,

1.1% caproic acid,

1.3% 2-methylvaleric acid,

27.6% ε-hydroxycaproic acid,

1.4% succinic acid,

3.2% glutaric acid,

12.0% adipic acid,

2.4% cyclohexanol and 0.6% cyclohexanone.

The remainder to 10-0% are other, unidentified acids and esters.

This concentrate is esterified and partially polyesterified with a mixture of 450 g of 2-ethylhexanol-50 g of pentaerythritol, with an admixture of 6.2% dipentaerythritol. During the esterification of 11 h, 180 g of water are obtained, of which 80 g is water. After completion of the reaction, a fraction ® containing mainly unreacted 2-ethylhexanol and low boiling volatile esters weighing 128 g is distilled off from the crude esterification product under reduced pressure (2.7 kPa).

The residue in the distillation flask, crude esters, was subjected to fractional distillation on a molecular evaporator at 4 Pa. At a heating medium temperature of 160 ° C, the first fraction of the ester oil was obtained in an amount of 195 g and at a temperature of 250 to 280 ° C II. 197 g fraction. The distillation residue has a kinematic viscosity at:

° C 1080 mm ² .s ^-1 ;

density 1037 kg. m ^-3 ;

acid number 1.6 mg KOH / g;

saponification number 321 mg KOH / g and? content of groups 0.7 wt.

The properties of the ester oils obtained are as follows:

Flash point I = 186.0 ° C,

II. fraction = 216.0 ° C;

pour point = -60 ° C, resp. —52 “C; kinematic viscosity at 20 ° C = 19.2, respectively.

59.7 mm ² . s ^-1 , at 95 ° C = 3.1, resp. 5,6 mm ² . s ^-1 . Example 2

The procedure is similar to that of Example 1 except that the esterification and pre-esterification catalyst is used in an amount of 1.5% by weight. temperature stable sulfocation (sulfonated polyphenylene ketone). Similar results were obtained, but within 7.5 h of esterification, transesterification and polyesterification.

Example 3

Concentration and crystallization of the acidic (waste waters specified in Example 1) gave 900 g of concentrate which was esterified in the first step with 35 g of dipropylene glycol in a nitrogen stream at 100 to 200 degrees Celsius for 9 h. 232 g of water were formed. the esterification mixture was cooled to 160 DEG C. and 750 g of 2-ethylhexanol were added thereto, and a second esterification step, carried out at 160 DEG-210 DEG C. for 8 hours, gave an additional 35 g of water.

After the esterification is complete, 350 g of a mixture containing unreacted 2-ethylhexanol and a mixture of low-boiling esters are distilled off under reduced pressure at 110 DEG C./36 mm Hg.

The crude ester, weighing 1020 g, was triturated on a three-stage molecular evaporator under conditions as in Example 1. 330 g of a light oil fraction (fraction I) and 381 g of a heavier fraction (fraction II ciaj) were obtained. in an amount of 290 g.

The light oil fraction (fraction I and heavier fraction II) has the following basic characteristics:

acid number 0,6, resp. 0.9 mg KOH / g ^-1 ; kinematic viscosity at 95 ^q C = 2.9, resp.

5.8 mm ² . s ^-1 ;

pour point = -60, resp. —55 ° C and flash point - ISO, resp. 220.0 ° C. Example 4

An aqueous solution of a mixture of organic substances formed by scrubbing the reaction product (oxidate) from the catalytic oxidation of cyclohexane to cyclohexanol and cyclohexanone (aqueous solution from DK-109), which is used in hydrolysis (in a hydrolysis column DK-102) to hydrolyze a mixture of polyesters and % of cyclohexene oxidation products such as. the by-product intermediate (MEK) is at a concentration of 35.4% by weight. (the remainder i.e. 64.6% by weight of water). A more specific characteristic is in Example 1.

This is concentrated by distilling off some of the water at 20 mm Hg and cooling the concentrated solution to 20 DEG C. ^and crystallizing a substantial portion of the crystalline solid from the solution which is collected by filtration. A concentrate having an acid number of 321.6 mg KOH / g, an ester number of 86.2 mg KOH / g and a water content of 20.9% by weight, as well as more specifically specified in Example 1, is obtained. it does not esterify with a mixture of 50 g of pentaerythritol with a 6.2% dipentaerythritol admixture with 450 g of 2-ethylhexanol, but only with 50 g of pentaerythritol at 160 and 220 for 7h and the second stage with 450 g of 2-ethylhexanol.

The fraction of fraction I (186 g of fraction I) and II. the fraction was obtained in an amount of 211 grams, with a pour point = -64 degrees Celsius.

Claims (2)

saponification number 321 mg KOH / g → 0.7% wt. The properties of the obtained ester oils are as follows: flash point I. fraction = 186.0 ° C, II. fraction = 216.0 ° C; freezing point = -60 ° C, resp. Kinematic viscosity at 20 ° C = 19.2, respectively; 59.7 mm2. s-1, at 95 ° C = 3.1, respectively. 5.6 mm2. EXAMPLE 2 A procedure similar to Example 1 was followed, using only 1.5% by weight of a temperature-stable sulfocation (sulfonated polyphenylene ketone) as the esterification and esterification catalyst. Similar results have been obtained, but for 7.5 h esterification, pre-esterification and polyesterification. EXAMPLE 3 Concentration and crystallization of the acidic waters (exemplified in Example 1 gives 900 g of concentrate which is esterified in the first step with 35 g of dipropylene glycol in a nitrogen stream at 100 to 200 degrees Celsius for 9 h. The reaction mixture is then cooled to 160 DEG C. in an esters and 750 g of 2-ethylhexanol are added and the second stage of esterification carried out at 160 DEG to 210 DEG C. for 8 hours yields 35 g of water. 50 g of a mixture containing unreacted 2-ethylhexanol and a mixture of low boiling esters are distilled off at 110 ° C / 2.67 kPa, the crude ester of 1 020 g is fractionally distilled on a three-step molecular evaporator under conditional conditions as in the example. 1. 330 g of a 1 ' light oil fraction (I fraction) and 381 g of a heavier fraction (II. Fraction 8 < tb > = dark brown viscous residue in a quantity of 290 g). ) have the following basic properties: acid number 0.6 and 0.9 mg KOH / g-1, kinematic viscosity at 95 qC = 2.9 and 5.8 mm2, s-1, freezing temperature = -60 and, respectively, 5555 ° C and a flash point of 180180 and 220.0 ° C, respectively. Example 4 An aqueous solution of a mixture of organic substances resulting from washing of the reaction product (oxidate) from the catalytic oxidation of cyclohexane to cyclohexanol and cyclohexanone (aqueous solution from DK) -109), which is used in hydrolysis (in a hydrolysis column DK-102) to hydrolyze a mixture of polyesters and esters of cyclohexane oxidation by-products, i.e. as a byproduct intermediate (MEK), is at a concentration of 35.4% by weight (the remainder, ie 64.6 ° / o by weight, forms water). concentrating by distilling off a portion of the water at a pressure of 5.3 kPa and cooling a substantial portion of the crystalline base from the solution by cooling this concentrated solution to a concentration of 321.6 mgKOH. (g), an ester number of 86.2 mg KOH / g and a water content of 20.9% by weight, also specified in Example 1. However, unlike Example 1, this concentrate is not converted and is not esterified with a mixture of 50 g of peneterythritol admixed with 6, 2 DEG C. dipentaerythritol with 450 g of 2-ethylhexanol, but most preferably with 50 g of pentaerythritol at 160 DEG C. and 220 DEG C. for 7 hours and a second step with 450 g of 2-ethylhexanol. The fraction of I fraction (186 g of I. fraction) and II. the fraction is obtained in an amount of 211 grams, with its freezing point = - 64 degrees Celsius. PREPMET A process for the production of a synthetic lubricant and / or a lubricating oil component, based on a mixture of oxygenated organic compounds, catalyzed or non-catalyzed by esterification, transesterification and / or polyesterification of a by-product from the oxidation of cyclohexane to cyclohexanol and cyclohexane, % consisting of 60 to 98 wt. carboxylic acids, semi-esters, esters and hydroxyl compounds, containing one or more aliphatic monovalent alcohols C6 to C24 and / or bivalent to monohydric alcohols at 60 to 280 ° C, the product so obtained is sophysically chemically selected as the effect of adsorbents followed by their removal, selective by hydrogenation, additivation and / or separation into two to four fractions, characterized in that the by-product is isolated from the acidic waters obtained by washing of the sulfur oxide containing 30 to 90 wt. water, with an acid number of 70 to 200 mgKOH / g, a mixture of at least two dicarboxylic acids C4 to C6 and at least two monocarboxylic acids C 1 to C 6 and / or hydroxycarboxylic acids C 8 to C 6 contents of hydroxycaproic acid of 1 to 16% by weight, lactones semi-esters of ester-unsaturated organic compounds which are concentrated by distilling off the water and crystallizing, yielding a by-product concentrate having a water content of 0.5 to 25% by weight, with an acid value of 400 to 800 mg 2 US 576 9 KOH / g, a bromine number of 0 to 5 g Br / 100 g, containing at least two dicarboxylic acids, of which adipic acid is 35 to 80%, is carried out for esterification, esterification and / or polyesterification. 2. Process according to claim 1, characterized in that the esterification and / or the esterification is carried out in two stages, at least one divalent to quadruple alcohol being used in the first stage and in the second stage preferably at least one monovalent alcohol.