DE1493235C - Process for the preparation of acidic mixtures rich in vinegar - Google Patents

Description

1 2

The invention relates to a process for the production of salts, for example naphthenates, octylates or Development of acetic acid-rich mixtures of low-molar acetates or inorganic salts, such as carbonacular compounds Fatty acids by oxidation of carbons or nitrates, or oxides, hydroxides or Hydrogen with low boiling areas. free acids are used, wherein the metals

For the catalytic oxidation of higher molecular weight ali- 5 as ions are present, such as stannic acid, or as phatic hydrocarbons of the type of paraf- salts or complex salts of free acids, or the fins one already has alkali permanganese-containing catalysis metals can also be used in metallic form used. will. With particular advantage they can be in shape

It is also already known that hydrocarbons of salts with organic acids, which are soluble in the reaction with a boiling point below 200 ° C with an oxygen ίο tion system, are used,
containing gases in the liquid phase in the presence of a suitable amount of catalyst (as metal

To oxidize cobalt-containing mixed catalyst. This calculates) is between 0.001 and 5 percent by weight, relatively low-acid oxidation, preferably 0.005 and 1 percent by weight, based on mixtures, whose acid numbers are approximately between 30 based on the weight of the charge,
and 70 lie. It is also known that the fractions of the oxidized products obtained in the presence of water below 99 ° C. and the fractions of the oxidized products obtained in the presence of water below 99 ° C. leave boiling first runnings in the circuit In the oxidation process, it can generally be traced back to the following three fractions. divide:

The invention has set itself the task of the 20th

Acetic acid yields in this process to stei- ^l - ^be _n ^Dis? temperatures lower than about

like to obtain and oxidation mixtures whose " ^{c distilled in the} presence of water

Acid number is about 300. This goal under additional fractions, hereinafter referred to as »light frac-

pushing back the formation of formic acid will be ^{denoted <<} ,

according to the invention achieved in that the oxy- 25 2. those from aliphatic monocarboxylic acids with 1 dation at 140 to 200 ° C in the presence of a catalyst with up to 4 carbon atoms and water

lysators, which in addition to a cobalt salt also contain the fractions and

at least one salt of the following metals: sodium, 3 _{residues with higher} boiling points than about

Potassium Calcium Magnesium, Copper, M Cad- _{17QO Q the following} / _as »residue

mium, barium, aluminum, tin, BIe, nickel and 30 _{u high boiling point <<} ^.

Iron, in an amount from 5 to 10,000 weight *

percent, based on the weight of the cobalt and The »light fractions« represent a mixture,

calculated as metal. that mainly consists of non-acidic compounds. B. is between 50 and 150 ° C boiling, such as various alcohols, esters and car fraction (66.2 percent by weight paraffinic carbonyl compounds. The residue with high boiling hydrogen, 29.5 percent by weight naphthenic point consists mainly of naphthenic hydrocarbons and 4.3 percent by weight aromatic and various keto acids and hydroxy acids table hydrocarbons) of a petroleum from the and contains higher alcohols, esters and carbonyl Middle East with air in the liquid phase with compounds together with dibasic acids, a reaction temperature between 160 and 165 ° C, 40 like succinic acid and adipic acid,
a pressure of 40 to 45 atmospheres to 95% oxidized.

the ratio of acetic acid to formate lower fatty acids was additionally obtained between 14.3 and 18.5 when using a den. For example, if one is between 50 and binary Co-Ni catalyst, while this value 3.9 150 ° C boiling fraction of a petroleum from the Mittbis 4.4 when no catalyst was used and 45 ler east was oxidized with air until the absorption was the same using a lead catalyst, 2.8 tion of oxygen practically ceased, with Reakbis 4.0 using Cr, Mg, Fe, Ni and the like at temperatures of 144 to 156 ° C, a pressure alone as a catalyst and 1.7 to 2.3 or 2.0 to 3.1 from 35 atmospheres and as a catalyst a mixture using a Mn or Ce catalyst cobal naphthenate and nickel naphthenate (Co: Ni fraud. Even if the between 30 and 100 ° C sie- 50 == 1: 1.5) were used in such an amount that the end fractions (with a content of 42.7 Ge, the total amount of catalyst, calculated as percent by weight paraffinic hydrocarbons, thaw, was 0.1 weight percent of the feed, 52.2 percent by weight of naphthenic hydrocarbons - 60.2 percent by weight of acetic acid, 3.8 substances and 2.9 percent by weight aromatic carbon percent formic acid, 10.5 percent by weight lenhydrogen) of a natural gasoline in the 55 light fractions and 28.8 percent by weight return liquids Phase under similar reaction conditions with a high boiling point, based on the counterpart, as indicated above, oxidized weight of the converted hydrocarbons obtained, the ratio of acetic acid to Wenn was now a mixture of 1 part of the light frac-formic acid 8.3 to 11.5 again using one tion and 2 parts by weight of the batch Co-Na-Ba ternary catalyst, 8.5 to 11.2 under 60 under the same conditions as oxy use above of a binary Co-Pb catalyst and dated became 84.2 weight percent vinegar-7.0 to 8.8 with the following binary catalysts: acid, 5.1 percent by weight formic acid and Co and Al, Co and K, Co and Mg or Co and Fe, 15.0 weight percent light fractions, based on while this value is 2.5 to 2.9 without a catalyst on the total hydrocarbons consumed, Sator, 1.8 to 2.3 obtained with an Mn catalyst and 2.5 65, the production ratio <v of to 3.8 with a Cr catalyst. Acetic acid to formic acid was 16.5.

The metals of such Co-containing excess constituents - if, on the other hand, the

Partial catalysts can be obtained in the form of the organic petroleum listed below

high boiling point mixed with 200 weight percent crude hydrocarbons and the mixture was oxidized again under the same conditions, the ratio of acetic acid to Formic acid 1.2 to 1.6 without a catalyst, 1.0 to 1.5 with Cr, Mg, Fe or Ni, 1.0 to 1.3 with Mn or Ce and 3.0 to 3.5 with Co; this increased in the presence of cobalt-containing multicomponent catalysts However, ratio to 7.2 to 8.8 when using Co-K or Co-Ca, to 6.5 to 9.7 with Co-Cu, Co-Zn and Co-Cd, to 6.0 to 8.5 with Co-Sn, to 8.5 to 11.3 with Co-Ni, to 10.5 to 13.4 with Co-Pb and to 10.2 to 15.0 with Co-Na-Ba.

When using the residue with a high boiling point, it may be advisable to use divalent Acids - such as succinic acid - to be removed beforehand.

The process can be carried out either individually or continuously.

The reaction temperature can be 120 to 240.degree. C., preferably 140 to 200.degree. If you are higher than 240 ° C, the yields of lower fatty acids are lower and the corrosion of the Reaction vessel is a serious problem.

Oxygen or a gas containing oxygen - such as air - is used as the oxidizing gas. It is advisable to set the partial pressure of the oxygen higher. When the hydrocarbon feeds having boiling points of 50 to 150 ° C or 100 to 200 ° C (vapor pressures are 8.3 kg and 1.5 kg / cm ² at 150 ° C) are oxidized, the appropriate reaction pressure is usually 10 to 80 or 5 to 60 atm.

All paraffinic hydrocarbons and naphthenic hydrocarbons can be used as starting material and mixtures thereof with boiling points below 200 ° C can be used. The presence aromatic hydrocarbons do not interfere with the oxidation reaction; but there are aromatic hydrocarbons hardly take part in the formation of the lower fatty acids, the content of aromatic Hydrocarbons are preferably low. Untreated petroleum and petrol are suitable natural gasoline. If the starting material contains a large amount of substances that interfere with oxidation, contains, for example, sulfur compounds, it is purified, preferably by known processes, for example by treatment with concentrated sulfuric acid, aluminum chloride and hydrogen.

example 1

The oxidation system consisted of a vertical stainless steel autoclave with a capacity of 11 with a vertical stirrer of the electromagnetic type, a gas inlet and a system for Measurement of temperature was equipped. The autoclave was filled with 265 g fractions from 50 to 150 ° C (with a content of 66.2 percent by weight paraffinic hydrocarbons, 29.5 percent by weight naphthenic hydrocarbons and 4.3 percent by weight aromatic hydrocarbons) of a petroleum from Kuwait in which 2.6 g of cobalt naphthenate and 3.4 g of nickel naphthenate are dissolved became. The temperature was increased while air was charged at a rate of 200 l / h - at normal pressure - was initiated. The oxidation was carried out under a pressure of 40 atmospheres and at carried out at a temperature of 139 to 165 ° C.

The exhaust gas was discharged at the end of the reflux condenser. After the conversion reached 95 ⁰ Zo, the reaction was stopped, and there were 430 g of the oxidized liquid. The oxidized liquid contained 8.6 g of formic acid, 145 g of acetic acid and 31.5 g of propionic acid and butyric acid.

To compare the effects achievable by the method of the present invention, the same thing was done

ίο starting material oxidized without a catalyst until the conversion of 95 ⁰ Zo under the same conditions. 435 g of an oxidized liquid containing 28.2 g of formic acid, 115 g of acetic acid and 5.6 g of propionic acid and butyric acid were obtained.

Example 2

The oxidation system consisted of a stainless steel autoclave with an internal diameter of 8 cm In length, with an air inlet and a liquid outlet at the bottom and a reflux condenser was equipped to discharge the exhaust gas on the upper part.

The autoclave was filled with 2 l of a natural gasoline with a boiling range of 30 to 100 ° C and of the composition listed below. The reaction temperature was 160 to 165 ° C and the pressure was kept at 45 atü. The air supply speed was gradually increased so that that after 1 hour it was 1250 l / h (calculated at normal pressure); then became the feed rate held at this value. After an inducing period of about 1 hour, oxygen absorption ceased powerful. After 9.5 hours, the reaction system was put into continuous operation. This was added after 9.5 hours from 200 to 230 ml of the feed oil containing 2.8 g of sodium naphthenate and a mixture of 0.6 g cobalt acetate, 0.2 g barium acetate, 1.3 g water and 6.5 g Acetic acid was introduced into the reaction vessel through the liquid inlet every hour. During the implementation the oxidized liquid was withdrawn through the liquid outlet so that the liquid was kept at a constant level in the reaction vessel. It became oxidized within 35 to 45 hours Product obtained which contains formic acid, acetic acid and propionic acid and butyric acid in yields of 5.3 percent by weight, 57.8 percent by weight and 13.4 percent by weight, based on the weight of the oxidized hydrocarbons fed.

For comparison, 2 liters of the same starting oil were initially used in the same reaction unit with 8.6 g of manganese naphthenate added and the reaction for 8 hours at a reaction temperature of 160 to 165.degree and a pressure of 45 atm. Subsequently, the system was in continuous operation taken. The system was fed from 220 to 250 ml / h of a feed oil at 0.6% by weight Manganese naphthenate introduced while the reaction liquid was withdrawn, so that the Liquid in the reaction vessel was kept at a constant level. The yields of formic acid, Acetic acid and propionic acid + butyric acid in the during the reaction / citraums from 25 to The product obtained for 35 hours was 18.5, 41.2 and 9.2 percent by weight, based on weight of the oxidized added hydrocarbons.

Claims (2)

5 6 The composition of the starting oil, which is converted into tertiary acid, based on 100 parts by weight of this Example used was the following: th hydrocarbons. The ratio of vinegar acid to formic acid was 13.6. The light fractions did not accumulate in the percentage by weight oxidation Neopentane 1.0 5 and the high boiling point residue. 2-methylbutane 3.5 ■. . n-Pcntane 6.2 Example 5 Dimethylbutane 0.5 The autoclave described in Example 1 was Cyclopentane 8.3 with 260 g of a boiling point between 130 and 200 ° C Cyclohexane 15.0 io fraction consisting of 19.0 percent by weight paraffinic 2-Methylhcxan \ η ^ hydrocarbons, 80.0 percent by weight naphtha 3-methylhexane) 'niche hydrocarbons and 1 percent by weight Dimethylcyclohexane 5.2 aromatic hydrocarbons, charged, 2-Mcthylpciuan 1 5 g including 0.1 weight percent cobalt naphthenate and 3-methylpentane J ^? 15 0.2 percent by weight blcinaphthenate was added n-Hcxan 7.1 den. The mixture was heated with oxygen Methylcyclopentane 13.7 rend 6 hours at a reaction temperature of Benzene 1.5 125 to 147 ° C and a pressure of 25 atm n-heptane 11.3 oxidized the induction period. From the oxidizing Toluene 1.4 20 th product were 12.6 g of formic acid and 111 g Other 2.2 acetic acid obtained and 116g residue with In the amt ΰχΗ) high boiling point separated by distillation. the ⁰ residue with a high boiling point was 232 g Starting oil containing the above-listed catalyst weight percent _{25 sa} t _O ren, mixed, and the mixture was -. ^ Slaphthenic hydrocarbons .. 52.2 again with oxygen 6 hours after the induction Paraffinic hydrocarbons .... 42.7 period under the above reaction Aromatic hydrocarbons .... 2.9 oxidized in conditions. The oxidized product Other 2.2 held 6.3 parts by weight of formic acid and 61 parts 3 parts by weight of acetic acid, based on 100 parts by weight of bis η ie 1 3 ^ ^{er of reacted} hydrocarbons. The relationship from acetic acid to formic acid was 9.7. For comparison, the above procedure was used for 9.5 hours same starting material using the - using only 0. 2 percent by weight of the same oxidation system and repeated using the same 35 cobalt naphthenate as a catalyst. The action conditions as set out in Example 2; The product of the second oxidation contained 16.7. The system was then taken in continuous oxy parts by weight of formic acid and 51.9 parts by weight of dalionic acid, with the reaction temperature of acetic acid, based on 100 parts of the converted temperature, being 16 () "to 182 ° C and the pressure to 65 to hydrocarbons, the ratio of acetic acid to 75 atmospheres was increased, and the addition of 200 to 40 formic acid was only 3.2 in this case.
230 ml / h hydrocarbons. 40 ml.'h light fractions, 0.3 gh cobalt acetate, 7.6 g. h aluminum claim "
ucctut. 1.3 gh water. 6.5 gh acetic acid and 1250 l / h Air, calculated at normal pressure. Process for the production of acetic acid within 20 hours the were 5.0 parts by weight of formic acid. 68.8 rich mixtures of low molecular weight fatty acids parts by weight acetic acid and 12.2 parts by weight pro by oxidation of hydrocarbons with pionic acid and butyric acid, based on 100 Ge a boiling point lower than 2 (K) - C with acidic parts of the converted hydrocarbons, substance or an oxygen-containing gas in liquid keep. ger phase in the presence of a cobalt-containing B is η ie 1 4 ⁵ ° mixed catalyst, characterized by ¹ net. that the oxidation at 140 to 200 ^c C The continuous oxidation was carried out in the presence of a catalyst which Turn the feed tunnel as in Example 3, with at least one salt in addition to a cobalt salt led, with a further 75 ml h of the residue with the following metals: Na. K, Ca. Mg, Cu, Zn, high boiling point were added. Within 55 Cd, Ba. Al. Sn, Pb, Ni and Fe, in a lot For 25 hours, the oxidized product contained 6.1 Ge from 5 to 10,000 percent by weight, based on formic acid by weight. 83.2 parts by weight of vinegar- the weight of the cobalt and calculated as acid and 15.6 parts by weight propionic acid and metal butt.