2-ethylhexanal production process

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to improved process for production of 2-ethylhexanal, which is raw material for production 2-ethylhexanoic acid and/or 2-ethylhexanol. Starting material of invention is bottom residue from rectification of butyl alcohols produced in oxo synthesis, from which bottom residue a fraction mainly containing saturated and unsaturated C8-alcohols with 5-15% of C12-acetals is isolated on two columns operated at column top residual pressure 50-90 mm Hg. This fraction is subjected to vapor-phase processing at atmospheric pressure on copper-containing catalyst at 200-300°C followed by rectification of catalysate on two columns to isolate, as first-column top distillate, fraction obtained at 20-50 mm Hg and containing light components and 2-ethylhexanal, which fraction is fed into second column operated at column top residual pressure 60-100 mm Hg to isolate distilled fraction containing light components and 30-60% of 2-ethylhexanal, whereas desired 2-ethylhexanal is recovered as bottom product or as product tapped from the side of bottom column section.

EFFECT: improved quality and yield of desired product.

2 cl, 14 ex

 

The present invention relates to the chemical, petrochemical, and in particular to an improved method for producing a 2-ethylhexanol - an intermediate in the production of 2-ethylhexanoic acid and 2-ethylhexanol.

2-Ethylhexanoyl acid is obtained by oxidation of 2-ethylhexanal. It is mainly used in the paint industry for the production of driers. In addition, cobalt salts of this acid are used to prepare the catalyst stage hydroformylation in producing aldehydes, alcohols, acids, esters, method of oxosynthesis.

2-Ethylhexanol is produced by hydrogenation of 2-ethylhexenal and used as raw material in the production of plasticizer is dioctylphthalate, used in the manufacture of PVC, artificial leather, plastic building materials, and for some other purposes (Obtaining aldehydes and butyl alcohol oxosynthesis. Sat. scientific papers of the Institute-Neftekhim, part 2, L., 1977, 122 S.).

A method of obtaining 2-ethylhexanal raw material for the production of 2-ethylhexanoic acid used for preparation of the catalyst of hydroformylation (Ed. mon. The USSR №1697381, 1992).

According to this method, 2-ethylhexanal get by selective hydrogenation of the double bond of unsaturated aldehyde C8- 2-ethylhexan-2-al-1 (hereinafter abbreviated as 2-ethylhexanol), which, in its PTS who lived, obtained by condensation of n-butyric aldehyde using as the catalyst the alkali or salts of cobalt (Ed. mon. The USSR №791737, 1980; Katsnelson MG, Alekseeva K.A. and other Chemical industry. - 1976. No. 11. - S-813). Selective hydrogenation of 2-ethylhexenal carried out using a catalyst of palladium supported on alumina and additives allylboronates at pressures of 0.1-5.0 MPa, a temperature of 80-130°C.

The resulting hydrogenation product separated in the separator gas and liquid phases. The gas phase containing mainly hydrogen and volatile components, recycle on stage hydrogenation. The liquid phase containing mainly 2-ethylhexanal and alkylbetaine, direct to the stage of oxidation of obtaining oxidate from which the rectification give 2-ethylhexanoyl acid and alkylbetaine.

The disadvantage of this method is the necessity to process the additional agent - allylboronates that leads to the complication of the technological scheme, as it requires the organization of a separate production allylboronates or import such products are not produced in Russia), as well as developing a scheme of regeneration and purification from impurities.

A method of obtaining 2-ethylhexanal raw material for the production of 2-ethylhexanoic acid from byproduct synthesis oil is Legalov the propylene hydroformylation (Ed. mon. No. 1732639, 1997 - prototype).

According to the method prototype by-product of propylene hydroformylation, containing in its composition, wt.%: 2-ethylhexenal of 10.05-13,71; 2 ethylhexanol - 23,0-43,48; 2-ethylhexanol - 2,48-17,77; butyl alcohol - 3,90-25,97; unidentified impurity - 2,34-23,05; BCP - 0,49-33,86, is subjected to hydrogenation in the volumetric feed rate of the raw material of 0.5-1.7 h-1and the ratio of hydrogen:feedstock (100-400):1 catalyst of 0.25-0.5% of palladium deposited on Al2About3at a temperature of 95-105°C, a pressure of 0.12 MPa. The result is a hydrogenation product containing 2-ethylhexanal that without special division is directed to obtain 2-ethylhexanoic acid.

The disadvantage of this method is the use of high quality raw materials intermediate fractions production of 2-ethylhexanol, which leads to irreversible loss of 2-ethylhexanol, taken in processing the composition of the feedstock (raw materials of examples 1-7, 9-12 contains 17.77 % 2-ethylhexanol).

Studies have shown that allocate 2-ethylhexanoyl acid with a yield higher than 92 wt.% and purity higher than 97 wt.% from oxidative 2-ethylhexanal obtained by the method in examples 1-7, it is not possible even if its rectification for high efficiency columns and large reflux numbers.

When using the raw materials shown in example 8, sod is rasciesa impurities BCP number 33,86% allow 2-ethylhexanoyl acid with a yield no higher than 86 wt.% and purity of no higher than 96 wt.%.

This is due to the feature used in the process of raw materials significant amounts of impurities of 2-ethylhexanol and BCP in the composition of the raw material during subsequent oxidation of the hydrogenated feed is separated form the impurity components, giving azeotropy 2-ethylhexanoic acid.

When the hydrogenation concentrate 2 ethylhexanal obtained by the method prototype in examples 1-7, produces concentrates of 2-ethylhexanol, of which there are commodity 2-ethylhexanol, meets the requirements of GOST 26624-85 as raw materials of examples 1-7 and 9-12, as mentioned above, an intermediate fraction, resulting in the technology of industrial production of 2-ethylhexanol.

When the hydrogenation concentrate 2 ethylhexanal obtained by the method prototype in example 8, we obtain concentrates of 2-ethylhexanol, highlight of which 2-ethylhexanol, meets the requirements of GOST 26624-85 on such parameters as the concentration of unsaturated compounds, the concentration of 2-ethyl-4-methylpentanol, usually used for this purpose by the method of rectification is not possible.

The purpose of the present invention is to improve the quality and yield of 2-ethylhexanal obtained on the basis of the departure process of oxosynthesis, with the possibility of receiving on its base with a high yield of 2-ethylhexanoic acid with a purity not less than 98 wt.%, 2-ethylhexylacrylate not less than 99 wt.% and other characteristics, meets the requirements of GOST.

In contrast to the known methods of obtaining 2-ethylhexanal of products oxosynthesis, in the proposed method as a source of raw materials process using the VAT residue production butyl alcohol, which is obtained after distillation target butyl alcohol from the product of the hydrogenation of aldehydes of oxosynthesis. It contains, wt%: light components (water, oil aldehydes, alcohols, C4-C7the ketones7bodyformat) 3-8; ethers and esters of C88-12; limit alcohol C810-30; unsaturated alcohols C820-50; high-boiling by-products (WFP) 30-60, including acetals C1220-40 (acetals With12the product of the interaction of molecules n-oil or samalanga aldehyde with two molecules of n-butyl or isobutyl alcohols; A.P. Pisarenko, SA havin. The course of organic chemistry, ed. 3. M.: Higher school, 1975, 507 S.).

From this VAT residue by distillation under vacuum at a residual pressure in the top of the column 50-90 mm RT. senior emit a narrow fraction of alcohols C8containing 5-15 wt.% acetals With12. It was established experimentally that at the specified concentration range acetals With12in the "narrow" faction is the maximum selection of 2-ethylhexanol and the isomeric 2-ethylhexanol from their potential content is tion in the original VAT residue, and these spirits are the source of the target 2-ethylhexanal in the subsequent catalytic processing of narrow fractions.

Selected narrow fraction is passed through a reactor filled with a copper-containing catalyst, where in the vapor phase at atmospheric pressure, a temperature of 200 to 300°C, space velocity of the raw material 0,2-0,7 h-1get catalysate containing 60-80 wt.% 2 ethylhexanal. Turning fractions can be done without hydrogen, and in his presence in the volumetric feed rate of 5-10 h-1.

The product of the transformation narrow faction - produce 2-ethylhexanol is subjected to rectification in two vacuum columns efficiency 30-40 TT the Distillate of the first column at a residual pressure of top 20-50 mm RT. senior release fraction containing light components and 2-ethylhexanal, which is sent in the power of the second distillation column operating at a residual pressure of top 60-100 mm RT. senior Distillate from this column identify the fraction containing light components and 30-60 wt.% 2 ethylhexanal, kubovy product or lateral sampling of the lower section of the target 2-ethylhexanal. VAT product of the first column is sent to the raw materials of the process.

The method allows to obtain 2-ethylhexanal, the oxidation of which it is possible to produce 2-ethylhexanol acid purity 98-99 wt.% and above, PR is suitable for the production of plasticizers and drying of the highest quality.

The hydrogenation obtained by this method 2-ethylhexanal on alumina-Nickel-titanium catalyst at a pressure of 25-30 MPa, a temperature of 140-180°With possibly getting 2-ethylhexanol, meets the requirements of GOST brand top grade (see examples).

Salient features of the process are:

- use as a raw material of the process of obtaining 2-ethylhexanal VAT residue from the distillation of butyl alcohol oxosynthesis;

- selection from the specified VAT residue by distillation at a residual pressure in the top of the column 50-90 mm RT. Art. "narrow" faction limit and unsaturated alcohols C8containing 5-15 wt.% acetals C12;

catalytic processing of narrow fractions on copper-containing catalyst at atmospheric pressure in the vapor phase and the temperature of 200-300°With; to improve the stability of the catalyst for the transformation of narrow fractions can be carried out in the presence of hydrogen supplied with a bulk velocity of 5.0-10.0 h-1;

- rectification of the received catalyzate on two columns emitting distillate of the first column at a residual pressure of top 20-50 mm RT. Art. fraction containing light components and 2-ethylhexanal, which is sent to the second column operating at a residual pressure of top 60-100 mm RT., with the release fraction containing light the components and 30-60 wt.% 2 ethylhexanal, and kubovy product or lateral sampling of the lower section of the column - target 2-ethylhexanal.

It should be noted that the allocation of narrow fractions of VAT residue of butyl alcohols production in industry is technically possible to carry out the rectification in two ways two-column scheme. In the first embodiment of the distillate of the first column from the original VAT residue allocate the fraction of light components, and the cubic product of this column distillate allocate target "narrow" faction. On the second diagram in the first column of produce distillate fraction containing light components with alcohols C8from which kubovy product of the second column emit a narrow fraction of alcohols C8. As shown by calculations and experimental runs on pilot plants, both schemes perhaps the selection of narrow fractions of approximately the same composition close to potential output and the cost of heat and cold separation (see examples).

On the contrary, to select from catalyzate "narrow" faction concentrate 2 ethylhexanal, the hydrogenation of which it is possible to obtain 2-ethylhexanol, meets the requirements of GOST, it is important to use the above scheme rectification catalyzate "narrow" faction.

Industrial applicability of the proposed method is illustrated by examples.

Example 1 (average values of the requested parameters).

VAT residue production butyl alcohol oxosynthesis composition, wt.%: light (water, oil aldehydes, alcohols, C4-C7the ketones7bodyformat) - 6,25; ethers and esters With8- of 8.37; limit alcohol C8- 32,45; unsaturated alcohols C8- 20,15; acetals C12- 21,16; other runway - are 11.62 with a flow rate of 1000 kg/h is subjected to distillation column efficiency 30 TT at a residual pressure of top 70 mm RT. Art., the temperature of the top 85°C, the temperature in the cube 132°C.

The distillate of the column allocate 166,4 kg/h of product composition, wt.%: light - 36,12; ethers and esters With8- 41,17; limit alcohol C8- being 9.61; unsaturated alcohols C8- 4,33; acetals C12- 8,77.

CBM product composition, wt.%: light - 0,29; ethers and esters With8- 1,82; limit alcohol With8- 37,01; unsaturated alcohols C8- 23,31; acetals With12- 23,63; other runway - 13,94 with consumption 833,6 kg/h to send in the power of the second distillation column efficiency 30 CT, where at a residual pressure of 70 mm RT. Art., the temperature of the top 114°, cube 160°To produce a distillate "narrow" faction with the consumption of 578 kg/h composition, wt.%: light - 0,42; ethers and esters of C8- 2,63; limit alcohol With8- 52,80; unsaturated alcohols C8- 32,73; acetals C12 - 9,72; other runway is 1.70. Kubovy product columns distinguish the fraction of WINES with consumption 255,6 kg/h composition, wt.%: limit alcohol C8- 1,29; unsaturated alcohols C8- 1,99; acetals C12- 55,09; other runway - to 41.63 sent for recycling for more quantity of butyl alcohol.

Selected narrow fraction is subjected to catalytic conversion in the presence of hydrogen with a heterogeneous catalyst in the vapor phase at atmospheric pressure.

In a reactor filled with a catalyst composition, wt.%: CuO - 51,0; ZnO - 9,5; Cr2About3- 15,5; Al2O3- 21,6; graphite else, at a temperature of 260°C, space velocity, hydrogen 10 h-1serves 578 kg/h narrow fractions with a bulk velocity of 0.5 h-1from which you get a 569,33 kg/h catalyzate composition, wt.%: light - 0,42; ethers and esters of C8- 2,63; limit alcohol C8- 6,87; unsaturated alcohols C8- 4,91; acetals C12- 9,72; other runway is 1.70; 2 ethylhexanol - 69,33; 2-ethylhexenal - 3,81; 2-ethyl-4-methylpentanol - 0,43; 2-ethyl-4-methylpentanol - 0,19.

Catalysate directed to the selection of 2-ethylhexanal rectification in two distillation columns. On the first column efficiency 30 TT at a residual pressure of the top of the column 37 mm RT. Art., the temperature of the top 69,4°in Cuba 133°allocate the fraction of light component is s and 2-ethylhexanal composition, wt.%: light - 0,56; ethers and esters of C8- 3,36; limit alcohol C8- 0,65; unsaturated alcohols C8to 0.44; acetals C12- 0,77; 2 ethylhexanol - 91,02; 2-ethylhexenal - 2,36; 2-ethyl-4-methylpentanol - 0,59; 2-ethyl-4-methylpentanol - 0.25 s flow 418,50 kg/h

The distillate of the first column refer to the power of the second column efficiency 30 TT working at a residual pressure of top 80 mm RT. Art., the temperature of the top 65°With, in the cube 102°C. the Distillate of the second column identify the fraction of light components of the composition, wt.%: light - of 7.90; ethers and esters of C8- 34,61; 2 ethylhexanol - 38,18; 2-ethylhexenal - 14,37; 2-ethyl-4-methylpentanol - to 4.41; 2-ethyl-4-methylpentanol - 0,53 with consumption 29,93 kg/h, and side by selection with 5 TT from Cuba columns distinguish concentrate the target 2-ethylhexanal composition, wt.%: ethers and esters C8- 0,95; limit alcohol C8- 0,71; unsaturated alcohols C8- 0,47; acetals C12- 0,83; 2 ethylhexanol - 95,09; 2-ethylhexenal - 1,43; 2-ethyl-4-methylpentanol - 0,29; 2-ethyl-4-methylpentanol - 0,23 with consumption 388,57 kg/h

VAT product of the first column of the composition, wt.%: ethers and esters C8- 0,61; limit alcohol C8- 24,10; unsaturated alcohols C8- 17,32; acetals C12- 34,55; other runway - 6,40; 2 ethylhexanol - 9,16; 2-ethylhexenal - 7,86 with consumption 150,83 kg/h recycle in the process.

The yield of 2-is telekanala in the calculation for the amount of unsaturated and limit alcohol C 8contained in the original VAT residue production butyl alcohol oxosynthesis taking into account the recycling of alcohols C8contained in the bottom product of the first rectification column catalyzate, represents 92.7 wt.%.

Obtained by the proposed method concentrate 2 ethylhexanol used as feedstock to obtain a 2-ethylhexanoic acid and/or 2-ethylhexanol.

2-Ethylhexanoyl acid obtained by liquid-phase oxidation of the obtained concentrate oxygen at a temperature of 50°C, a pressure of 0.3 MPa. The rectification of the received oxidate on the column efficiency 30 TT working at a residual pressure of the top 30 mm of the RT. the senior was selected 2-ethylhexanoate acid purity of 99.2 wt.% with the output from potential (calculated on the amount of unsaturated and limit alcohol C8contained in the original VAT residue) to 86.7 wt.%.

2-Ethylhexanol is produced by hydrogenation of the specified faction 2-ethylhexanol at a temperature of 180°C, a pressure of 26 MPa, the space velocity of the feedstock 0.5 h-1on alumina-Nickel-titanium catalyst was obtained hydrogenation product from which the rectification column efficiency 40 TT at a residual pressure of top 50 mm RT. the senior was selected commodity 2-ethylhexanol purity of 99.4 wt.% and on other indicators meet the requirements of GOST product high quality is its variety with the release of 93 wt.% in the calculation for the amount of 2-ethylhexanal and 2-ethylhexanal in the faction, coming to hydrogenation.

Example 2 (the lower bound of the residual pressure in the top of the columns to highlight the "narrow" faction, the selection of the concentrate of the target 2-ethylhexanal cube of the second column).

VAT residue production butyl alcohol oxosynthesis composition given in example 1 is processed analogously to example 1 with the difference that the residual pressure at the top of distillation columns to highlight the "narrow" fraction corresponds to the bottom of the claimed boundary, namely 50 mm RT. Art. and concentrate the target 2-ethylhexanal take the cube of the second column.

The result is a concentrate of 2-ethylhexanol with the content of the basic substance is 90.2 wt.% with the output potential of 95.4 wt.%.

Oxidation of the concentrate 2 ethylhexanal in the conditions of example 1 get oxidat from which the rectification give 2-ethylhexanoyl acid purity of 98.5 wt.% with the output potential of 87.3 wt.%.

The hydrogenation concentrate 2 ethylhexanal and the rectification section of hydrogenated feed under the conditions of example 1 to give 2-ethylhexanol purity rate of 99.0 wt.% and other indicators of quality that meets the requirements of GOST, with the output from the potential to 94.3 wt.%.

Example 3 (the upper bound of the residual pressure in the top of the columns to highlight the "narrow" faction, the lower bound of hydrogen supply).

VAT residue of butyl alcohols production oxazin the zoom of the composition, described in example 1 is processed analogously to example 1 with the difference that the residual pressure at the top of distillation columns to highlight the "narrow" fraction corresponds to declare the border, namely 90 mm RT. Art. and catalytic conversion of narrow fractions is carried out at a flow of hydrogen 5,0 h-1.

The result is a concentrate of 2-ethylhexanol with the content of the basic substance 93,7 wt.% with the output potential of 89.7 wt.%.

Oxidation of the concentrate 2 ethylhexanal in the conditions of example 1 get oxidat from which the rectification give 2-ethylhexanoyl acid purity to 98.4 wt.% with the output from potential 87,7 wt.%.

The hydrogenation concentrate 2 ethylhexanal and the rectification section of hydrogenated feed under the conditions of example 1 to give 2-ethylhexanol purity rate of 99.0 wt.% and other indicators of quality that meets the requirements of GOST, with the output from potential was 92.3 wt.%.

Example 4 (the lower bound concentration acetals With12in the "narrow" faction, without hydrogen).

VAT residue production butyl alcohol oxosynthesis composition given in example 1 is processed analogously to example 1 with the difference that the concentration of acetals With12in the "narrow" fraction corresponds to the bottom of the claimed boundary, namely 5 wt.%, and catalytic conversion of narrow fractions spend without water what kind.

The result is a concentrate of 2-ethylhexanol with the content of the basic substance 95.6 wt.% with the output potential of 85.2 wt.%.

Oxidation of the concentrate 2 ethylhexanal in the conditions of example 1 get oxidat from which the rectification give 2-ethylhexanoyl acid purity 98,0 wt.% with the output from potential 89,4 wt.%.

The hydrogenation concentrate 2 ethylhexanal and the rectification section of hydrogenated feed under the conditions of example 1 to give 2-ethylhexanol purity of 99.1 wt.% and other indicators of quality that meets the requirements of GOST, with output capacity of 87.8 wt.%.

Example 5 (the upper bound concentration of acetals With12in the "narrow" faction, the selection of the concentrate of the target 2-ethylhexanal cube of the second column).

VAT residue production butyl alcohol oxosynthesis composition given in example 1 is processed analogously to example 1 with the difference that the concentration of acetals With12in the "narrow" fraction corresponds to declare the border, namely 15 wt.%, and concentrate the target 2-ethylhexanal take the cube of the second column.

The result is a concentrate of 2-ethylhexanol with the content of the basic substance of 94.8 wt.% with the output from potential 86,0 wt.%.

Oxidation of the concentrate 2 ethylhexanal in the conditions of example 1 get oxidat from which the rectification give 2-ethylhexanol is islote purity that 98.9 wt.% with the output from the potential for 87.2 wt.%.

The hydrogenation concentrate 2 ethylhexanal and the rectification section of hydrogenated feed under the conditions of example 1 to give 2-ethylhexanol purity to 99.6 wt.% and other indicators of quality that meets the requirements of GOST, with the output from potential 90,4 wt.%.

Example 6 (the lower limit temperature in the reactor catalytic conversion of narrow fractions).

VAT residue production butyl alcohol oxosynthesis composition given in example 1 is processed analogously to example 1 with the difference that the temperature in the reactor catalytic conversion of narrow fractions corresponds to the bottom of the claimed boundary, namely 200°and the volumetric feed rate of hydrogen is equal to 5 h-1.

The result is a concentrate of 2-ethylhexanol with the content of the basic substance 95,0 wt.% with the output from the potential for 87.4 wt.%.

Oxidation of the concentrate 2 ethylhexanal in the conditions of example 1 get oxidat from which the rectification give 2-ethylhexanoyl acid purity of 98.3 wt.% with the output from the potential to 85.8 wt.%.

The hydrogenation concentrate 2 ethylhexanal and the rectification section of hydrogenated feed under the conditions of example 1 to give 2-ethylhexanol purity rate of 99.0 wt.% and other indicators of quality that meets the requirements of GOST, with output capacity of 85.1 wt.%.

Example 7 (upper limit temperature in the catalytic reactor is about turning "narrow" faction).

VAT residue production butyl alcohol oxosynthesis composition given in example 1 is processed analogously to example 1 with the difference that the temperature in the reactor catalytic conversion of narrow fractions corresponds to declare the border, namely 300°and the volumetric feed rate of hydrogen is 10 h-1.

The result is a concentrate of 2-ethylhexanol with the content of the basic substance 93,2 wt.% with the output potential of 91.3 wt.%.

Oxidation of the concentrate 2 ethylhexanal in the conditions of example 1 get oxidat from which the rectification give 2-ethylhexanoyl acid purity of 99.4 wt.% with the output from the potential to 82.1 wt.%.

The hydrogenation concentrate 2 ethylhexanal and the rectification section of hydrogenated feed under the conditions of example 1 to give 2-ethylhexanol purity of 99.5 wt.% and other indicators of quality that meets the requirements of GOST, with the output from potential 90,4 wt.%.

Example 8 (the lower bound of the residual pressure in the first column rectification catalyzate).

VAT residue production butyl alcohol oxosynthesis composition given in example 1 is processed analogously to example 1 with the difference that the residual pressure in the first column rectification catalyzate corresponds to the bottom of the claimed boundary, namely 20 mm RT. Art. and catalytic pre the treatment of narrow fractions carried out without hydrogen.

The result is a concentrate of 2-ethylhexanol with the content of the basic substance 97,2 wt.% with the output from the potential for 93.4 wt.%.

Oxidation of the concentrate 2 ethylhexanal in the conditions of example 1 get oxidat from which the rectification give 2-ethylhexanoyl acid purity of 99.1 wt.% with the output from the potential for 87.4 wt.%.

The hydrogenation concentrate 2 ethylhexanal and the rectification section of hydrogenated feed under the conditions of example 1 to give 2-ethylhexanol purity of 99.3 wt.% and other indicators of quality that meets the requirements of GOST, with the output from potential 93,7 wt.%.

Example 9 (upper bound of the residual pressure in the first column rectification catalyzate).

VAT residue production butyl alcohol oxosynthesis composition given in example 1 is processed analogously to example 1 with the difference that the residual pressure in the first column rectification catalyzate corresponds to declare the border, namely 50 mm RT. Art.

The result is a concentrate of 2-ethylhexanol with the content of the basic substance 96,7 wt.% with the output from potential 86,5 wt.%.

Oxidation of the concentrate 2 ethylhexanal in the conditions of example 1 get oxidat from which the rectification give 2-ethylhexanoyl acid purity of 98.3 wt.% with the output from potential 84,2 wt.%.

The hydrogenation concentrate 2 ethylhexanal the rectification section of hydrogenated feed under the conditions of example 1 to give 2-ethylhexanol purity of 99.2 wt.% and other quality indicators, meets the requirements of GOST, with the output from potential 93,7 wt.%.

Example 10 (the lower bound of the residual pressure in the second rectification column catalyzate).

VAT residue production butyl alcohol oxosynthesis composition given in example 1 is processed analogously to example 1 with the difference that the residual pressure in the second rectification column catalyzate corresponds to the bottom of the claimed boundary, namely 60 mm RT. Art.

The result is a concentrate of 2-ethylhexanol with the content of the basic substance of 92.9 wt.% with the output potential of 91.6 wt.%.

Oxidation of the concentrate 2 ethylhexanal in the conditions of example 1 get oxidat from which the rectification give 2-ethylhexanoyl acid purity by 98.7 wt.% with the output potential of 88.3 wt.%.

The hydrogenation concentrate 2 ethylhexanal and the rectification section of hydrogenated feed under the conditions of example 1 to give 2-ethylhexanol purity of 99.1 wt.% and other indicators of quality that meets the requirements of GOST, with output capacity of 91.5 wt.%.

Example 11 (the upper bound of the residual pressure in the second rectification column catalyzate).

VAT residue production butyl alcohol oxosynthesis composition given in example 1 is processed analogously to example 1 with the difference that the residual pressure in the second column of the rivers is eficacia catalyzate corresponds to declare the border, namely 100 mm Hg

The result is a concentrate of 2-ethylhexanol with the content of the basic substance br93.1 wt.% with the output potential of 89.2 wt.%.

Oxidation of the concentrate 2 ethylhexanal in the conditions of example 1 get oxidat from which the rectification give 2-ethylhexanoyl acid purity of 99.1 wt.% with the output from potential 87,59 wt.%.

The hydrogenation concentrate 2 ethylhexanal and the rectification section of hydrogenated feed under the conditions of example 1 to give 2-ethylhexanol purity of 99.2 wt.% and other indicators of quality that meets the requirements of GOST, with the output from the potential for 87.4 wt.%.

Example 12 the lower limit of the concentration of 2-ethylhexanal in the distillate of the second rectification column catalyzate).

VAT residue production butyl alcohol oxosynthesis composition given in example 1 is processed analogously to example 1 with the difference that the concentration of 2-ethylhexanal in the distillate of the second rectification column catalyzate corresponds to the bottom of the claimed boundary, namely 30 wt.%.

The result is a concentrate of 2-ethylhexanol with the content of the basic substance 95,0 wt.% with the output from potential 90,4 wt.%.

Oxidation of the concentrate 2 ethylhexanal in the conditions of example 1 get oxidat from which the rectification give 2-ethylhexanoyl acid purity of 99.5 wt.% with output capacity of 5.6 wt.%.

The hydrogenation concentrate 2 ethylhexanal and the rectification section of hydrogenated feed under the conditions of example 1 to give 2-ethylhexanol purity of 99.7 wt.% and other indicators of quality that meets the requirements of GOST, with output capacity of 88.6 wt.%.

Example 13 (the upper bound concentration of 2-ethylhexanal in the distillate of the second rectification column catalyzate).

VAT residue production butyl alcohol oxosynthesis composition given in example 1 is processed analogously to example 1 with the difference that the concentration of 2-ethylhexanal in the distillate of the second rectification column catalyzate corresponds to declare the border, namely 60 wt.%, target concentrate 2 ethylhexanal take the cube of the second column.

The result is a concentrate of 2-ethylhexanol with the content of the basic substance to 94.3 wt.% with the output from the potential to 88.4 wt.%.

Oxidation of the concentrate 2 ethylhexanal in the conditions of example 1 get oxidat from which the rectification give 2-ethylhexanoyl acid purity rate of 99.0 wt.% with the output potential of 86.9 wt.%.

The hydrogenation concentrate 2 ethylhexanal and the rectification section of hydrogenated feed under the conditions of example 1 to give 2-ethylhexanol purity of 99.1 wt.% and other indicators of quality that meets the requirements of GOST, with the output from the potential to 86.4 wt.%.

Example 14 (another scheme is adelene "narrow" faction).

VAT residue production butyl alcohol oxosynthesis composition given in example 1 is processed analogously to example 1 with the difference that a narrow fraction of alcohols C8allocate scheme, according to which of the original VAT residue distillate of the first column identify the fraction of light components and alcohols C8from which the distillate of the second column between "narrow" faction.

The result is a concentrate of 2-ethylhexanol with the content of the basic substance of 93.3 wt.% with the output potential of 94.9 wt.%.

Oxidation of the concentrate 2 ethylhexanal in the conditions of example 1 get oxidat from which the rectification give 2-ethylhexanoyl acid purity of 99.1 wt.% with the output from potential 83,7 wt.%.

The hydrogenation concentrate 2 ethylhexanal and the rectification section of hydrogenated feed under the conditions of example 1 to give 2-ethylhexanol purity to 99.6 wt.% and other indicators of quality that meets the requirements of GOST, with the output from potential was 92.3 wt.%.

1. The method of obtaining 2-ethylhexanal of the departure process of propylene hydroformylation, including catalytic processing fractions containing mainly marginal and unsaturated alcohols With8allocated from the waste by distillation, characterized in that the feedstock of the process using the VAT residue from which ectification butyl alcohols of oxosynthesis, from which the rectification produce a fraction containing mainly marginal and unsaturated alcohols With8and 5-15 wt.% acetals With12,in two columns at a residual pressure of the top of the columns 50-90 mm Hg, which is then subjected to processing in the vapor phase at atmospheric pressure on a copper-containing catalyst at a temperature of 200 to 300°followed by distillation catalyzate on two columns emitting distillate of the first column at a residual pressure of top 20-50 mm Hg fraction containing light components and 2-ethylhexanal, which is sent to the second column operating at a residual pressure of top 60-100 mm Hg, emitting a distillate fraction containing light components and 30-60 wt.% 2 ethylhexanal and kubovy product or lateral sampling of the lower column section allocate the target 2-ethylhexanal.

2. The method according to claim 1, wherein processing the fractions containing mainly marginal and unsaturated alcohols With8and5-15 wt.% acetals With12, is carried out at a volumetric feed rate of raw materials 0,2-0,7 h-1and the space velocity of hydrogen 5-10 h-1above catalyst composition, wt.%: CuO - 51,0 - 57,0; ZnO - 9,5-12,5; Cr2About3- 12,5-15,5; Al2O3- 19,6 - 21,6; graphite - rest.



 

Same patents:

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the hydroformylation process of olefins with using rhodium catalyst for preparing aldehydes comprising 3-21 carbon atoms. Reaction products from the hydroformylation reactor are separated for: (a) gaseous and liquid phase; (b) liquid phase is fractionated for a head fraction containing unreacted olefins and aldehydes and a vat fraction containing by-side products and rhodium catalyst, and (c) the vat fraction is cooled to temperature lower than the hydroformylation point into reactor, preferably, to 10-120°C. Then the vat fraction is saturated with carbon monoxide-containing gas under partial pressure of carbon monoxide 0.1-300 bars. The vat fraction containing catalyst and carbon monoxide are recovered completely or partially into the hydroformylation reactor. Invention provides prolonged working life of catalyst due to prevention of its inactivation in stages for isolation of the end product.

EFFECT: improved preparing method.

11 cl, 3 tbl, 3 dwg, 2 ex

FIELD: organic chemistry, in particular production of carbonyl compounds such as aldehydes and ketones.

SUBSTANCE: claimed method includes reaction of nitrous oxide with alkenes in presence of inert gas as diluent. Reaction is carried out in gas phase at 401-700°C and under pressure of 2-300 atm. Target compounds represent value intermediates for precise and base organic synthesis.

EFFECT: method of high selectivity in relation to target products and improved explosion proofing.

5 cl, 1 tbl, 14 ex

FIELD: chemical technology.

SUBSTANCE: invention describes a method for realization of the multiphase reaction of hydroformylation of olefins in tube reactor wherein a catalyst is in the continuum liquid phase and at least one the parent product is in the dispersed phase. The hydroformylation reaction is carried out at the loading coefficient B 0.8 or above that is calculated as a quotient from the pressure fall PD length value and the static pressure PS value wherein PD = Cw x g/2 x w2/D and PS = (M/V) x g wherein Cw means a tube reactor resistance coefficient; D means diameter of tube reactor; W means a flow rate moving; S means a density value of flowing phase; M means a weight flow of all components in reactor; V means a volume flow; g = 9.81 m/c2.

EFFECT: improved method, enhanced output of process.

11 cl, 1 dwg, 9 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing concentrate of butyric aldehydes by oxonation. Method is carried out by the hydroformylation reaction of propylene with synthesis-gas in two in-line connected reactors at temperature 120-150°C, under pressure 250-300 kgf/cm2 and with heat removing by circulation of cooling agent through Field's tubes installed in hydroformylation reactors followed by separation of reaction products. The hydroformylation process in the first reactor is carried out in regimen when the ratio of volume consumptions of cooling agent circulating in Field's tubes and propylene feeding into reactor is (18-28):1. Invention provides enhancing yield of end products, improving energetic indices due to effective heat transfer in the hydroformylation reactor.

EFFECT: improved preparing method.

1 tbl, 4 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: technology for separation of hydroformylation products by naphthenate-evaporating schedule of oxo-synthesis. Separation of propylene hydroformylation products after its decolbatization is carried out by a single evaporation under atmosphere pressure with separation of distillate - fraction of butyric aldehydes from the vat residue - cobalt salts solution in high-boiling by-side products. Indicated evaporation with separation of vapor phase from liquid phase is carried out in separator device under atmosphere pressure, at temperature of liquid phase 90-115°C or 130-170°C with reinforced circulation of liquid phase through boiler at the circulation ratio = (3-30):1. Then the successive additional extraction aldehydes and alcohols from the vat residue are carried out by a single evaporation under vacuum. Method provides reducing loss of cobalt catalyst at the stage for separating products of oxidative decolbatization, and improved economic indices.

EFFECT: improved method for separating.

9 ex

The invention relates to a method for producing carbonyl compounds with the number of atoms2-C40
The invention relates to methods of obtaining and purification of 3,3-dimethylbutyramide

The invention relates to a method for producing an aldehyde intermediate of organic synthesis

The invention relates to a method for saturated monoallelic - intermediate products of organic synthesis

The invention relates to the field of production of oxygen-containing organic compounds, ketones, unsaturated alcohols and possibly aldehydes by isomerization WITH5-epoxides in the presence of a homogeneous catalyst

The invention relates to a method of separation of cyclohexane from the reaction mixture for the synthesis of cyclohexanone and cyclohexanol and may find application in the chemical industry for preparation of caprolactam

The invention relates to a method of obtaining a trademark of acetone, select it from the products of decomposition of cumene hydroperoxide multistage rectification
The invention relates to chemical technology, namely the allocation method n-butyric aldehyde (IA) in the process of oxosynthesis

The invention relates to chemical technology, more specifically to an improved method of allocating n-butyric aldehyde (IA) from mixtures also containing somelady aldehyde (IMA), pentane-hexane fraction of saturated hydrocarbons (PGF), bodyformat forming intangible assets with azeotropic system

FIELD: alcohol production.

SUBSTANCE: method comprises direct distillation of concentrate of top ethyl alcohol impurities or rectification of intermediate ethyl alcohol fraction in presence of an alkali agent selected from sodium and potassium oxide, carbonate, and bicarbonate hydrates, and aqueous ammonia in case of top ethyl alcohol impurities processing and selected from sodium and potassium oxide, carbonate, and bicarbonate hydrates, calcium oxide, and aqueous ammonia in case of intermediate ethyl alcohol fraction rectification at alkali agent concentration 0.01 to 3.0 wt % and vat temperature 80-86°C. Desired processing product is commonly used as a binary mixture component and vat residue obtained in distillation and rectification operation is commonly used as additional component of fuel oil.

EFFECT: achieved wasteless processing of alcohol production wastes and utilization of all processing products.

6 cl

FIELD: method for production of alcohol-containing solvents based on waste from ethanol production from food-grade raw materials.

SUBSTANCE: claimed method includes reprocessing of etheraldehyde fraction of concentrate containing ethanol main admixtures from starch- and/or sugar-containing raw materials. Process is carried out in rectifier at vapor phase temperature in still of 60-90°C. Nitrosolvent is obtained by mixture sampling at 60-70°C. Degreasing solvent is obtained by mixture sampling at starting temperature in column top of 73°C or more when ethers are detected in distillate. Claimed nitrosolvent (degreasing solvent) contain (mass %): acetate-type ethers 10-30 (0.8-2.9); aliphatic alcohols 51-74 (87-89); acetaldehyde 5-9 (0.2-1.5), and water 8-10 (8-10).

EFFECT: simplified and economy method for reprocessing of waste from ethanol production; enhanced assortment of alcohol-containing solvents.

3 cl, 1 dwg, 3 ex, 3 tbl

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to improved process of high-purity solvent-grade fluorinated alcohol production, which comprises reaction of methanol with tetrafluoroethylene or hexafluoropropylene in presence of alkylperoxide. Process leads to formation of fluorinated alcohol having general formula: H(CFR1CF2)nCH2OH (I), wherein n=1 or 2; when n=1, R1 represents F or CF3 and, when n=2, R1 represents F. After completion of reaction, reaction mixture is distilled on distillation column in presence of water and HF to produce (i) top fraction containing alcohol formed from alkyl peroxide, water, and HF and (ii) bottom liquid containing fluorinated alcohol of formula (I). Bottom liquid is purified to recover desired fluorinated alcohol.

EFFECT: increased yield of product.

7 cl, 3 dwg, 2 ex

The invention relates to a method distillative get monoethylene glycol of high purity of the product of hydrolysis of ethylene oxide using a bog of water under pressure, vacuum Stripping of water and subsequent distillative purification, characterized in that at least the first Stripping column under pressure in the cascade equipped with a distillation unit having at least one degree of separation, and part of the flow of the top of the column (columns) bog water under pressure, equipped with(local) unit of distillate, derived from the process, the temperature in the zone below the point of input power in the first column of the cascade is more than 80With, and the pressure in the distillation unit is at least 1 bar

The invention relates to an improved method of distillation selection of high-purity monoethylene glycol from the hydrolysis product of ethylene oxide by dehydration in cascade for dewatering under pressure, in which at least the first column contains a distant section of the at least one separation stage in which the temperature is below the point of supply columns to dehydration under pressure is above 800With, and the pressure in distant sections is not less than 1 bar, with the removal of a portion of the flow from the system, then dehydrated under vacuum, to remove water stream containing monoethylene glycol in a concentration of less than 1 wt.%, preferably 0.1 wt.%, srednetepa components and low-boiling components, removing it from the system, possibly after further processing, with subsequent distillation purification in the distillation column purification, in which between the selection of the head of the stream from the top of the column and the side-wall of monoethylene glycol is from 1 to 10 separation stages, with dehydration under vacuum is carried out in two columns for dehydration under vacuum to remove the above-mentioned water flow in the form of the head stream of the second column of the water flow from the column dehydration under vacuum in the form of a side stream, and the head stream of the column distillation purification of monoethylene glycol return in the middle part of the column for dehydration under vacuum or last column for dehydration under vacuum

The invention relates to a method of separation of cyclohexane from the reaction mixture for the synthesis of cyclohexanone and cyclohexanol and may find application in the chemical industry for preparation of caprolactam
Up!