CS261653B1 - Pressure sensor for contaminated and mean thickened liquid mixtures - Google Patents

Abstract

The process for producing 2,2-dialkoxypropane is carried out podlá čs. certificate 260,295, with an aliphatic donor Alcohols C, C5 to C5 is an additive (predominantly aliphatic alcohols C2 to C, -,) or at least one by-product from a petrochemical process consisting of 60 to 93 wt. of at least two aliphatic alcohols such as oxoprocess, mainly consisting of a mixture of n-butanol and isobutanol and alcoholic byproduct from process of cyclohexane oxidation consisting of: mainly from alcohols C, t to C5. while the first stage of production is conducted in the presence radical inhibitors a the other in the presence of a water trap. Trial it is important for a comprehensive assessment and by-products from biochemical and petrochemical procesoiv.

Description

The present invention relates to the production of 2,2-dialkoxypropane in which the alkoxy groups have a carbon number of 1 to 5, using technically low-deposition by-products from chemical, particularly petrochemical and biochemical products.

Dialkoxypropanes increasingly find their application mainly as intermediates in organic syntheses, including industrial organic synthesis. Thus, dialkoxypropanes by heating with low porous alumina give isopropenylalkyl ethers [Romanian Pat. 79 846; Banciu M., Popescu A., Bull. Inst. Politech. Cheorghe Cheorghiu - Dej, Bucharest, sar. chim. - motal. 42, No 1, 101 (1980)] and on high porosity at 275-500 ° C to hexamethylbenzene. Various reactions give compounds of the formula Me _: SiMa (COi with the co-enrichment of carbon monoxide [Gladyaz JA, Marši M .: Organometallic 1, 1 467 (1982); Tetrahedron Lett, 23, 631 (1982)) and others.

However, dialkyl ketals are prepared by reacting ketones with alcohols in the presence of acidic condensation catalysts (U.S. Pat. No. 2,827,494) and co-enriching 2.5-5 moles of anhydrous copper sulfate per mole of ketone. Thus, in the case of the preparation of 2,2-diinethoxypropane, e.g. from 11.5 moles of acetone and 23 moles of methanol under the catalytic action of one mole of hydrochloric acid and the co-enrichment of 30 moles of anhydrous calcium sulphate yields a major product in 87% yield (patent application pending German Patent 2,636,278).

The process for the preparation of 2,2-dialkoxypropane of the general formula represents a significant progress

OR ¹ /

(CHJoC '\

OR ² in which

R ¹ and R ³ -alkyl C 1-6 alkyl; to R ¹ wherein R ¹ and R ² may be identical but different according to MS. No. 260,295, such that a hydrocarbon mixture comprising an alene and / or methylacetylene in an amount of 2 to 98 wt. is reacted with at least one aliphatic alcohol C1 to C ₅ or at least one aliphatic C ₁ to C ₅ alcohol % to C ₅ with admixtures of 0.01 to 25 wt. water under the catalytic action of at least one metal compound Ia and / or II.b of a subset of the Periodic Table of the Elements at a temperature of 100 to 250 degrees Celsius, molar ratio of alcohol to total alene and / or methylacetylene content of 1: 6 to 6: 1; up to 1 MPa, wherein the reaction product as such or after separation of hydrocarbons, including unconverted alene and / or methylacetylene, containing mainly acetone, unconverted alcohol or alcohols, 2-alkoxypropene or 2-alkoxypropenes leads to condensation at -50 to 35 ° ^C C with an acid catalyst or a combination of an acid catalyst and a basic catalyst.

However, it does not exhaust all technically available and significant sources of alcohol donors, resp. alcoholic raw materials. Thus, a process for preparing 2,2-dialkoxypropene of the general formula

OR ¹ /

(Ci-Ubc \

OR ² in which r 1 _and r 2 _and alkyl c _(az c _n) wherein R ¹ and R ² may be identical or different, is carried out on stage c. 260 295 by reaction of a mixture of hydrocarbons containing 2 to 98 wt. alene and / or methylacetylene with C 1 -C 5 alcohols, the source of the alcohols being fusions containing a predominant mixture of C ₂ -C 5 aliphatic alcohols and / or at least one by-product of the petrochemical process, consisting of 60-98% of at least two C 1 -C ₅ alcohols .

Advantages of the process according to the invention are higher yields of the main component namely 2,2-dialkoxyropanes, widening of the assortment of donors of mainly alcoholic raw materials to the production of 2,2-dialkoxypropanes, using low-valued by-products from chemical, petrochemical and biochemical production. Last but not least, with the “alcoholic” raw material, the water present in the soil will be appreciated, which would otherwise have to be removed in a more energy-intensive manner.

Suitably a mixture of at least two alcohols to C- containing 0.1 to 25 wt. addition of water and optionally also organic compounds are flammable the fusel fermentative production of ethanol, the mixture of alcohols having C ₂ to C, - "even higher than C _5, alcohols and water. Then, from the butanol, isobutanol and 2-ethylhexanol production plant, an oxoprocessome from propene, synthesis gas (a mixture of carbon monoxide with hydrogen) and hydrogen, as well as other petrochemical processes.

The waste water from the alcohols mentioned in the production is stripped, resp. distillates mainly organic fractions, so-called. Strip-ol waste oil, consisting mainly of n-butanol, isobutanol, n-butyraldehyde, isobutyraldehyde, toluene and water, and optionally admixed with triisobutylamine and butyl formates. Indeed, the components are already in virtually negligible quantities.

The water content of the strip-ol is usually in the range of 6 to 23% by weight, isobutyraldehyde 0.3 to 2% by weight, n-butyraldehyde 0.5 to 6% by weight, isobutanol 20 to 40% by weight,

% 261652 of n-butanol 35 to 60% and toluene 1 to 6% by weight.

The alcohol donor of the present invention is also a by-product from cyclohexanone production via an intermediate cyclohexanol-cyclohexanone intermediate mixture by catalytic oxidation of cyclohexane. In addition to the main and other by-products, a leading alcoholic by-product is obtained, isolated by rectification of a predominantly cyclohexanol-cyclohexanone mixture on a column (FK-102). The density of this colorless liquid at a temperature of 20 ° C is 255 kg. m ~ ³ and distils 95% over a range of 92 to 142-100 kPa; acid number - 0.95 mg KOH / g; saponification number == 21.0 mg KOH / g; bromine number - 27.8 g Br / 100; hydroxyl groups - 14.3% by weight; % carbonyl groups = 1.6 wt.

It contains mainly around (% by weight) 52 pere. amyl alcohol, 4% isoainylalcohol, 10% n-butanol, 6% isobutanol, 1% sec-butyl alcohol, 10% cyclohexanone, 8 washes. cyclopentanol, 3% cyclopentanone and 3% water. The admixtures of cyclohexane, cyclohexene and cyclohexanol make up about 1%.

Last but not least, of the invention with a suitable alcohol C-donor _{(and C,} may be the product hydrokondenzácie mixture of hydrogen with carbon monoxide, in particular zinočuato-chromium, iron, zinc chromite at elevated temperature and pressure, the products of Fischer raodifikovanej Then, the acetylene-initiated hydrocondensation, or the initiated Fischer-Tropsch synthesis and isosynthesis, will also find "crude" methanol, or distillation residues from the rectification of methanol and higher alcohols.

According to the present invention, they are used as inhibitors of radical reactions! salts of the medium, such as copper sulphate, and if it is anhydrous, it can simultaneously act as a water scavenger. Bottom) nitrites, organic micro compounds, phenols and polyvalent phenols, sulfur compounds and the like.

Particularly ground calcium sulfate, anhydrous sodium sulfate, anhydrous iron sulfate, anhydrous potassium sulfate and the like are suitable as water scavengers in addition to the anhydrous salts mentioned above.

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

Example 1

A 15 cm @ ³ pressure reactor equipped with pressure and temperature control is charged with 8 g of a 0.3 to 0.5 mm particle size catalyst containing 23.1 wt. % zinc acetate, together with 1.7 wt. copper acetate on activated carbon of a specific surface area of 750 m ² / g and 2 g of a catalyst containing 29% by weight % sodium hydroxide with 2.3 wt. copper acetate on γ-aluminum. After the air was purged with nitrogen, the reactor was heated to 180 ° C and the feed was fed through a preheater heated to 180 ° C with a fissure of 7.0 cm ³ / h and 5.1 dm ³ / h of C ₃ gas fraction. The fissure has the following composition (per feather mass):

ethanol - 5,2 n-propanol - 1,7,

2-propanol = 1.8. butanol = 8.8, isoamyl alcohol 67.3, higher alcohols - 2.6 and water - 12.65.

The fissure has an acid number of 1.82 mg KOH / g and a hydroxyl number of 621.5 mg XOH / g. Of this, 96% distils over a boiling range of 84 to 132.5 ° C. The feed pyrolysis residual _{C, the} fractions containing with the pen 31. wt. methylacetylene with 1,2-propadiene. The temperature in the reactor is then increased to 200 ° C and the feedstock is adjusted and maintained at the fusing value (calculated as alcohol C ₅ ): methylacetylene with propadiene - 1.8: 1.

The reaction mixture is passed through a condenser to a gas separator, where a substantial portion of the C 1 _J hydrocarbon is separated from the liquid phase, including the unconverted allene with methylacetylene. It is further passed through an efficient condenser where it cools down to -24 ° C. and further pumped into a tubular jacketed reactor containing at the top and bottom after. 30 cm ^{3 of} antionite (Ostion AD in OH form) and in the middle 140 cm ^{3 of} cationite (cation exchanger Ostion KS in H-form) in active forms, the cationite being mixed with another 40 cm ^{3 of} powdered copper sulfate. The reactor is tempered to -28 to -23 ° C. From the bottom of the reactor, the reaction mixture is continuously discharged to the container through an external aerated air drop at a height of 4 cm above the anionite gaming layer. Partially hydrated calcium sulphate (CaSO 4 · 0.5 H? O) is added to the reservoir semi-continuously and taken off almost completely (CaSO 2 · 2 H, O).

The reaction mixture contains 0.2 wt. mixture. ^2-n -alkoxycarbonyl open (U i to the nlkoxyskupiuami C.-,), 28.4% by weight. % of a .alpha.-dialkoxypropane mixture, 4.1 wt. acstoms, 2.1 wt. mixtures of hydrocarbons and residues up to 100% non-converted alcohols. This whole mixture is a suitable component for motor gasoline.

Example 2

The procedure is similar to that of Example 1, but as a starting alcoholic raw material, the stripped " oil " from the waste water of the n-butanol, isobutanol and 2-ethylhexanol production plant is injected with an oxoprocess. 'Stripol' with an acid number of 1,33 mg KOH / g; saponification number = 5.09 mg KOH / g; OH = 17.95%

I

281652 wt .; CHO = 0.89% by weight; water = 21.89 washes. materials .; Medium pier. weight (determined cryoscopically) - 118.6 g. mol ^-1 ; by liquid-gas chromatography, the following was identified: 0.5 wt. isobutyraldehyde; 0.9 wt. n-butyraldehyde; 1.5 wt. toluene; 26.1 wt. % isobutanol and 53.2 wt. n-butanol.

However, in the second stage of the production process (in part in the first stage), in addition to the catalysis of acetone with C ₄ alcohols, acetalization of the aldehydes C ₄ with alcohols takes place.

Example 3

The procedure is similar to Example 2 except that the composition of "siripol" is partially different. It consists of (in% w / w) of 1,1,45% water, 1,02% isobutyraldehyde, 4,08% n-butyraldehyde, 4,92% toluene, 32,71% isobutanol, 45,82% n- butanol and 0.13% organic nitrogen compounds, mainly triisobutylamine. The fuel additive obtained, in particular diesel fuel, consists of 30.2 wt. 2.2-dialkoxypropanes, 4.8 wt. acetals _l2 C, 3.9% by weight. hydrocarbons and the remainder up to 100 wt. consist of unconverted components mainly from injected stripol.

This additive is present in an amount of 22.3% by weight. adds “Special” to petrol according to ČSN 65 6505 oCVM = 91.1. The gasoline obtained by this additive has an OCVM of 96.6.

Example 4

The procedure is similar to that of Example 2, except that instead of the by-product from the "strip-ol" oxoprocess by the alcohol donor, the by-product (FK-102) is a predominantly mixture of aliphatic alcohols C ₄ to C ₅ from the cyclohexane oxidation process of this specification: liquid (FK-102) at 20 ° C = 855 kg. m ^-3 and 95% distillate in the range of 92-142 ° C / 101 kPa; acid number - 0.95 mg KOH / g; saponification number - 21.0 mg KOH / g; hydroxyl groups = - 14.3% by weight; carbonyl groups - 1.6 wt%; amyl alcohol - 52% by weight; isoalmyl alcohol = 4 wt%; butanol = 10%; isobutanol = 6% by weight; sec.butyl alcohol = 1 wt%; cyclopentanol = 6 wt%; cycloipentanone = 3 wt%; water - 3% by weight; 10% wt. cyclohexanone.

The admixtures of cyclohexane, cycloliexene and cyclohexanol make up about 1 wt. and other unidentified oxygenated organic substances also about 1 wt.

Total alcohols C 1 to C ₅ , including cyclopentanol, convert to 1 pass (per pass) in 2,2-dialkoxypropanes of 67% and water of 92%.

Claims (4)

The present invention relates to the preparation of 2,2-dialkoxypropane in which the alkoxy groups are the number of carbons 1 to 5, utilizing technically advanced chemical products, especially petrochemical and chemical chemistry. Dialkoxypropanes are increasingly useful mainly as intermediates in organic synthesis, including industrial organic synthesis. Thus, dialkoxypropanes with low-porous aluminum oxide give isopropenylalkylethers [ru-mun pat. 79 846; Banciu M., Popescu A.:Bull. Inst. Politech. "Cheorghe Cheorghiu — Dej", Bucuresti, sar. chim. - motal. 42, No.1, 101 (1980)] and hexamethylbenzene on high-porosity at 275-500 ° C. Rapid reactions give the compounds of general formula Me: SiMa (CO) 5 as co-compounds of carbon monoxide [Gladyaz J.A., Marši M.:Organometallic 1, 1467 (1982); Tetrahedron Lett, 23, 631 (1982)] and p. However, dialkyl ketals are prepared by rooting ketones with alcohols in the presence of acidic condensation catalysts. 2 827 494) and co-activities of 2.5-5 moles of anhydrous copper sulphate per mole of ton. Thus, in the case of the preparation of 2,2-diinethoxy-propane, e.g. from 11.5 moles of acetone and 23 moles of methanol with a catalytic effect of one mole of hydrochloric acid) and 30 moles of anhydrous calcium sulphate, the main product is obtained in 87% yield (patent application NSR 2) 636,278). Significant advancement is represented by the production of 2,2-dialkoxypropane of formula OR 1 / (CH 3 CO 2 OR 2 in which R 1 and R 3 - alkyl C 1 to C 3 'wherein R 1 and R 2 may be the same or different base of certificate 260 295, wherein the hydrocarbon-containing mixture of alene and / or methyl-acetylene in an amount of from 2 to 98% by weight is reacted with at least one aliphatic alcohol C 1 to C 5 or at least one aliphatic alcohol C 1 to C 5 with the amino group 0, From 1 to 25% by weight of water under the catalytic effect of at least one of the compounds Ia and / or II.b of the subgroup of the periodic system of elements at a temperature of 100 to 250 degrees Celsius, with a molar ratio of alcohol to the total content of alene and / or methylacetylene of 1: 6 up to 6: 1 and a pressure of 0.1 to 1 MPa, the reaction product itself or the separation of hydrocarbons, including unconverted alene and / or methylacetylene, comprising mainly acetone, unconverted alcohol or alcohols, 2-alkoxypropene and The 2-alkoxypropenes are fed to condensation at a temperature of -50 to 35 ° C with the co-formation of an acid catalyst or a combination of acidic with a basic catalyst. However, it does not exhaust all the technically available and significant sources of alcohol-donor or donor donors. alcoholic raw materials. Thus, the production of 2,2-dialkoxypropene of the general formula OR 1 / (CH 2) 2 C OR'3 in which R 1 and R 2 are (c) to wherein R 1 and R 3 are identical or different may be carried out. -takes the podium of MS. by the reaction of a hydrocarbon mixture stretching from 2 to 98 wt. alene and / or methyl acetylene with C 1 to C 5 alcohols, the source of alcohols being the contents of the predominantly aliphatic alcohols C2 to C5a or at least one by-product of the perchloric process consisting of 60 to 98% of at least two alcohols Cj to C5. An advantage of the process of this invention are the higher yields of the main component, namely 2,2-dialkoxyropanes, an extended range of donor predominantly alcoholic substances for the production of 2,2-dialkoxypropanes, using low-valued chemical, petrochemical, biochemical manufacturing products. Last but not least, with the "alcoholic" raw material, the water that is usually present is the most valuable one, which has to be removed in an energy-intensive way. A suitable mixture of at least two alcohols to C- containing from 0.1 to 25% by weight the admixture of water and possibly also the combustible organic compounds is an additive of fermentation ethanol production, containing alcohols C2 to C, even higher alcohols such as C5 and water. Thereafter, from the butanol, isobutanol and 2-ethylhexanol by means of a process of propene, synthesis gas (including carbon monoxide with hydrogen fluoride) and hydrogen, as well as from other petrochemical processes. they mainly distill off organic stripes, the so-called "strip-ol", mainly consisting of n-butanol, isobutanol, n-butyraldehyde, isobutyraldehyde, toluene and water and possibly admixture of triisobutyl amine Other components are already in practically negligible amounts, typically in the range of 6 to 23% by weight of isobutyraldehyde, 0.3 to 2% by weight, n-butyraldehyde of 0.5 to 0.5% by weight of the strip-oil. 6 wt%, isobutanol 20 to 40 wt%,