CS227744B1 - Production of organic oxygenic compounds from the alcohol group,ethers esters - Google Patents

Description

The invention relates to the production of organic oxygen compounds, in particular alcohols, ethers and esters, from olefins, alcohols, water and carboxylic acids.

It is known that the addition of alcohols to unsaturated hydrocarbons under the catalytic action of acids creates ethers (Kirk-Othmer: Encyclopedia of Chemical Technology, Vol. 8, (1965); U.S. Pat. No. 2,720,547). Strong mineral Bronsted acids or Lewis acids such as ferric chloride, zinc chloride, bromine fluoride are used as catalysts in this reaction. However, the disadvantage of the above mentioned catalytic systems is the considerable corrosion of the device and the need to remove it! catalyst from the reaction mixture. Advantages have additional processes in which cationic resins are used as catalysts, e.g. sulfonated 3-styrene-divinylbenzene resins (NSR Pat. No. 868,147). The acid ion exchangers (cation exchangers) may also be based on other sulfonated polymers having acidic functional groups, such as -SO4H or -COOH (U.S. Pat.

721 222; NSR pat. no. 1,224,294). Aliphatic ethers can be prepared from C ^-C C-isoolefins and C až-C] 'alkohol alcohols (BSA Pat. No. 2,480,940). It is also possible to prepare ethers from olefins, but the reaction rate is lower. Not only aliphatic primary alcohols, but also aliphatic diols to polyols, a mixture of di- to polyols, or mixtures thereof with aromatic or cycloaliphatic primary and secondary alcohols can be used for this addition (cf. No. 190 755).

Similarly, unsaturated ethers are prepared from unsaturated alcohols and isooolefins (U.S. Pat. No. 190,716). Although the use of ion exchangers reduces or eliminates corrosion problems in the equipment, problems in heterogeneous phase work are increasing, because of the lower ion exchange activity compared to strong inorganic acids, in particular with sulfuric acid, up to 10 times the amount of ion exchange is required. In addition, the use of ion exchangers is limited to a use temperature of up to 130 ° C, since they are destroyed relatively quickly above this temperature.

And in the case of the addition of alcohols to olefins or eycloolefins, the reaction rate is sufficient only when using sulfuric acid or olea as a catalyst or other catalyst, as a rule a temperature above 130 ° C. A similar preparation of carboxylic acid esters can be carried out by reacting monoolefins to C8 with an organic acid C12 to O10 on acid catalysts (U.S. Pat. No. 3,492,341). Sulfo-containing ion exchangers (NSR Pat. No. 2,306,586; USSR Author's Certificate No. 560,875) or sulfuric acid (NSR Pat. No. 1,668,537) can be used for this reaction. Similarly, alkyl esters of carboxylic acids can be made by reacting carboxylic acids with an alkyl tert-alkyl ether in the presence of an acid catalyst such as sulfuric acid, sulfonic acid, and heteropolyacids (Belg. Pat. No. 866,037). In addition to the corresponding carboxylic acid ester, an olefin is formed. The 3β8 method can be used to separate olefins with simultaneous preparation of esters. In addition to sulfuric acid, a mixture of bismuth sulphate and hydrobromic acid can also be used to prepare the esters (Jap. Pat. J 5 4,022,314).

• Problems in the preparation of carboxylic acid esters are similar to those in the preparation of ethers, with the presence of organic acids increasingly imposing corrosion resistance requirements on the apparatus, in particular when using inorganic acids. Similarly, ethanol from ethylene, isopropyl alcohol from propylene and secondary and tertiary alcohols from higher olefins and isooolefins can be prepared from olefins and water in a two-step process by hydrating olefins in sulfuric acid at 60-90 wt%, through alkylsulfuric acid, and hydrolysing with alkylsulfuric acid. this in the second stage or by direct hydration of the alkenes by the sulfuric acid in the liquid phase at high temperature and pressure (NN Lebedev: Chemistry and technology of basic organic and petrochemical syntheses, Alfa Publishing,

Bratislava (1979); USSR copyright certificate no. 202,912). Alkyl tert-alkyl ethers are also prepared from isooolefins and alkanols in the presence of cation exchangers in which the metal of VII is stored in elemental form. or VIII. sub-group of the Periodic Table of the Elements (DE-A-3,026,504 A1).

The above disadvantages are eliminated sp8sob manufacture of organic oxygen-containing compounds from alcohols, ethers, esters, addition of water, alcohols, C, to C _12, or a carboxylic acid C ₁ to C ₁₂ to olefins C ₂ to C, ₂ catalyzed by mineral acids, sulfonic acids, or cation exchangers at a temperature of -5 to 200 ° C, wherein the addition is carried out with the addition of at least one element or compound from the subgroup of medium, tin, arsenic, chromium, manganese, iron of the periodic table in amounts of 0.001 wt. % to 2.0 wt. with the exception of manganese and iron subgroup elements using a cation exchanger for the manufacture of tert-alkyl ethers.

An advantage of the process of the present invention is the higher reaction rate and hence the unit's production, but in particular significantly less corrosion and thus much longer service life of the production equipment. SpSsob makes it possible to extend the application possibilities for the use of sulfuric acid and other strong acids as catalysts, since they are among the most efficient and technically available and inexpensive catalysts. In addition to the high efficiency, the catalyst system positively affects the quality of the products prepared. The method of manufacture according to the invention is technically simple and does not require special modifications to conventional equipment. It can therefore also be carried out on the down-flowing devices in a discontinuous, semi-continuous and continuous arrangement.

Transition metal transition, resp. the compounds or transition metal compounds may be carried out separately or together with an acid catalyst, e.g. with sulfuric acid or together with the starting hydroxy or carboxylic acids. Saturated and unsaturated alcohols, di- to polyols, in particular having a carbon number of 1 to 16, as well as other organic compounds containing at least one hydroxy group per molecule can be used for the production of ethers. However, also preparation with other alcohols, ethyl alcohol, butyl alcohol, 2-ethylhexanol, allyl alcohol, respectively. The mixture may also be present in the presence of water.

Suitable olefins are, in particular, isobutene, isopentene as well as lower and higher olefins, also diolefins and eycloolefins, as well as mixtures of olefins with other hydrocarbons. Owing to the substantially higher reaction rate of the isooolefins compared to the n-olefins, olefin mixtures, e.g. pyrolysis C ^ -, respectively. The mixture is reacted with alcohols to selectively form the corresponding alkyl tert-butyl ether or alkyl tert-amyl ether.

Of acids and olefins, respectively. of the ethers prepared in the first stage as olefin precursors, it is again possible to prepare esters of the corresponding acids by the above process. Of the acids, most suitable are formic and acetic acids, but also highly saturated and unsaturated acids can also be used. In addition, the process can also be applied to transesterification, i. j. from said ester using said catalyst system and an alcohol or acid, respectively, to prepare another ester, e.g. transesterify vinyl laurate with lauric acid to vinyl laurate and the like.

For the preparation of alcohols, the alkenes C8 to C18 are particularly suitable, as are the cycloalkenes C8 to C18 in one or two stages. As transition metal compounds it is possible to use oxides, hydroxides and salts of organic acids as well as inorganic acids, in particular transition metal sulphates, namely formates and acetates, in particular media, iron, tin, arsenic and antimony. These can be applied to the cell directly into the environment, or applied in a stream together with one of the reactants. The compounds can be applied as such or prepared in situ by the addition of starting elements or metals in the pure form or in the form of alloys which form cations of the compounds in the environment. For example, it is also possible to apply the cell itself or alloys thereof, or carbonates, which is converted to the corresponding sulfate or other suitable compound by the addition of sulfuric acid and the like. These are low additions of transition metal substances. E.g. with the use of copper sulfate, the addition of 0.01 wt. The batch has substantial positive properties, but it is also possible to use amounts of transition element compounds, most preferably in the range of 0.05 to 0.5% by weight. on the handle.

As acid catalysts, the use of sulfuric acid and sulfonic acids, whether benzenesulfonic, naphthalenesulfonic, optionally with close substituents (alkyls) on aromatic rings, is most suitable in this process.

A specific embodiment of the reactions can be seen from the examples, which, however, do not exhaust all possible combinations.

Example 1

The allyl-tert-butyl ether is made in pressure cylinders of cylindrical shape of 300 cm. Weigh the appropriate amount of allyl alcohol and catalyst into the tube; The tube is cooled with solid carbon dioxide, filled with isobutene. After closure is tested for leaks and then fixed to the support frame and immersed in a glycol bath and equilibrated starts rotation (40 revolutions min. ^- ', rotation perpendicular to the cylinder axis). The results obtained are listed in Table 1.

While experiments 1, -2, 5, 6, 7, 13 and 14 were carried out with additions of 0.1 wt. on the cuprous sulfate, cupric oxide, ferric sulfate, tin powder, arsenic oxide and antimony sulfate, experiments 3, 4, 8 to 12 are comparative; j. without the addition of salts.

The following results are obtained by polarographic analysis of products prepared without the addition of transition elements:

v v

v v

product experiment 3 (% by weight): 1,6.10 ^-3 Cr; 1,1.10 ^-3 Ni; 4 , 1.10 ^-3 fe product experiment 4 (% by weight): 7,1.10 ^-4 Cr; 1,1.10 ^-4 Ni; 1 , 3.10 ^-4 fe product experiment 13 (% by weight): 1,0.10 ^-4 Cr; 1.6.10 ^-4 Ni; 7 , 5.10 ^-4 fe product experiment 14 (% by weight): 4,4.10 ^-5 Cr; 4,0.10 ^-5 Ni; 3 , 1.10 ^-5 fe

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In other cases, in the products of the experiments carried out in addition with the addition of transition elements, the concentrations of chromium, nickel and iron are up to ten times lower than in the products using sulfuric acid or sulfuric acid, respectively. p-toluenesulfonic acid with no additions.

When using cationic resins in H-form (cation exchange) experiments 9 to 12, four times the amount of cation exchanger is required than with sulfuric acid and, in addition, a lower selectivity to the desired allyl tert-butyl ether is achieved,

Example 2

In the apparatus of Example 1, allyl t-butyl ether is prepared from allyl alcohol and de-butadiene-pyrolyzed C 1 -fraccis having a composition (.wt.%): Propane 0.08; propane-s-isobutane 2.97} n-butene 10.83; 1-butene 27.47; isobutene 43.3; isopentane + trans-2-butene 9.01; cis-2-butene 4.42; 1,3-butadiene 1.78.

At a reaction time of 60 _t min using 1.0 wt. % sulfuric acid and 0.2 wt. CuSO4 to allyl alcohol, reaction temperature of 80 ° C and a molar ratio of allyl alcohol: isobutene in C 1 -fraction = 1: 4 results in the conversion of allyl alcohol with 100% selectivity to allyl tert-butyl ether and the product after degassing at 20 ° C contains 96 % allyl tert-butyl ether and 1 wt. t erc.butylalkoh olu.

The loss of stainless steel type 17246 is, after recalculation, 0.36 g.m * \ h 'in case the addition of copper sulphate is not used. If the addition of copper sulphate was used, the decrease would decrease to 0.05 g / m &lt; 2 &gt; of the stainless steel material.

Example 3

274 g of sulfuric acid, conc.

% wt. and 112 g of a mixture of n-butene with isobutene and a 42 x 11.5 x 1 mm, 1073 mm stainless steel top plate of class 17246.4 are placed in an autoclave. The autoclave was stirred at 40 ° C for 60 min. To 50 g of the autoclave product is then added 250 g of distilled water. After distilling off the mixture of water and alcohols in the presence of a stainless steel plate, 210 g of distillate are obtained in a yield of 75% of 2-butanol and 85% of isobutanol for the olefins to be mounted. During the reaction in the autoclave, the loss of the stainless steel plate is 0.01162 g, after distillation the loss of 0.2497 g (in 2.5 h at 60 ° C, distillation is carried out under reduced pressure). In another experiment, under otherwise similar conditions, but additionally with the addition of 0.05 wt. copper sulfate, during the reaction! in an autoclave, the weight loss of the stainless steel sheet is practically difficult to weigh, reaching 0.0054 g after distillation. The yield of alcohols is similar to that of the previous experiment.

2

While in the first case the material loss is 2.02 g / m, h in the autoclave and 41.4 g / m. H in the distillation, in the second case using the addition of copper sulphate the material loss

2 0.00 g / m / h in the preparation of butylsulphuric acid and 0.89 g / m / h during distillation.

Example 4

In a 300 cm @ 3 stainless steel tube according to Example 1, weigh 60 g of acetic acid and 56 g of isobutene with a detailed amount of sulfuric acid at 80 ° C in the presence of a 40 x 10 x 1 mm plate of 17347 grade stainless steel. The results obtained for the preparation of tert-butyl acetate are shown in Table 2.

227744 6

Table 2

Effect of reaction time and catalyst amount on acetic acid conversion at 80 ° C and mol. isobutane / acid ratio acetic = 1.0

number experiment Catalyst acid sulfuric 1% by weight) Reaction time (min) Weight of product after degassing (G) Acid Conv. octovej na terc.- butyl (%) 1 0.0 120 69.2 2.0 2 0.5. 120 110.8 60.8 3 1.25 120 117.0 75.2 4 1.25 20 103.5 45.7 5 1.25 45 104.8 54.1 6 1.25 80 116.0 73.2

The stainless steel plate should achieve a loss of 3 to 0.1021 g in 2 hours in the test without the use of copper sulphate, with an addition of 0.05% by weight. copper sulfate, respectively. equal amounts of ferrous sulphate, antimony sulphate, stannous sulphate and arsenic trioxide achieve only a drop in the can of 0.0006 to 0.0015 g.

Example '5

In pressure tubes according to Example 1, allyl tert-butyl ether is synthesized from 0.5 moles of allyl alcohol and a C 1 fraction (composition in Example 2) containing 2.0 moles of isobutene. 0.5 wt. sulfuric acid at a reaction temperature of 80 ° C and a reaction time of 60 minutes and various additions.

A stainless steel test specimen of the type

17246 with dimensions 40 x 10 χ 1 mm, surface 900 mm. Upon completion of the synthesis, the tubes were cooled to 20 ° C and degassed carefully. The product is analyzed for allyl-tert-butyl ether and allyl alcohol and the test specimens are weighed.

Up to 100% conversion of allyl alcohol and 95-100% selectivity regardless of the type of addition used.

The loss of the test piece without the additions of 0.35 gm ^-2 .h ^- \ with additions of 0.001 wt%. 0.02 gm ^-2 .h ^-1 , with an addition of 0.1 wt. arsenic trioxide 0.1 g.m ^{-1 * 2} .h ^-1 , with an addition of 0.1 wt. of hexammonium hexammonium phosphate loss of 0.06 gm .hjs by addition

0.0001 wt. % copper sulfate 0.17 g / m &lt; 0.05 &gt; potassium dichromate 0.08 g. - 2 - 1 - 2 - 1 µm, 0.2% w / w; manganese sulphate 0.15 g.m.h.

Claims (2)

OBJECT OF THE INVENTION Processes for the preparation the preparation of organic oxygenated compounds of the group of alcohols, ethers, esters, addition of water, alcohols Ci to C ^ g, or karboxylovýoh acid C ₁ to C ^ g to olefins Cg-C ^ g catalyzed by mineral acids, sulfonic acids or cation exchangers in the A temperature of -5 to 200 ° C, characterized in that the addition is carried out with the addition of at least one element or compound from the subgroup of medium, tin, arsenic, chromium, manganese, iron of the periodic table in amounts of 0.001 wt. % to 2.0 wt. with the exception of manganese and iron subgroup elements using cation exchanger for the manufacture of tertiary alkyl ethers.