SU994461A1 - Process for hydroformylating olefins - Google Patents

Description

The invention relates to petrochemical synthesis, in particular, to the process of hydrophorenealing olefins.

The known method of hydroformylation of olefins according to a triad scheme involving the stages of carbonyl-formation by passing through a prepared catalyst containing CoO on pumice, a solvent of the pentalhexane fraction or toluene and synthesis gas at 120-200 ° C and a pressure of 200-300 atm, hydroforming the olefin by feeding into a 0.020, 2% aqueous solution of carbonyl co, balt, olefin, solvent and syngas gas at 130-170 ° C, synthesis gas pressure of 200-300 atm and decobalization of the hydroforming products containing: cobalt carbonyls, by putting them through pumice stone containing cobalt oxide, where, at 14018 ° C and a hydrogen pressure of 200-300 atm -1, there is a deposition of cobal1, that in the form of metal. The hydroformylation product freed from cobalt is hydrogenated in the presence of heterogeneous catalysts to butyl alcohols and rectified to isolate the target

products. The yield of butyl alcohols on the supplied propylene (at its 95% conversion) is 85% of the theory of til.

The disadvantage of this method is the instability of the thermal mode of cobaltisation and dekobaltisation. With small deviations from the mode of the process or the technology of preparation of a cobalt catalyst of Soki co10 balt on pumice stone, temperature flashes t rise in temperature (up to) and decompaction in the high pressure system are observed. This creates emergencies in industrial production and leads to a sharp decrease in the yield of propylene hydroformylation products. The cabal that remained on the nozzle after the temperature flash practically does not enter into a rebalancing action. Often, the catalyst's ability to react with carbonyl-formation is low for unknown reasons. In such cases, the cobaltization process takes 425–16 days, instead of the regulated 2–4 days, and the resulting cobalt carbonyls have a small active ability to catalyze the reaction of hydrochloroforming of propylene, which comes from

the duction period is 2-5 days. When switching the cobalt reactor to the de-butchetization and when using the catalyst, cobalt oxide on the pumice stone for the cobaltisation process, side reactions can occur, which are characterized by a large thermal effect. The most significant of these are the reactions of heterogeneous hydrogenation of oily aldehydes to butyl alcohols. Thermal effect 18 kcal / g-mol), methanation of CO (49 kcal / g-mol) and conversion of the water vapor formed to CO (10.85 kcal / gmol. The duration of the expositive course of these reactions is 1-2 minutes. The yield of the target butyl alcohols in such cases is 60-64% of the theory (instead of 85%). The aim of the invention is to simplify the method. olefins comprising the carbonyl stage formation by treatment of cobalt NI, as they use cobalt oxide or cobalt carbonate, or cobalt naphthenate, or cobalt metal, using synthesis gas in an organic solvent to hydroformylate olefin at 130-170 ° C and synthesis gas pressure 200- 300 atm and decobalt stage of hydroformylation products containing cobalt carbonyls by thermal decomposition. Cobalt oxide or cobalt carbonate, or cobalt naphtch nat, or metallic cobalt are used as cobalt compounds. Thermal decomposition of cobalt carbonyls is carried out on pumice. The method is carried out as follows. Cobalt carbonyls are obtained in a separate apparatus (cobaltiser) at 130-170 ° С, pressure 200-300 atm for 2-180 minutes instead of 4-16 t according to the prototype) from various cobalt compounds dissolved or suspended in an organic solvent. As a starting cobalt compound, cobalt oxide, cobalt naphthenate, cobalt carbonate or metallic cobalt suspended or dissolved in hydrocarbons, alcohols, bottom products and other solvents are used. During this time, 99-100% conversion of cobalt compounds to carbonyls is achieved. The resulting solution of cobalt carbonyls is used in the reaction of hydroprophication of olefins, carried out under the following conditions: temperature 120-180 ° C, pressure 200-300 atm, concentration of cobalt carbonyls 0, 02-0.20 Bvs.%. The products of hydroformylation are subjected to decobaltiation on pure pumice at 100-170 ° C and a hydrogen pressure of 200-300 atm. Cobalt precipitates in the form of metal on pumice, cobalt is deposited after the completion of the cycle of applying it to pumice stone, and cobaltation is carried out under the conditions described, and the hydroformylation product is hydrogenated to butyl alcohols and rectified to isolate them. The advantages of the proposed method over the known method are the simplification of the technological scheme of production (the catalyst preparation shop is disposed of cobalt oxide on pumice, the installation is trouble-free), the equipment productivity is increased, as the first carbonylation cycle time decreases from 4-16 days to 3 h and there are no thermal flashes, which will increase the plant performance by 30%. The yield of the target products increases. Example. 253.2 g of cobalt oxide suspension in n-butanol containing 3.22 g of cobalt oxide (2.5 g of Co) f and 100 liters of synthesis gas (CO: HI 1: 1) are fed to the cobalt-containing reactor with a capacity of 0, 3l. At a pressure of 280 atm and a temperature of 155–160 s, cobalt carbonyls are formed in a cobalt reactor at a pressure of 280 atm. A homogeneous solution of cobalt carbonyls containing 2.5 g of carbonyls (in terms of cobalt) is sent to a hydroformylation reactor with a capacity of 2 liters. 1400 iir pentane-hexane fraction, 1000 g of propylene and 1500 g of synthesis gas are also served here. At 150 ° C and a synthesis gas pressure of 280 atm, the hydroformylation reaction occurs. 3337, 6 g of reaction products containing 7.6 g of cobalt carbonyls (2.5 g of Co 1460 g of oil aldehydes, 290 g of bo-alcohol and alcohols, 1400 g of pentane-hexane fraction, 130 g of hydroformylation by-products, and 50 g unreacted propylene, cooled in a refrigerator and fed to the separation in a high pressure separator (SVD). ATS separates gases from liquid products. 3337, 6 g of hydrochloride catadizate 3) Arrange at 180 s and 280 atm pressure of hydrogen, decobalt in a 2000 ml decobalizer, filled with 1700 ml of pure pumice. Cobalt metal is deposited on pumice, and 3327 g of a de-cobalt product containing 1720 g of oily aldehydes and butyl alcohols, 1400 g of solvent, 150 g of by-products, and not more than 0.0007% by weight of cobalt are sent for hydrogenation. After the content of cobalt on pumice reaches 15-17%, and the decoaltizer perekl is readied for cobaltisation and the cobalt carbonyls are washed out with a pentahexane fraction. The yield of the desired products — aldehyde oil and butyl alcohols — is 90% of the theory for converted propylene. 1 PRI me R 2. It is similar to Example 1, however, 100 tons of cobalt-naphthenate in hexane (1.5 g of Co) are used as a cobalt compound. The formation of cobalt carbonyls in a cobaltiser quantitatively occurs at 170 ° C and 200 atm of syngas for 5 yut. The steps of propylene hydroformylation and decobaltization are carried out as in Example 1. The yield of oily aldehydes and butyl alcohols is 1,450 g or 89% of the theory of the converted propylene (at 95% conversion of propylene;). The residual cobalt content in the decobalanced gyroformylation product is primed at 0.0001 ° C. .., Frozen. It is similar to Example 1, however, cobalt metal suspended in toll is used as a cobalt compound. The formation of cobalt carbonyls in a kobapichiser occurs quantitatively with and. 300 atm of synthesis gas per 180 min. The steps of hydroformylation of propylene and dekobaptizing are carried out as in Example 1. The yield of the target products — oily aldehydes and butyl alcohols — equals 1,460 g or 89.4% of the theory of the converted propylene (at 0.4% conversion of propylene. Residual cobalt content in dekobalized propylene hydroformylation product with 0.0002 wt.% Co. Example 4. (for comparison). Similar to example 1, however, a suspension of cobalt oxide in n-butanol and synthesis gas is supplied by a liquid pump to a 600 ml cobalt reactor filled with / 3 n At a pressure of 280 atm and a temperature of 155-100C, the formation of cobalt carbonyls occurs within 15 hours. During the carbonylation process, the reactor is blocked by a catalyst that has not been converted to carbonyls, thermal flashes are observed (up to 600 ° C). At the same time, part of the catalyst and solvent, as well as synthesis gas is discharged into the emergency line, part of the catalyst is deposited on pumice and is subsequently removed from the cobaltization reactor with great difficulty (over 6–8 days). Thus obtained homogeneous cobalt carbonyl solution in n-butanol, containing 2.5 g of cobalt, is sent to a hydroformylation reactor with a capacity of 2 liters. 1400 g of pentane-hexane fraction, 1000 g of nponiuieHa and 1500 l of synthesis gas fall here. At a pressure of 280 atm and 95% hydroformylation, the reaction proceeds only with a five-fold recirculation of the supplied gas-liquid mixture through the reactor. Under these conditions, 3337.6 g of catalysate hydroformylation are obtained, containing 1240 g of oily aldehydes, 310 g of butyl alcohols, 330 g of by-products, 1400 g of solvent, 50 g of propylene, 7.6 g of cobalt carbonyls (2.5 g of Co) . After separation from the gases, dehydration of the hydroformylation catalyzate is carried out under the conditions of Example 1. 3,300 g of de-cobalted hydroformylation product contain 1,490 g of aldehydes and butyl alcohols, 420 g of by-products and propylene, 1400 g of solvent. The yield of the target products - butyric aldehydes and butyl alcohols per converted propylene is 80%. PRI me R 5. 255.0 suspensions of basic cobalt carbonate in C – Cg alcohols containing 5.0 g of basic cobalt carbonate (2.5 g of Co, and 100 liters of synthesis gas (CO: H 1: y are fed by a liquid pump to the cobalt reactor with a capacity of 0 , 3 L. In the cobalt reactor at a pressure of 300 atm and a temperature of 2 hours, the formation of cobalt carbonyls occurs. A homogeneous solution of cobalt carbonyls containing 2.5 g of carbonyls (in terms of cobalt, is sent to a 2l capacity hydroformylation reactor. 2500 g fraction of olefins Cg- - Cj and 1750 l of synthesis gas. At 130s and pressure 300 atm hydroformylation reaction occurs. 3547.5 g of reaction products containing 7.5 g of cobalt carbonyls (2.5 g of Co, 2680.0 g of aldehydes C – Cg, 306 g of alcohols Cg – Cg, 250.0 g of olefins Cj – Cy and 304.0 g of by-products, cooled in a refrigerator and separated into SED from dissolved gases and subjected to decalbalization at 170 ° C and a hydrogen pressure of 250 atm in a 2-liter debaltiser filled with pure pumice. Cobalt metal is deposited on pumice, and 3540.0 g of a de-cobalt product containing 2986 g of aldehydes and C-Cg alcohols and 554.0 g of by-products and unreacted C-C7 olefins and 0.0005% by weight of Co are sent for hydrogenation . After the cobalt content on the pumice stone reaches l / 20%, the debaltizer is switched to cobaltization and the cobalt carbonyls are washed out.

fraction olefins Cg - Su. The yield of the target aldehydes and alcohols C Cg is 90% of the theory on converted olefins.

Example It is similar to Example 5, however, as a cobalt compound, 255.0 g of a suspension of basic cobalt carbonate (2.5 g of Co) in alcohol C and 100 liters of synthesis gas are used. 257.5 g of a homogeneous solution of cobalt carbonyls in alcohol C 9 and 2500 g of n-octene and 2000 liters of synthesis gas are fed to the hydroformylation reactor at a pressure of 200 atm. The hydroformylation product is separated from the excess gases in the SVD and is treated with hydrogen at a pressure of 200 atm in a dekobaltiser filled with pure pumice. This gives 3420.0 g of a de-balanced product containing 2787 g of aldehydes and C alcohols, 250 g of unreacted n-octene, 292 g of by-products, and not more than 0.0005 May,% Co. The decobaltism is switched to a cobaltiser when the content of cobalt on pumice stone reaches not less than 17.0 wt.% (Counting on cobalt) and the cobalt carbonyls are washed off with n-octene. ,

the yield of aldehydes and alcohols CQ is 90% of the theory for the converted n-octene.

Claims (1)

1. Regulations for the design of production of butyl alcohols according to the triad scheme. L., VNIINEFtekhim, 1969 C prototype).