KR20110116629A - Method for producing aldehyde by hydroformylation of olefin - Google Patents

Abstract

The present invention relates to a process for preparing aldehydes by hydroformylation of olefins, specifically to continuously reacting carbon monoxide and hydrogen with an olefinically unsaturated compound in the presence of a catalyst and separating one or more of the reaction products from others. A method for producing an aldehyde in a continuous hydroformylation process, the method comprising discharging water and at least some aldehyde compounds from the separation zone in the process as a mixed vapor stream and supplying some or all of them to the outside of the separation zone in the vapor state. do. According to the present invention, it is possible to improve the operating efficiency of the vaporizer by reducing the water content in the vaporizer corresponding to the separation region.

Description

Process for production of aldehydes by hydroformylation of olefins {A process for production of aldehyde by hidroformyl of olefin}

The present invention relates to a process for producing aldehydes by hydroformylation of olefins, and more particularly, to a vaporizer by effectively discharging a mixed vapor stream containing aldehyde and water in the reaction product produced by hydroformylation to the outside of the separation zone. It relates to a method of improving the efficiency of the.

Hydroformylation reaction, commonly known as OXO reaction, is a linear increase in the number of carbon atoms in an olefin due to the reaction of various olefins and syngas (CO / H ₂ ) in the presence of metal catalysts and ligands. linear, normal) and branched (iso) aldehydes are produced. The oxo reaction was first discovered by Otto Roelen of Germany in 1938, and as of 2001, around 8.4 million tonnes of various aldehydes (including alcohol derivatives) are produced and consumed through the oxo process worldwide ( SRI report , November 2002, 682. 700 A).

Specifically, the olefins react with syngas (CO / H ₂ ) in the presence of a catalyst to produce normal-aldehydes and iso-aldehydes. After the reaction, products such as aldehydes, unconverted olefins, catalyst mixture solutions and other reaction byproducts are present. This reaction mixture is sent to a separation system to separate the aldehyde and other low boiling materials and catalyst mixture solution. The separated catalyst mixed solution is circulated to the reaction system, the unconverted olefins and syngas in the aldehyde and other low boilers are circulated to the reaction system, and the aldehyde is separated through the normal purification process and the normal- and iso-aldehyde, respectively. Normal-aldehyde is introduced into the aldol condensation reactor to produce aldehydes having an increased carbon number by condensation and dehydration, and then transferred to a hydrogenation reactor, whereby alcohol is produced by hydrogenation. The reactant at the outlet of the hydrogenation reactor produces an alcohol product after separation.

As such a hydroformylation process, generally an olefinically unsaturated compound is continuously reacted with carbon monoxide and hydrogen in the presence of a catalyst, and a reaction product containing the catalyst and aldehyde product discharged from the reactor is fed to a catalyst separation process to separate the aldehyde product. A liquid circulation type hydroformylation process that is then circulated back to the reactor; After the olefinically unsaturated compound is continuously reacted with carbon monoxide and hydrogen in the presence of a catalyst, and a reaction product containing aldehyde product, unreacted olefinically unsaturated compound and by-products discharged from the reactor is fed to the separator to separate the aldehyde product, Fixed catalyst type hydroformylation processes are known which recycle the residue to the reactor.

In the hydroformylation process, the separation process of the aldehyde and the catalyst mixture solution is attached as a whole process flow diagram shown in FIGS. 1 and 2 and a partial enlarged view of the separation region.

In addition, some water is present in the hydroformylation reaction system. This is because the condensation dehydration reaction occurs as a side reaction in the hydroformylation reaction system to form water as a by-product, as well as contains a mixed gas of hydrogen and carbon monoxide as a raw material, and the water incorporated into the hydroformylation reaction system is not negligible. to be. The concentration of water to be contained in the synthesis gas varies depending on the type of the synthesis gas production process and the operating conditions. For example, methane or naphtha is subjected to steam reforming and aqueous gas reaction together with carbon dioxide, steam, and the like at a high temperature of about 800 ° C., and subjected to a partial oxidation reaction to obtain a decomposition gas containing hydrogen, carbon monoxide, carbon dioxide, steam, and the like. In this case, the decomposed gas is introduced into the absorption tower and subjected to the absorption of carbon dioxide by an alkanolamine or hot aqueous potassium carbonate solution (hereinafter referred to as the 'decarbonation process') to obtain a pure synthetic gas, which is obtained The purified synthesis gas contains saturated water vapor under the working pressure and temperature conditions of the absorption tower in the decarbonation process, so that even if most of the water is removed by subsequent compression and cooling condensation, 0.2 to 0.7% by volume of water As it is usually carried as water vapor, the moisture is incorporated into the hydroformylation reaction system. In addition, in the catalyst separation and recovery process, the catalyst-containing solution (hereinafter referred to as 'catalyst liquid') may be subjected to a contact process with water such as water washing, and then circulated for use in the hydroformylation reaction. And the catalyst liquid contains at least nearly saturated solubility water, so that when the catalyst liquid is directly supplied to the hydroformylation process, the water is conveyed to the process.

In addition, the reaction mixture after the reaction of the olefin and syngas (CO / H ₂ ) in the presence of the catalyst mixture solution flows into the vaporizer. At this time, aldehydes, unconverted olefins, and the like, which are reaction products present in the reaction mixture, are low boiling point materials. It is removed from the furnace and part is circulated to the reaction system, and part is recovered to the target material after purification.

The catalyst mixture solution separated from the vaporizer is circulated to the reactor with a high boiling point material, in which the transition metals and ligands are decomposed by aldehydes having high boiling point (aldehydes having 6 or more carbon atoms) or in the presence of water. Degradation of the activity of the catalyst and the decomposition of the ligand has a problem of lowering the efficiency of the reaction by reducing the function of the circulating catalyst.

Accordingly, the present inventors continued to solve the above problems, and as a result, in the continuous hydroformylation process, some or all aldehyde products and water are discharged as mixed vapor streams from the separation zone of the hydroformylation process, and the steam type is maintained as it is. The present invention has been accomplished by discovering that the water concentration in the separation zone can be efficiently and economically reduced when it is supplied and treated outside the separation zone.

That is, an object of the present invention is to reduce the water concentration in the separation zone and to effectively discharge the aldehyde product in the continuous hydroformylation process using a rhodium phosphine-based or rhodium phosphite-based complex as a catalyst to improve the efficiency of the vaporizer and to increase the aldehyde efficiency. It is to provide a method for efficiently manufacturing.

In order to solve the above problems, a method for producing an aldehyde by hydroformylation reaction from the olefin of the present invention,

In the presence of a catalyst of metal elements and organophosphorus compounds belonging to Groups 8 to 10, carbon monoxide and hydrogen and the olefinically unsaturated compound are continuously reacted, and at least one component is continuously separated from the reaction product, wherein a part of the separation zone is used. The first step in which the aldehyde product and the water are discharged as a mixed vapor stream; And

And a second step in which part or all of the mixed vapor stream is supplied to the outside of the separation region as it is.

In addition, the method for producing an aldehyde by hydroformylation reaction from the olefin of the present invention,

At least a rhodium phosphine-based or rhodium phosphite-based complex catalyst obtained by a continuous hydroformylation reaction of an olefinically unsaturated compound with carbon monoxide and hydrogen in the presence of a catalyst of metal elements and organophosphorus compounds belonging to groups 8 to 10, and A first step of withdrawing the reaction product containing the aldehyde product from the reactor and feeding it to the vaporizer;

A second step of discharging some or all of the aldehyde product and water from the top of the vaporizer as a mixed vapor stream;

A third step of discharging the mixed vapor stream out of the separation zone as it is in the vapor type; And

The liquid phase from the bottom of the vaporizer is a fourth step of performing a catalyst separation process to separate and recover the aldehyde product and then circulating in the reactor as a reaction medium.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

According to a conventional hydroformylation process, some or all of the reaction products containing unreacted olefinically unsaturated compounds, aldehyde products and water are discharged as mixed vapor streams containing unreacted olefinically unsaturated compound gases and the like in the reaction process. Thereafter, the resultant is cooled by a condenser or the like to form a condensate from some water together with the unreacted olefin and the aldehyde product, and the part of the condensate is returned to the reaction process to improve the conversion rate of the olefin. It can be a competitive enough approach .

That is, in the process of the present invention, by separating some or all of the aldehyde product and water from the separation zone during the process as a mixed vapor stream, some or all of the mixed vapor stream is supplied to the outside of the separation zone in the steam type or as it is, It is possible to reduce the water concentration in the region and to inhibit degradation of the organophosphorus compound ligand in the separation region. The separation zone referred to in the present invention means a zone for separating gaseous aldehyde products and means a process including a vaporizer, a gas liquid separator and a catalyst separation process. Thus, in the present invention, the aldehyde product and water from the vapor phase of the reactor vent gas, gas liquid separator or the like can be supplied to the outside of the separation zone as it is in the vapor type.

Specifically, the continuous hydroformylation process in the present invention is a liquid circulation type in which a reaction product containing at least a catalyst and an aldehyde product discharged from the reactor is fed to a catalyst separation reaction to separate the aldehyde product and then circulated to the reactor. It is preferred that this is a hydroformylation process.

The continuous hydroformylation process is a fixed catalyst type continuous hydroform that separates the aldehyde product by supplying a reaction product containing an aldehyde product, an unreacted olefinically unsaturated compound, and a by-product discharged from the reactor by gas stripping or the like to a separation process. It may be a densification process.

In general, the hydroformylation process of the present invention employs a continuous reactor such as that shown in FIG. 1 to remove olefinically unsaturated compounds in the presence of a catalyst of metal elements and organophosphorus compounds belonging to groups 8-10. It is not particularly limited as long as it continuously reacts with hydrogen and carbon monoxide and then separates one or more components from the reaction product. As the type of the reactor, a stirring tank type, bubble column type, tubular type, gas stripping type or the like can be used.

As the olefinically unsaturated compound to which the hydroformylation reaction of the present invention is applied, preferably any α-olefin or internal olefins such as linear olefinically unsaturated compounds and branched olefinically unsaturated compounds generally used are used.

Specific examples include α-olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-tridecene, 1-tetradecene, 1- Pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 2-butene, 2-methylpropene, 2-pentene, 2-hexene, 2-heptene, 2-ethylhexene, 2-octene, styrene, 3-phenyl-1-propene, 1,4-hexadiene, 1,7-octadiene, 3-cyclohexyl-1-butene, allyl acetate, allyl butyrate, Methyl methacrylate, vinyl methyl ether, vinyl ethyl ether, allyl ethyl ether, n-propyl-7-octenoate, 3-butenenitrile, 5-hexenamide, 4-methylstyrene, 4-isopropylstyrene Especially preferred are propylene, 1-butene, 2-butene, 1-hexene, 1-octane, 1-dodecene and 1-tetradecene.

In the hydroformylation reaction of the present invention, catalysts of metal elements and organophosphorus compounds belonging to groups 8 to 10 are used. Specifically, the metal elements belonging to Groups 8 to 10 can use one or more selected from the group consisting of ruthenium, rhodium, iridium, nickel, palladium, and platinum, and particularly preferably rhodium.

As the rhodium source, rhodium complexes such as acetylacetonatorodium and [Rh (COD) (OAc)] ₂ , organic salts such as rhodium acetate, inorganic salts such as rhodium nitrate and oxides such as rhodium oxide are used. Here, COD represents cyclooctadiene and Ac represents an acetyl group.

Although such a rhodium source may be directly supplied to the hydroformylation process, a rhodium complex catalyst prepared in advance by reacting carbon monoxide, hydrogen, and organophosphorus compounds in a solvent under high temperature and high pressure conditions outside the hydroformylation process may be added to the hydroformylation process. Can supply

In addition, as the organophosphorus compound, a phosphine-based or phosphite-based compound having a performance as a single-site ligand or a multi-site ligand and easily decomposed in the presence of water may be used. Specifically, trivalent phosphite as a ligand Bis (3,6,8-tri-t-butyl-2-naphthyl) phenyl phosphite, bis (3,6,8-tri-t-butyl-2-naphthyl) (4-biphenyl) as a compound Phosphite or neopentyl (2,4,6-t-butyl-phenyl) phosphite and ethylene (2,4,6-t-butyl-phenyl) phosphite and the like can be used, in particular triphenyl phosphite desirable.

In addition, specific examples of the phosphine compound include triphenylphosphine, tri-o-tolylphosphine, 1-naphthyldiphenylphosphine, 4-methoxyphenyldiphenylphosphine, tris (2,4,6 Triaryl type single seat phosphines, such as-trimethoxyphenyl) phosphine, tris (3, 5- diphenylphenyl) phosphine, and 4-dimethylaminophenyl di-2- naphthyl phosphine; Diphenyl-n-propylphosphine, n-octadecyldiphenylphosphine, di (3-t-butyl-2-naphthyl) methylphosphine, isopropyl-2-naphthyl-p-tolylphosphine, 2 Single seat phosphine of the diaryl monoalkyl type, such as ethylhexyldi (4-fluorophenyl) phosphine; Dimethylphenylphosphine, diethyl-4-methoxyphenylphosphine, di-n-octylphenylphosphine, tert-butyl-n-octyl-3,5-dimethylphenylphosphine, diisopropyl- Monoaryldialkyl type single-dented phosphines such as 2-naphthylphosphine and isobutyl-n-pentyl-4-acetylphenylphosphine; Trimethylphosphine, triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, tri-n-octadecylphosphine, n-octadecyldimethylphosphine, Diethyl-n-octylphosphine, ethylmethyl-n-propylphosphine, tri-2-ethoxyethylphosphine, isobutyl neopentyl-n-hexylphosphine, tri-2-ethylhexylphosphine, tribenzyl Phosphine, trineopentylphosphine, triisopropylphosphine, tri-t-butylphosphine, tri-2-butylphosphine, di-n-hexyl-1,1-dimethylpropylphosphine, 3-phenylpropyl Single alkyl phosphine of trialkyl type, such as di-t- butylphosphine and 2-butyl- n-propyl-3, 3- dimethoxypropyl phosphine, is mentioned.

Among the above specific examples, the most preferred single-dented phosphine is trimethylphosphine, triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, tri-n- Octadecylphosphine, n-octadecyldimethylphosphine, diethyl-n-octylphosphine, ethylmethyl-n-propylphosphine. As the phosphine compound, phosphine having the ability as a bidentate ligand or a polydentate ligand can also be used. Moreover, these organophosphorus compounds can also be used in combination.

In general, the solvent used for preparing the catalyst may be selected from the reaction solvents to be described later, but need not necessarily be the same as the reaction solvent. The preparation of the catalyst is generally carried out under a pressure of from normal pressure to 100 kg / cm ² G and a temperature condition of from normal temperature to 150 ° C.

In the hydroformylation process of the present invention, the organic phosphorus compound may be used in excess and exist as a ligand liberated in the hydroformylation process. For example, the phosphine compound or the phosphite compound may be used in an amount of 1 molar equivalent or more relative to the metal elements belonging to Groups 8 to 10 present in the reaction medium. It may be used in an amount of about 100 molar equivalents or more relative to the metal elements belonging to Groups 8 to 10 present in the reaction medium. As used herein, the reaction medium refers to a liquid in a reactor containing a solvent, a catalyst, a liberated ligand, an olefinically unsaturated compound, an aldehyde product, and the like.

Generally, the total amount of phosphine ligands or phosphite ligands coordinated (complexed) or free (non-complexed) or belonging to metal elements belonging to Groups 8-10 present in the reaction medium (phosphine compounds or phosphates) The content of pit compound) is generally about 1 to 500 moles, preferably 1 to 100 moles per mole of metal element. In addition, to maintain the amount of phosphine compound or phosphite compound in the reaction medium, phosphine ligands or phosphite ligands may be added to the reaction medium by any method. Moreover, homogeneous ligands may be used as coordination ligands or free ligands of the metal element phosphine or phosphite based catalysts, but individual ligands may be used if necessary, and mixtures of two or more different ligands may be used.

The amount of catalyst present in the reaction medium of the hydroformylation process of the present invention may be such that a sufficient reaction rate is obtained. The concentration of the metal element in the reaction medium is generally 1 to 1,000 ppm, preferably 10 to 500 ppm, more preferably 25 to 350 ppm.

In the hydroformylation reaction of the present invention, the use of a solvent is not essential, but an organic solvent such as toluene, or an olefinically unsaturated compound as a raw material may be used, and a mixture of two or more may be used. In general, it is desirable to reuse high boiling aldehyde condensation by-products (hereinafter referred to as 'high boiling product') and / or aldehyde products formed in the hydroformylation reaction process. For example, even when any primary solvent is used at the start of the continuous process, the primary solvent generally becomes an aldehyde product and a high boiling point product due to the nature of the continuous process.

If desired, the high boiling product may preferentially be preformed in the hydroformylation reaction process. The amount of solvent used is not critical to the present invention, but may be an amount sufficient to maintain the desired specific metal concentration in a given process and the solvent to serve as the reaction medium.

In general, the solvent may be from about 5% to about 95% by weight based on the total weight of the reaction medium. For the hydroformylation reaction conditions of the present invention, the hydroformylation process is preferably a sum of hydrogen, carbon monoxide and olefinically unsaturated compounds of less than 100 kg / cm ² G, more preferably less than 50 kg / cm ² G. It is carried out under gas pressure. The minimum total gas pressure is limited by the amount of reaction raw material required to achieve the initial reaction rate.

In addition, in the hydroformylation reaction of the present invention, the partial pressure of carbon monoxide is preferably 0.1 to 100 kg / cm ² , more preferably 0.3 to 2.0 kg / cm ² ; The partial pressure of hydrogen is preferably 0.1 to 100 kg / cm ² , more preferably 1 to 8 kg / cm ² . In general, the molar ratio (H ₂ : CO) of hydrogen to carbon monoxide gas is 1:10 to 100: 1, more preferably 1:10 to 10: 1.

In addition, the reaction is generally carried out at a temperature of 30 ° C to 120 ° C, preferably 40 ° C to 100 ° C, more preferably 50 ° C to 90 ° C. Even when the reaction temperature exceeds 120 ° C., the yield is not greatly enhanced and the catalyst activity may decrease, which is not preferable.

As the manner of the hydroformylation process of the present invention, a conventionally known manner can be used. For example, a liquid circulation type hydroformylation process may be employed in which a reaction product containing at least a catalyst and an aldehyde product exiting the reactor is fed to a catalyst separation process to separate the aldehyde product and then circulate the catalyst liquid into the reactor. Can be.

The liquid circulation type continuous hydroformylation process includes various embodiments and is not particularly limited but generally consists of at least a reaction process and a catalyst separation process. Preferably, it comprises at least a reaction step, a catalyst separation step, and a recovery step of the catalyst and unreacted olefins. The catalyst separation process and the recovery process of the catalyst and the unreacted olefin may be installed in the above order or in the reverse order.

The catalyst separation process is a process of separating the aldehyde product from the catalyst liquid. As separation means, any separation operation and apparatus such as distillation, evaporation, gas stripping, gas absorption, and extraction can be selected. Generally, a distillation column is used to distill out the aldehyde component from the column top, and the catalyst liquid flows out of the column bottom. Furthermore, for the recovery process of unreacted olefins, any means and apparatus may be used, but a countercurrent contact tower is generally used. Gas liquid separators and the like are suitably provided between the respective devices.

In addition to the catalyst separation process and the recovery of unreacted raw materials, a catalyst regeneration process, a purification process, such as a tower of aldehyde products, and the like may be included. In addition, the reaction product may contain, in addition to the desired aldehyde product, unreacted raw materials, solvents, medium boiling point or high boiling point byproducts, and the like. A process for separating the compound may be provided by any means.

As one example of a particular embodiment of the liquid circulation type hydroformylation process, in a continuous hydroformylation process in which carbon monoxide and hydrogen are continuously reacted with an olefinically unsaturated compound in the presence of a catalyst and continuously separating one or more components from the reaction product. A process for producing an aldehyde, wherein at least a part of the aldehyde product and water are discharged from the separation zone as a mixed vapor stream in the process, and some or all of them are supplied as it is out of the separation zone to reduce the water concentration in the separation zone. Liquid circulation type hydroformylation processes may be used.

In this case, the outside of the separation zone refers to a process after the mixed vapor stream is discharged as it is, and is supplied to a heat exchanger or to a catalyst separation tower or a catalyst recovery tower.

In such a case, it is preferable that some or all of the mixed vapor stream containing some or all of the aldehyde product and water discharged from the separation zone is discharged as it is and then fed to the heat exchanger.

Moreover, as another example of a specific embodiment of the liquid circulation type hydroformylation process, at least rhodium phosphate, obtained by the continuous hydroformylation reaction of an olefinically unsaturated compound with carbon monoxide and hydrogen in the presence of a rhodium phosphine-based or rhodium phosphite-based complex catalyst The reaction product containing the fin or rhodium phosphite complex catalyst and the aldehyde product is discharged from the reactor and fed to the vaporizer, and after vaporization, the liquid phase is subjected to the separation and recovery of the aldehyde product in the catalyst separation process, which is then reacted as a reaction medium. An aldehyde manufacturing method in a liquid circulation type hydroformylation process circulated in a process, the process comprising: discharging some or all of the aldehyde product and water from the top of the vaporizer in the process as a mixed vapor stream, and leaving the mixed vapor stream as it is. By Lee area discharged to the outside, there is a process of reducing the moisture concentration in the isolation region may be used.

In this case, it is preferable to discharge some or all of the mixed vapor stream containing some or all of the aldehyde product and water discharged from the upper part of the vaporizer as it is, and then supply it to the heat exchanger. Alternatively, some or all of the mixed vapor stream containing some or all of the aldehyde product and the water discharged from the upper part of the vaporizer may be discharged as it is, and then supplied to the catalyst recovery tower or the catalyst separation tower.

The catalyst recovery tower or the catalyst separation tower is not limited thereto, and a cyclone device type effective for catalyst separation may be used.

In addition, purification processes such as rectification towers of aldehyde products may be provided. The amount of aldehyde contained in the reaction medium and the high boiling product generated in the reaction process is generally 0.6 or more, preferably 1 or more, in terms of the weight ratio of aldehyde / high boiling product. If the ratio of aldehyde is high, the amount of gas used for stripping may be small. Thus, the above operation can make the equipment compact and economical.

In the present invention, the amount of water contained in the mixed vapor to be discharged from the separation zone is at least 30%, preferably at least 40% of the total amount of water to be formed in the reactor and to be supplied to the reactor. It is also desired to supply to the outside of the separation zone an amount of at least 30%, preferably at least 40%, of the moisture contained in the mixed vapors exiting from the separation zone. Further, the amount of water supplied outside the separation zone is at least 30%, preferably at least 34% of the total amount of water supplied to the reactor and water formed in the reactor.

Specific embodiments of the process within the present invention are described below with reference to the process flow diagram of FIG. 1 and the partial enlarged view of FIG. 3. In Fig. 3, reference numerals 5, 11, 14, 17 and 19 denote a vaporizer, a catalyst separation tower, a catalyst recovery tower and a gas liquid separator, respectively.

In the embodiment of FIG. 3, the reaction product liquid containing the aldehyde product, catalyst, water, solvent, and the like is introduced into vaporizer 5 via line 4, followed by evacuation of the gaseous aldehyde product from the top of vaporizer 5 via line 20. It is supplied to the heat exchanger 17 or to the catalyst separation tower 11 or the catalyst recovery tower 14 described later.

On the other hand, the residual liquid in the vaporizer 5 is transferred to the catalyst separation tower 11 via line 10 to discharge the catalyst through line 12 and the residual gas is introduced into the catalyst recovery tower 14 via line 13; The recovered catalyst is recycled to catalyst separation column 11 via line 15.

Further, the gas discharged from the tower of the catalyst recovery tower 14 is passed through the heat exchanger 17 via line 16 and supplied to the gas / liquid separator 19 via line 18. The catalyst separated in the gas / liquid separator 19 is circulated through line 21 to catalyst recovery tower 14 or through line 22 to catalyst separation tower 11, so that only the aldehyde product is discharged through line 6.

As a result, the moisture in the separation zone is easily removed during the process, which not only reduces the water concentration in the separation zone but also improves the vaporizer efficiency.

According to the present invention, there is provided a process for inhibiting degradation of a ligand in a separation region in a continuous hydroformylation process, in particular a 30% reduction in water concentration in the separation region that causes ligand degradation, and hydroformylation using a catalyst. By inhibiting ligand degradation in the reaction, aldehydes can be produced efficiently and economically since it does not degrade the quality of the catalyst circulated to the hydroformylation reactor.

1 is a flow diagram of an overall process representing an embodiment of the method of the present invention.
FIG. 2 is a partially enlarged view illustrating an isolation region according to the prior art of the entire process of FIG. 1.
3 is a partially enlarged view showing a separation area according to the present invention in the overall process of FIG.

Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded.

Example

1 and 3, the hydroformylation reaction of propylene was performed. The reaction was carried out in the presence of a rhodium bisphosphite based complex catalyst (Rh concentration: 500 mg / l, P / Rh (molar ratio) = 8).

Propylene was continuously fed via line 1 to a 100 m ³ continuous stirred reactor (CSTR) 2 and circulated with the catalyst liquid in an amount of 11,000 kg / hr. In addition, syngas containing 4.0 wt.% Moisture (H ₂ / CO = 1.0) was fed and circulated through reactor 3 into reactor 2.

The reactor was maintained at 89 ° C. and a total pressure of 18 kg / cm ² , and the supply of propylene and synthesis gas was adjusted to maintain the pressure of the reactor at 18 kg / cm ² . As a result, the amount of propylene supplied was 16,600 kg / hr, and the amount of syngas supplied was 11,800 kg / hr.

The reaction product liquid containing aldehyde product, catalyst, water, solvent and the like produced in CSTR reactor 2 was introduced via line 4 to vaporizer 5, and the gaseous aldehyde product was discharged from the top of vaporizer 5 to heat via line 20. Feed to exchanger 17.

Subsequently, the residual liquid in vaporizer 5 was transferred to catalyst separation tower 11 via line 10, then the catalyst was discharged via line 12 and then recycled to the reactor and residual gas was introduced into catalyst recovery tower 14 via line 13. At this time, the recovered catalyst was recycled to the catalyst separation column 11 via line 15.

In addition, the top off-gas of the catalyst recovery tower 14 was passed through the heat exchanger 17 via line 16 to the gas / liquid separator 19 through line 18. The catalyst separated in the gas / liquid separator 19 was circulated through line 21 to catalyst recovery tower 14 or through line 22 to catalyst separation tower 11, thus obtaining aldehyde product alone via line 6.

The moisture concentration at the outlet of vaporizer 5 during this reaction was 1.6% by weight. At this time, the moisture concentration in the vaporizer | carburetor 5 was 1.0 weight%. From this result, the total amount of the high boiling point product / ligand obtained by the following formula was 6% by weight.

Scheme 1

High boiling product / ligand total (% by weight) = moisture concentration at the vaporizer outlet—water concentration in the vaporizer

Comparative example

1 and 2, hydroformylation of propylene was carried out. That is, the same operation and reaction conditions as in Example were used except that the gaseous aldehyde product was not discharged directly to the heat exchanger 17 on the vaporizer 5 tower. At this time, the moisture concentration in the vaporizer was 1.5% by weight. From this result, the total amount of the high boiling point product / ligand obtained by the chemical formula was 5% by weight.

In other words, according to the method of the embodiment according to the present invention (6% by weight), it was confirmed that the resulting yield improved compared to the comparative example (5% by weight) according to the conventional method that does not supply the mixed vapor stream to the vaporizer as it is. .

1, 3, 4, 6, 7, 10, 12, 13, 15, 16, 18, 20, 21, 22: line
2: hydroformylation reactor
5: separator (carburetor)
8: hydrogenation reactor
11: catalytic separation tower
14: catalyst recovery tower
17: heat exchanger
19: Gas / Liquid Separator

Claims (11)

In the presence of a catalyst of metal elements and organophosphorus compounds belonging to Groups 8 to 10, carbon monoxide and hydrogen and the olefinically unsaturated compound are continuously reacted, and at least one component is continuously separated from the reaction product, wherein a part of the separation zone is used. The first step in which the aldehyde product and the water are discharged as a mixed vapor stream; And
A second step in which part or all of the mixed vapor stream is supplied to the outside of the separation zone as it is in the vapor type;
Process for producing aldehydes by hydroformylation of olefins.
The method of claim 1,
The second step is to supply a mixed vapor stream to the aldehyde separation process outside the separation zone to circulate the catalyst solution remaining after separation of the aldehyde product to the reactor;
Process for producing aldehydes by hydroformylation of olefins.
The method of claim 1,
Wherein the second step is to discharge the mixed steam as it is steam type and supplying to the heat exchanger;
Process for producing aldehydes by hydroformylation of olefins.
At least a rhodium phosphine-based or rhodium phosphite-based complex catalyst obtained by a continuous hydroformylation reaction of an olefinically unsaturated compound with carbon monoxide and hydrogen in the presence of a catalyst of metal elements and organophosphorus compounds belonging to groups 8 to 10, and A first step of withdrawing the reaction product containing the aldehyde product from the reactor and feeding it to the vaporizer;
A second step of discharging some or all of the aldehyde product and water from the top of the vaporizer as a mixed vapor stream;
A third step of discharging the mixed vapor stream out of the separation zone as it is in the vapor type; And
The liquid phase from the bottom of the vaporizer comprises a fourth step of performing a catalyst separation process to separate and recover the aldehyde product and then circulating in the reactor as a reaction medium;
Process for producing aldehydes by hydroformylation of olefins.
The method of claim 4, wherein
Wherein the third step is to discharge the mixed steam as it is steam type and supplying to the heat exchanger;
Process for producing aldehydes by hydroformylation of olefins.
The method of claim 4, wherein
The third step is the step of supplying the mixed vapor stream as a steam type to the catalyst separation tower or catalyst recovery tower;
Process for producing aldehydes by hydroformylation of olefins.
The method according to claim 1 or 4,
The amount of high boiling point products and ligands formed in the reaction process and the aldehyde contained in the reaction medium in the reactor is characterized in that more than 6% of the total amount
Process for producing aldehydes by hydroformylation of olefins.
The method according to claim 1 or 4,
The reaction temperature of the olefinically unsaturated compound is characterized in that in the range of 30 ℃ to 120 ℃
Process for producing aldehydes by hydroformylation of olefins.
The method according to claim 1 or 4,
The olefinically unsaturated compound is ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 2-butene, 2-methylpropene, 2-pentene, 2-hexene, 2-heptene, 2-ethyl Hexene, 2-octene, styrene, 3-phenyl-1-propene, 1,4-hexadiene, 1,7-octadiene, 3-cyclohexyl-1-butene, allyl acetate, allyl butyrate, methyl methacryl Those selected from the group consisting of latex, vinyl methyl ether, vinyl ethyl ether, allyl ethyl ether, n-propyl-7-octenoate, 3-butenenitrile, 5-hexenamide, 4-methylstyrene, 4-isopropylstyrene Characterized
Process for producing aldehydes by hydroformylation of olefins.
The method according to claim 1 or 4,
The metal element belonging to the group 8 to 10 is at least one selected from the group consisting of ruthenium, rhodium, iridium, nickel, palladium and platinum
Process for producing aldehydes by hydroformylation of olefins.
The method according to claim 1 or 4,
The organophosphorus compound is characterized in that the phosphine coordination compound or phosphite coordination compound
Process for producing aldehydes by hydroformylation of olefins.

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