SU1168548A1 - Method of obtaining aliphatic mixture of aldehydes and c4-c15 alcohols - Google Patents

Abstract

A method for producing a mixture of aliphatic aldehydes and alcohols by hydroforming olefins at 160–200 s and a pressure of 4–30 MPa in the presence of a cobaltcarbonylphosphine catalyst and iron pentacarbonyl, wherein the process is carried out in the presence of a trialkylphosphine formula p rrp rine formula p rone p r. -, y-alkyl, with a molar ratio of trialkylphosphine: iron pentacarbonyl

Description

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ABOUT)

00 ate 4; bo 1 The invention relates to an improved method for producing a mixture of aliphatic aldehydes and alcohols, j-hydroformylation of olefins in the presence of a phosphate-modified cobalt catalyst in the presence of iron carbonyls or other catalytic compounds in the system. The aim of the invention is to simplify the technology of the process of hydrophore grinding of iron flowing under pentocarbonyl, which alters the activity and selectivity of the catalyst. Example 1. Hydroformylation of propylene in the presence of the equivalent effect of iron pentacarbonyl at high concentrations (comparative example). In a steel autoclave with a capacity of 250 ml equipped with a stirrer, 54.7 (72.88 May.%) Heptane, 0.036 g (0.05 May.%) Co ,, (CO), 0.213 g (0.27 May.% ) (n-C.H9) zR (P / Co 5.1 mol / molj and 0.25 g (0.33 May.%) Fe (CO) j (Fe / Co 6/1 mol / mol). Autoclave Fill the synthesis gas with CO2 1: 1 to a pressure of 10 MPa, heat up to 180 ° C with stirring and maintain at this temperature for 2 hours. 20.11 g (26.79% by weight) of liquid propylene and wire t hydroformylation process at constant pressure (10 MPa) for 1.5 hours. The initial flow rate is taken as a measure of the reaction rate van of the synthesis gas (mol CO / min) from the supply tank (100 ml). Receive: - reaction rate 7.2-10 mol CO / min, conversion of propylene to 70%, the yield of alcohols 12 on the reacted prod, contains The products of normal structure in the amount of aldehydes and alcohols are 56%. Example 2. Hydroforming of propylene with a toxic effect of Fe (CO) j in small concentrations (comparative example). The process is carried out in the same way as in Example 1, but the amount introduced Fe (CO) j 0.0412 g (0.055 wt.%) which corresponds to the ratio of Fe / Co (1/1 mol / mol). Receive: reaction rate 1, CO / min, the yield of alcohols on the reacted propylene 21%, the content of products 482 normal structure 87%. In the product, an absorption maximum is observed in the UV spectrum at 260 nm. Example 3. Hydroformylation of propylene (1/1 mol / mol). The process is carried out as described in example 1, but in the presence of an additional amount (.) P 0, 0404 g (0.054% by weight), (P / Fe 1/1 mol / mol) introduced into the autoclave together with the catalyst and Fe (CO) (total amount of (). 0, 253 g or 0.337 wt .-%. Get: reaction rate 2.8-10 mol CO / min, conversion of propylene 45%, outputs to unreacted propylene: products of normal structure - 89% , alcohols - 22% (3.07 g). Example 4. Hydroformylation of propylene (PRj / Fe 2/1 mol / mol). The process is carried out as described in Example 2, but in the presence of an additional amount () jP 0, 485 g (0.64 May.%) (P / Fe 2/1 mol / mol) introduced into the autoclave together with the catalyst and Fe (CO) (total amount (n-SLND) P 0 697 g or 0.927 May.%). Receive: reaction rate 2.8 CO / min, propylene conversion 45%, yields to unreacted propylene: products of normal structure 88%, alcohols 23% by weight (3.21 g). Example 5. Hydroformylation of propylene with continuous introduction of (n-C4H3) cP- (PRj / Fe 2: 1 mol / mol). The process is carried out as described in Example 1, but at the same time, from the feed tank together with synthesis gas, iron pentacarbonyl is continuously fed at a rate of 3 -10 mol / min. At the same time, (n-0 | H5) zR were continuously introduced into the reactor with a dispenser at a rate of 6–10 mol / min. Get: the reaction rate of 2.9-1SG mol CO / min, propylene conversion of 48%, the outputs on the reacted propylene: products of normal structure 89%, alcohols 22 wt.% (3.27 g). Example 6. Hydroformylation of a mixture of olefins of a composition with the toxic effect of Fe (CO) j using PR, where R is H (comparative example). To hydroformylate a mixture of olefins of composition

In a steel autoclave with a capacity of 350 ml, 30.6 g of olefins (81.51 wt.%), obtained by dehydrogenating paraffins followed by extension, 0, 62 g (1.65 wt.%) Coj (C0) V, 4.9 g ( 13.05 May.%) Trilauryl phosphine (P / Co 2.5 / 1 mol / mol) and 1.42 g (3.8 May.%) Fe (CO) y (Fe / Co 2/2 mol / mol) . The reactor is filled with synthesis gas to a pressure of 6 MPa, heated to and under a pressure of 9 MPa, and the mixture is kept under stirring. The pressure is kept constant by supplying gas as it is consumed. After completing the test, the product is analyzed by GLC. The duration of the experiment 21 minutes, the rate constant QlO c, the conversion of olefins 68.5%, the yield of alcohols and aldehydes composition to the reacted olefins 88 May. % (21.77 g), paraffins 6.11 May. % (1.29 g), the content of normal alcohols in the amount of alcohols and aldehydes is 46.5%.

Example 7. Hydroformylation of a mixture of olefins (composition olefins)

The process is carried out as described in Example 7 in the presence of an additional amount of trilauryl phosphine (P / Fe 3.1 mol / mol) introduced into the autoclave together with the catalyst and Pe (CO) 5. The total amount of trilauryl phosphine is 10.72 g (24.72 May.%), Which is 5.5 mol of phosphine per g-atom of Co).

After hydroformylation was carried out for 240 minutes, the reaction rate constant was 0.75 x 10, the conversion of olefins was 66.8%, the yield of alcohols and aldehydes to the reacted olefins was 77% by weight (18.57 g), and paraffins — 16.8 May . % (3.47 g), the content of normal alcohols of the composition in the amount of alcohols and aldehydes 75.6%.

Example 8. Hydroformylation mixture of olefins composition

The process is carried out as described in example 7, but at a pressure of synthesis gas 1CO: 2Hj 4 MPa and: content (.P 8.8 g k21.24 May.%) (P / Fe 2.1 mol / mol P / With 4.5 mol / mol).

After hydroformylation is carried out for 10 hours, the following is obtained: the reaction constant of 0.17.

43.6% of olefin cadre, spit and aldehyde yield to the reacted olefins 77.8 May.% (12.25 g), paraffins 14.0 May. % 1.89 g), the content of normal ethics composition of 76.8%.

Example 9. Hydroformylation of C-jf-C olefins using PRj, where R is CYJ-C Y.

31.4 g (70.55 May.%) Of olefins of the composition GIJ-C J, 0.64 g (1.44% by weight) of Co (CO 11.0 g (24.21% by weight) mixture) are charged into the autoclave. Phoefin composition (.) jP (P / Fe 2/1 mol / mol), (P / Co 4; 5.1 mol / mol), 1.47 g (3.3 wt.%) Fe (CO) 5- After the hydroformylation was carried out at a pressure of 1 ° C: 2H, j 30.0 MPa, the gas of the gas was found: a reaction rate constant of 3.5-10 s, conversion of olefins 73.5%, a yield of epyds and aldehydes of composition, on the reacted olefins 68.7 May (18.34 g), paraffins 19.6 wt.% (4.59 g). Example 10. The catalyst of Example 1 is distilled at atmospheric pressure to obtain a product with a content of At less than 1 pp, determined by atomic absorption, the iron content in the product obtained without using the proposed method is 0.1-1.0%, i.e. 1L -10 pp.

The process should be carried out at a molar ratio of trialkylphosphine pentacarbonyl of iron equal to (1-3): 1. Adding a larger excess of trialkylphosphine to the initial reaction mixture is impractical because of a significant decrease in catalyst activity with a large foefin / cobalt ratio. A smaller excess will not lead to the desired result due to the low concentration of PRj in the reaction mixture.

The introduction of PRj in the course of synthesis as Fe (CO) y accumulates allows Fe (CO) 5 to Fe (CO) PR3 and Fe (CO) jPRj, which are not catalytic dye with respect to the modified PRj cobalt catalyst; preserve the original ratio of P / Co in the sietem, thereby ensuring that the selectivity and activity of the catalyst is sown; it is easy to separate Fe from the reaction products by simple distillation, since these phosphine derivatives of iron pentacarbonyl are stable compounds and do not have a high volatility.

The application of the proposed method gives the stability of the catalyst under the conditions of the poisoning effect of impurities - catalytic poisons; simplified hydroformylation technology; use as an inhibitor of harmful impurities agent - modifying ligand - component of the catalyst mixture. There is no need for an additional step of purification of the carbonyls of iron from the reaction products and the possibility of carrying out a continuous process.

The method also allows to inhibit the action of some other

Dov, for example, oxygen, reducing the activity or selectivity of the process. All this greatly simplifies the process of hydroformylation.

Claims (1)

METHOD FOR PRODUCING A MIXTURE OF ALIPHATIC ALDEHYDES AND ALCOHOLS WITH ₄ ~ C _1U hydroforming of olefins at 160-200 ° C and a pressure of 4-30 MPa in the presence of cobalt-carbonylphosphine catalyst and iron pentacarbonyl, characterized in that, in order to simplify the technology, the process is carried out in the presence of trialkylphosphine of the formula pR ₃ , where R _s is C ₄ -C _u -alkyl, with a molar ratio of trialkylphosphine: iron pentacarbonyl (1-3): 1 (L CZ Q0 sl> 1 1168548 2