Hydroformylation process stabilisation

FIELD: chemistry.

SUBSTANCE: present invention relates to versions of a method of stabilising the hydroformylation process and a device for realising the said method. One version of the method involves reaction of one or more reagents, carbon monoxide and hydrogen in the presence of a hydroformylation catalyst to obtain an exhaust gas stream and a reaction product stream which contains one or more products, in which the method described above is realised at such partial pressure of carbon monoxide that, the rate of reaction increases when partial pressure of carbon monoxide falls, and falls when partial pressure of carbon monoxide increases; and in which the following steps of the process for stabilising the rate of reaction, total pressure, speed of the exhaust gas stream, reaction temperature or combinations thereof are carried out, process steps including at least one of the following process control schemata, selected from: Scheme A: (a1) setting a given total pressure; (a2) determination of total pressure and determination of the difference between the measured total pressure and the given total pressure; and (a3) based on the pressure difference measured at step (a2), manipulation of the stream of incoming gas which contains carbon monoxide in order to balance the measured total pressure to virtually the given total pressure; and Scheme B: (b1) setting a given speed of the exhaust gas stream; (b2) determination of the speed of the exhaust gas stream and determination of the difference between the measured speed of the exhaust gas stream and the given speed of the exhaust gas stream; and (b3) manipulation of the speed of incoming gas which contains carbon monoxide based on the difference in the speed of the exhaust gas stream measured at step (b2) in order to equalise the determined speed of the exhaust gas stream virtually with the given speed of the exhaust gas stream.

EFFECT: design of an efficient method of stabilising the hydroformylation process.

26 cl, 2 tbl, 20 dwg, 7 ex

This patent application claims the benefit of provisional patent application U.S. No. 60/598032 from August 2, 2004.

The LEVEL of TECHNOLOGY

The invention relates to a method of stabilizing process hydroformylation for rapidly, often extreme, changes or cyclical speed of the reaction and/or process parameters, such as total pressure, velocity exhaust flow process and temperature.

In the art it is well known that aldehydes can be easily obtained by the interaction of olefinic compounds with carbon monoxide and hydrogen in the presence of a complex ORGANOMETALLIC catalyst containing organophosphorus ligand, and that the preferred processes are continuous hydroformylation and recycling of the solution containing the complex catalyst based on a metal of group VIII and organophosphine ligand. The preferred metal of group VIII is rhodium. These are the examples in the patents US 4148830, US 4717775 and US 4769498. The aldehydes obtained by such methods have a wide range of applications, for example, as intermediates for the hydrogenation to aliphatic alcohols, for amination to aliphatic amines, aliphatic oxidation to acids, and aldol condensation to obtain a plasticized the ditch.

In this area it is considered that normal or unbranched aldehydes in General are more valuable than their ISO - or branched isomers. In addition, it is known that the ratio of normal to branched isomer depends on the partial pressure of carbon monoxide, and usually lower partial pressure of carbon monoxide yield products with higher normal connection to branching. The complex rhodium-organophosphine ligand, catalytic processes, shows highly desirable with respect to the normal isomers of branched to.

Despite the usefulness of such processes hydroformylation catalyzed by metal-complex catalysts containing organophosphorus ligands and, in particular, organophosphine ligands, stabilization of the catalyst is of great interest. The destruction of the catalyst or the loss of catalytic activity of the expensive rhodium catalysts result in undesirable side reactions can be detrimental to the desired aldehyde. Similarly, the destruction of organophosphorus ligand in hydroformylating may result in the formation of poisonous catalyst substances (for example, organophosphites), or inhibitors, or phosphoric acid by-products that can reduce catalyticallyactive rhodium catalyst. Production costs aldehyde products increases due to the lower performance of the catalyst.

In the processes of hydroformylating the main reason that causes the destruction organophosphine ligand and deactivation of the rhodium complex catalyst of such a ligand is due to hydrolytic instability organophosphine ligand. All organophosphate in varying degrees, sensitive to hydrolysis, and the hydrolysis rate of in General depends on the nature of organophosphites. In General, the bigger the spatial environment of the phosphorus atom, the slower can be the rate of hydrolysis. All such hydrolysis, however, has consistently given as the product of acidic phosphorus compounds, which are then themselves catalyze the hydrolysis reaction. Hydrolysis of the tertiary organophosphites, for example, gives toponomy acidic fluids, which, in turn, is hydrolyzed to phosphoric acid. Other adverse reactions of hydrolysis give strong allegedely. Indeed, even the most suitable sterically blocked organobentonite ligands, which are less susceptible to hydrolysis, can interact with the aldehyde products with the formation of toxic organophosphates that are not only catalytic inhibitors, but also significantly bol is e sensitive to hydrolysis and form as by-products of allegedely, for example, hydroxyethylphosphonate acid, as shown in patents US 5288918 and US 5364950. Hydrolysis organophosphine ligands can be considered as autocatalytic, and if it is not to influence the catalytic system of continuous liquid recirculated process hydroformylation will become more and more acidic from organophosphates and/or phosphoric acid by-products, linking the metal catalyst in the form inhibitory complexes. As a consequence, the activity of complex ORGANOMETALLIC catalysts containing organophosphine ligands decreases as the concentration inhibition of the complex increases. Thus, it is possible that under appropriate conditions the accumulation of unacceptable quantities of such toxic and inhibitory materials causes destruction organophosphine ligand, transforming catalyst hydroformylation ineffective (deactivated) and the resulting loss of valuable rhodium, for example, when precipitation and/or deposition on the walls of the reactor.

In this area, as shown in patent US 5763679, it is known that decontamination of complex ORGANOMETALLIC catalysts containing organophosphorus ligands caused any abscopal or toxic phosphorus compounds, may be directed in reverse with the horon or reduced by the process of hydroformylation in the region of the reaction, where the reaction rate of hydroformylation is negative or in reverse order by carbon monoxide. As this patent application, the reaction rate of hydroformylation, which is negative or has a reverse order in carbon monoxide, relates to the field of hydroformylation, in which the reaction rate of hydroformylation increases with decreasing partial pressure of carbon monoxide and decreases with increasing partial pressure of carbon monoxide. In contrast, the process of hydroformylation, which has a positive order in carbon monoxide, found in cases where the reaction rate of hydroformylation increases with increasing partial pressure of carbon monoxide and decreases with decreasing partial pressure of carbon monoxide. (Positive and reverse speed curve is illustrated further in this patent application.) With the increased partial pressure of carbon monoxide in the negative region or reverse curve speed carbon monoxide is more effectively coordinated and more effectively compete for the metal complex ORGANOMETALLIC catalyst containing organophosphorus ligand, compared to inhibited the forming or toxic phosphorus compounds. Thus, the concentration of free of inhibitory or toxic phosphorus compounds in the environment reaction hydroformylation increases, so inhibiting or toxic phosphorus compounds can easily be either hydrolyzed with water and/or weak connections. The final fragments of hydrolysis for the benefit of the process can be easily removed from the reaction medium.

Increased partial pressure of carbon monoxide in the negative region or reverse speed curve provides additional desirable benefits, which can reduce the loss of efficiency of olefin-hydrogenation. Increased partial pressure of carbon monoxide leads to increased catalytic activity and reducing the loss of effectiveness of alkanes. Moreover, it is also possible to reduce the undesirable isomerization of olefins.

Work near the peak of the curve responsiveness hydroformylation in the field of reverse partial pressure of carbon monoxide may have additional desirable benefits, in which the ratio of normal to branched isomeric product may increase, while the increase of catalytic efficiency and/or speed of reaction of hydroformylation.

However, the process of hydroformylation in neg the school region or reverse curve speed monoxide shows problems usually unnoticeable when working in the field of positive order of a speed curve. Namely, when the process of hydroformylation is in the field of positive order with respect to carbon monoxide, by increasing the speed of reaction is used for more of carbon monoxide, which consequently leads to a decrease in the partial pressure of carbon monoxide. The decrease in partial pressure of carbon monoxide (or concentration) slows the reaction rate so that it becomes possible to control the reaction temperature, partial pressure of carbon monoxide partial pressure of hydrogen and the total pressure. Accordingly, the process can be easily operated when the process is performed in the field of positive order with respect to carbon monoxide, but, as noted previously in the patent application, there is a constant decrease of catalytic activity due to the accumulation of inhibitory and toxic phosphate by-products and their metal-ligand complexes. Conversely, when the process is in the field of negative order in carbon monoxide, by increasing the speed of the reaction is carbon monoxide; but the ultimate low partial pressure of carbon monoxide further increases the reaction rate of hydroformylation. Moreover, the increase of the reaction rate bude is further amplified, due to thermal effect of the reaction, since the reaction of hydroformylation are exothermic. When the periodic process of recirculating closed system works in a way that can lead essentially to the rapid and complete depletion of a limited quantity of the reagent and the termination process hydroformylation. In continuous operation under negative about the responsiveness hydroformylation tends to be cyclical, as well as the total pressure, exhaust flow and/or temperature. Used here, the term "cyclic" refers to periodic and often critical changes in process parameters (e.g., speed of reaction, partial and/or total pressure, the exhaust flow and/or temperature). Cycle parameters adversely affects the stability. Thus, when working in the field of negative order of a speed curve, despite the fact that the negative impact of inhibiting phosphate by-products may be reversible or reduced, by itself, the process of hydroformylating becomes more difficult to stabilize and control. Moreover, in General, work in the negative procedure should be carried out under high partial pressure of carbon monoxide, far enough away from the peak of the curve depend on the particular speed hydroformylation from the partial pressure of carbon monoxide. Adversely that the work is far from the peak in the field of it negative order in carbon monoxide provides a low ratio of normal to branched isomer of the aldehyde product.

Patent US 5763679 discloses a method of controlling the cycle and maintain a constant speed of reaction and process parameters when working in the field of negative order in carbon monoxide. The open method implies that the management of the difference between the temperature of the reaction product outlet and a cooling coil temperature to less than 25°C. Adversely fact that in this method of the prior art requires a large and expensive heat exchangers. Also, because of the large heat load reaction fluid, the time constant of the reset, when an unexpected random temperature variation, can be unacceptably large.

EP-B1-0589463 discloses a method of controlling the stability of processes hydroformylation by varying the flow rate of the incoming synthesis gas or velocity exhaust stream to maintain a predetermined constant partial pressure of carbon monoxide in the process of hydroformylation. The reference does not provide information relative to the smooth variation of the partial pressure of carbon monoxide and work in a negative area of the or region reverse curve speed hydroformylation by carbon monoxide. Adversely the fact that the presented method is not adapted accordingly for processes of hydroformylation using hydrolytic organophosphorus ligands and, therefore, it is preferable to operate in the negative region or reverse speed curve.

SU-A1-1527234 discloses a method of controlling the stability of processes hydroformylation by changing the flow rate of olefin reactant at a constant exhaust flow, when the process of hydroformylation in the positive region of the curve speed olefin. Adversely the fact that the presented method is not adapted accordingly for processes of hydroformylation using hydrolytic organophosphorus ligands and, therefore, it is preferable to operate in the negative region or reverse speed curve.

From the point of view of the foregoing, it would be desirable to devise an improved method of hydroformylation, which can easily manage sudden random changes and/or cyclical process parameters and provides stability when operating in the mode in which the speed of reaction of hydroformylation or negative has the reverse order in carbon monoxide. It is desirable, so is th improved process also would increase the lifetime of the catalyst by minimizing the negative effects of inhibitory or toxic phosphate by-products. Moreover, it is desirable that such an improved method would provide a high ratio of normal to branched isomeric product, at the same time providing higher productivity of the catalyst and/or reaction speed hydroformylation acceptable service life of the catalyst, acceptable stability of the reactor, and minimum problems with circularity. The process, which has all the above properties will have a higher commercial appeal.

The INVENTION

The present invention described in this patent application provides a new and improved method of hydroformylation, including the interaction of one or more reactants, carbon monoxide and hydrogen in the presence of a catalyst of hydroformylation to receive the stream of reaction products comprising one or more products in which the above process is carried out with the high partial pressure of carbon monoxide, the reaction rate increases with decreasing partial pressure of carbon monoxide and decreases with increasing partial pressure; and in which are held the following stage of the process for the stabilization of the reaction rate, total pressure, velocity exhaust stream, the reaction temperature, or a combination of, the stage of the process, include the s, at least one of the following schemes management process selected from:

Scheme:

(A1) setting a given total pressure;

(A2) determining the total pressure and determining the difference between the measured total pressure and a given total pressure and

(A3) based on the pressure difference, measured in stage (A2), the manipulation of the flow of incoming gas, including carbon monoxide, to align the measured total pressure in fact, up to a given total pressure; and

Schema:

(b1) establishing a preset speed exhaust flow;

(b2) determining the speed of exhaust flow and determining the difference between the measured speed of the exhaust flow and the set speed exhaust flow; and

(b3) on the basis of the difference in the speeds of the exhaust stream, measured at the stage (b2), the manipulation of the flow of incoming gas, including carbon monoxide, to align a certain speed exhaust flow effectively to the target speed of the gas exhaust stream.

In another aspect of this invention stage of the process (A1) to (A3), inclusive, and the stage of the process (b1) to (b3), inclusive, are all conducted in order to align the measured total pressure in fact, up to a given total pressure and align certain speed exhaust photocapacitance to a predetermined velocity exhaust stream.

The term "total pressure" should be related to the total pressure of the gas in the process. The term "manipulation" means any of the following words, including "variations", "regulation", "adapting" or "change".

A new way of hydroformylation of the present invention described in this patent application, to effectively manage unexpected random changes and/or cyclical process parameters and provides stability when operating in the mode in which the speed of reaction of hydroformylation is negative or has a reverse order in carbon monoxide, provided that the reaction rate decreases with increasing partial pressure of carbon monoxide, and the reaction rate increases with decreasing partial pressure of carbon monoxide. In a new aspect, and unlike prior art, this invention takes into account the deviation or smooth change up and down the partial pressure of carbon monoxide, so that the speed of the reaction can be halted or speed up, depending on what is needed to stabilize the speed of reaction and process parameters. Favorably, the method of the present invention achieves this stability of the reaction and prevents and/or minimizes the cyclical nature of the process parameters in a simple and economy the Cesky effective manner by eliminating the need for large and expensive heat exchangers, used in the prior art. Moreover, compared with the prior art, the advantage of the method of the present invention is that it provides an improved and more rapid return to its original state after an unexpected random and extreme deviations. When stable operation in the negative region or reverse curve speed service life of the catalyst is increased by minimizing the negative impact of toxic or inhibitory by-products of phosphate ligands. As an additional advantage, the method of the present invention include the work in the field of reverse order at a partial pressure of carbon monoxide in the vicinity of the peak curve speed hydroformylation from the partial pressure of carbon monoxide (further illustrated in the patent application), which is for the benefit of the process provides higher responsiveness hydroformylation and/or productivity of the catalyst and higher with respect to the normal isomer to branched. There is no need to download excessive amounts of carbon monoxide in a process that is kinetically controlled. Managing kinetics, which leads to a higher reaction rate, is more prepact the tion, than currently existing methods of process control due to mass transfer. Primarily, the method of the present invention also provides for reduction of formation of alkanes and a decrease in the isomerization of olefins, which increases the efficient use of the olefin reactant. Finally, the method of the present invention provides a method of determining, for any selected organophosphine ligand, the optimal range of partial pressure of carbon monoxide within the field of reverse curve speed and provides a way of stable operation in this range.

In another aspect this invention is a novel device for the stabilization process of hydroformylation, including

the reactor includes a device for feeding one or more reactants; a device for feeding the synthesis gas; optionally, a device for supplying a secondary source of carbon monoxide; a feeding device of a solution of the catalyst; a device for removing reactive and inert gases; a device for extracting the reaction stream; a device for measuring the total gas pressure and the device for changing the speed of the gas exhaust flow of reactive and inert gases; and in which the device further includes at least one of the following structural diagrams,chosen from:

Design:

(A1) a device for determining the difference between the desired total gas pressure and the measured total gas pressure;

(A2) a device for generating a signal corresponding to the pressure difference;

(A3) a device for receiving a signal from (A2) and to determine and send a feedback signal to manipulate the flow rate of synthesis gas and/or secondary source of carbon monoxide to align the measured total pressure up to the specified total pressure; and

Design:

(b1) a device for determining the difference between the set speed exhaust flow and the measured speed of the exhaust flow;

(b2) a device for generating a signal corresponding to the difference of the velocities of the exhaust flow;

(b3) a device for receiving a signal from (b2) and to determine and send a feedback signal to manipulate the flow rate of synthesis gas and/or secondary source of carbon monoxide for aligning a measured speed exhaust flow to a predetermined velocity exhaust stream.

In an alternative embodiment of the present invention, the device may include all objects of a design with (A1) to (A3) inclusive and (b1) to (b3), inclusive.

Figure 1 illustrates a typical graph of the dependence of the reaction rate of hydroformylation pairs from the territorial pressure of carbon monoxide for hydroformylation of the olefin with carbon monoxide and hydrogen in the presence of a complex ORGANOMETALLIC catalyst, containing organophosphine ligand.

Figure 2 illustrates a plot of the total pressure of the reactor velocity of the incoming synthesis gas at constant speed exhaust flow. This graph also illustrates the method of selecting the minimum and maximum speeds of the initial stream of carbon monoxide and an incoming stream of synthesis gas in accordance with this invention.

Figure 3 illustrates the reactor hydroformylation continuous action with devices to control the flow of olefin, synthesis gas and exhaust flow, the reactor is designed to process, shown in figure 2.

Figure 4 illustrates the reactor hydroformylation continuous action with devices control the flow of olefin and exhaust flow, and in accordance with the present invention the control devices of the incoming primary and secondary streams of synthesis gas to control the total pressure of the reactor.

Figure 5 illustrates a graph of the dependence of the reaction rate of hydroformylation the duration of hydroformylation in the reactor is designed as in figure 4.

6 illustrates a graph of partial pressure on the duration of hydroformylation in the reactor is designed as in figure 4.

7 illustrates a traditional reactor HYDROFORM the financing of continuous operation with control devices olefin streams and the incoming synthesis gas and, in order to compare with the reactor in figure 4, the control device total pressure of the reactor on-line gas exhaust stream.

Fig illustrates a graph of the dependence of the reaction rate of hydroformylation the duration of hydroformylation in the reactor is designed as a 7.

Fig.9 illustrates a graph of the dependence of the rate of exhaust flow from the duration of hydroformylation in the reactor is designed as a 7.

Figure 10 illustrates a graph of the dependence of the reaction rate of hydroformylation velocity of the incoming synthesis gas to conduct hydroformylation in the reactor is designed as a 7.

11 illustrates a graph of the dependence of the reaction rate of hydroformylation the duration of hydroformylation in the reactor with a modified design as in figure 4, in accordance with this invention.

Fig illustrates a graph of partial pressure on the duration of hydroformylation in the reactor with a modified design as in figure 4, in accordance with this invention.

Fig illustrates the reactor hydroformylation continuous operation with control devices olefin streams and the incoming synthesis gas, the control device exhaust flow and managing your pressure, according to this invention, through the supply line of the secondary source of carbon monoxide.

Fig illustrates a graph of the dependence of the reaction rate of hydroformylation on the duration of holding hydroformylation in a reactor designed as Fig.

Fig illustrates a graph of partial pressure on the duration of hydroformylation in a reactor designed as Fig.

Fig illustrates the reactor hydroformylation continuous action with devices that control the flow of the olefin, carbon monoxide and the flow of incoming synthesis gas, and for comparison with reactor Fig, a device that manages the total pressure through the line sensor exhaust flow and control valve pressure.

Fig illustrates a graph of the dependence of the reaction rate of hydroformylation the duration of hydroformylation in a reactor designed as Fig.

Fig illustrates a graph of partial pressure on the duration of hydroformylation in a reactor designed as Fig.

Fig illustrates the reactor hydroformylation continuous operation with control devices olefin streams and the incoming synthesis gas and, in accordance with the invention, the device for controlling the total pressure using the regulator protystavlena is in line exhaust flow and device managing secondary incoming stream of synthesis gas, to control the rate of exhaust flow reactor.

Fig illustrates a graph of the dependence of the reaction rate of hydroformylation from the partial pressure of carbon monoxide for real propylene hydroformylation with carbon monoxide and hydrogen in the presence of specific complex catalysts having the composition of the metal-organophosphine ligand.

DETAILED description of the INVENTION

The invention described in this patent application relates to a new and improved process hydroformylation, which provides the advantages of working in a negative region or reverse curve speed hydroformylation regarding carbon monoxide when unexpected decrease accidental changes, cycles, and other manifestations of instability in the process parameters such as reaction rate, total pressure, velocity exhaust stream and the reaction temperature. An important aspect of this new and improved invention inherent in the use of carbon monoxide as a gas, the overwhelming response, and the deviation parameter to store a predetermined total pressure and/or a given predetermined speed exhaust flow from the reactor hydroformer the tion, as described in detail in this patent application.

As an illustration of the problem that need to be addressed with reference to figure 1, which depicts the dependence of the reaction rate of hydroformylation from the partial pressure of carbon monoxide in the consideration of theoretical model of hydroformylating olefinic compounds in the presence of carbon monoxide and hydrogen, and a complex ORGANOMETALLIC catalyst hydroformylation containing organophosphine ligand. In fact inverted U-shaped curve is typical of such processes and, in General, covers two areas: (1) the positive manner in which the rate of reaction of hydroformylation increases with increasing partial pressure of carbon monoxide and which decreases with decreasing partial pressure of carbon monoxide; and (2) the area of negative order in which the reaction rate decreases with increasing partial pressure of carbon monoxide and increases with decreasing partial pressure of carbon monoxide. Namely, figure 1 illustrates that the initial reaction rate increases with increasing partial pressure of CO, but after reaching a maximum, the rate sharply decreases with increasing partial pressure. Occurs radical changes which begins from positive to negative slope of the curve, since the reaction rate goes from positive to negative or inverse order in carbon monoxide. As noted earlier, the process of hydroformylating mainly conducted in the field of negative order curve speed hydroformylation, except that the catalyst is destroyed due to the formation of inhibitory or toxic phosphate by-products.

Although the work in the field of negative order curve speed hydroformylation offers proven benefits, the regulation of the operating parameters in this area curve speed is, to some extent, much more complex and problematic, so getting speeds reaction to the negative of the order of a speed curve, as shown in the hypothetical curve 1 is difficult. To demonstrate the difficulty, reference is made to figure 2, which depicts a plot of total pressure velocity of the incoming synthesis gas at constant speed exhaust flow for propylene hydroformylation (reaction conditions: molar ratio of N₂:WITH a, 1,04:1; the ow of propylene, 304 g/h; 75°C; constant overall speed of the exhaust flow, 32,67 normal liters per hour (NLC)). The graph shows a gradual decrease in the total pressure AP is sustained fashion 219 pounds per square inch (1510 kPa) at a flow of incoming synthesis gas from approximately 85,34 NLC to approximately 65 psi (448 kPa) at a flow rate of the incoming synthesis gas 215,77 NLC. Few outside of the value of this stream of incoming synthesis gas, when 220,60 NLC, the total pressure dramatically and disproportionately increases to over 370 psi (2551 MPa). The sharp increase in the pressure of the reaction indicates a sharp decrease of reaction rate and a concomitant sharp increase in the partial pressure of carbon monoxide and hydrogen, and also possibly drastic reduction in the reaction temperature. The loss of stability of the reaction occurs at this value of the stream of incoming synthesis gas, which has passed from a positive order in the area of negative order in carbon monoxide.

Such data, as presented above in this patent application, indicate that you need to control the process parameters, such as total pressure, temperature, speed exhaust flow and speed of reaction, when working in the field of a speed curve, namely negative order in carbon monoxide. The problem with the above patent application, can be removed easily and without any material costs when using the invention described in this patent application.

In one aspect the present invention provides a new and improved method of hydroformylation, including the interaction of one or more reactants, carbon monoxide, and in which oroda in the presence of a catalyst of hydroformylation for receiving the fluid reaction product, including one or more products in which the above process is carried out at a partial pressure of carbon monoxide, such that the reaction rate increases with decreasing partial pressure of carbon monoxide, and the reaction rate decreases with increasing partial pressure of carbon monoxide; and hosts the following stage of the process, in order to stabilize the reaction rate, total pressure, velocity exhaust flow, temperature or a combination stage of the process, including at least one of the following schemes management process selected from:

Scheme:

(A1) set the total pressure;

(A2) determining the total pressure and determining the difference between the measured total pressure and a specified total pressure; and

(A3) based on the pressure difference, measured in stage (A2), the manipulation of feed gas stream containing carbon monoxide, to align the measured total pressure, in fact, up to a given total pressure; and

Schema:

(b1) setting a preset speed exhaust flow;

(b2) determining the velocity of the incoming stream and determining the difference between the measured speed of the exhaust flow and the set speed exhaust flow; and

(b3) on the basis of the difference of the velocities of the exhaust flow, ISM is indigenous to the stage (b2), manipulating the flow rate of gas stream containing carbon monoxide, to align the measured speed exhaust flow essentially to a predetermined velocity exhaust stream.

In an alternative embodiment, the present invention stage of the process (A1) to (A3), inclusive, and the stage of the process (b1) to (b3), inclusive, all are made to align the total pressure, in fact, up to a given total pressure, and to adjust the measured speed of the exhaust flow, in fact, to a predetermined velocity exhaust stream.

The term "total pressure" should be used to denote the total pressure of the gas phase process comprising the sum of partial pressures of carbon monoxide, hydrogen, olefin, the reaction products and any inert gas related products and impurities of the gas phase.

In the preferred embodiment, this invention provides a new and improved method of hydroformylation, including the interaction of one or more olefinic compounds with carbon monoxide and hydrogen in the presence of a complex ORGANOMETALLIC catalyst containing organophosphorus ligand, and, as one option, the free organophosphorus ligand, to obtain a stream of the reaction product, the content is a first one or more aldehydes, in which the above process hydroformylation is carried out at a partial pressure of carbon monoxide, such that the reaction rate increases with increasing partial pressure of carbon monoxide, and the reaction rate decreases with decreasing partial pressure of carbon monoxide; and in which the following stages are carried out to maintain the equilibrium partial pressure of carbon monoxide in order to stabilize the reaction rate, total pressure, velocity exhaust stream, the reaction temperature, or a combination, stage of the process, including at least one of the following schemes management process selected from:

Scheme:

(A1) set the total pressure;

(A2) determining the total pressure and determining the difference between the measured total pressure and a specified total pressure; and

(A3) based on the pressure difference, measured in stage (A2), the control flow of the gas stream containing carbon monoxide, to align the measured total pressure, in fact, up to a given total pressure; and

Schema:

(b1) setting a preset speed exhaust flow;

(b2) determining the speed of exhaust flow and determining the difference between the measured speed of the exhaust flow and the set speed exhaust flow; and

(b3) n is the difference of the velocities of the exhaust stream, measured at the stage (b2), the speed control of the feed gas stream containing carbon monoxide, to align the measured speed exhaust flow, in fact, to a predetermined velocity exhaust stream.

In another aspect of the preferred option implementation stage of the process (A1) to (A3), inclusive, and the stage of the process (b1) to (b3), inclusive, all are made to align the total pressure, in fact, up to a given total pressure and in order to align the measured speed of the exhaust flow, in fact, to a predetermined velocity exhaust stream.

In a more preferred embodiment, this invention provides a new and improved method of hydroformylation, including interaction in the reaction zone one or more olefinic unsaturated compounds with carbon monoxide and hydrogen in the presence of a complex ORGANOMETALLIC catalyst containing organophosphorus ligand, and, as one option, the free organophosphorus ligand, to obtain the fluid reaction product containing one or more aldehydes, and split into at least one corresponding zone of one or more aldehydes from a complex ORGANOMETALLIC catalyst containing organophilicity leagues is nd, and, as an option, free organophosphine ligand; the improvement comprising conducting the process of hydroformylation at a partial pressure of carbon monoxide, such that the reaction rate increases with increasing partial pressure of carbon monoxide, and the reaction rate decreases with decreasing partial pressure of carbon monoxide; and in which the following stages are carried out to preserve the equilibrium partial pressure of carbon monoxide in order to stabilize the reaction rate, total pressure, velocity exhaust stream, the reaction temperature, or a combination; stage process that includes at least one of the following schemes management process selected from:

Scheme:

(A1) set the total pressure;

(A2) determining the total pressure and determining the difference between the measured total pressure and a specified total pressure; and

(A3) based on the pressure difference, measured in stage (A2), the control flow of the gas stream containing carbon monoxide, to align the measured total pressure, in fact, up to a given total pressure; and

Schema:

(b1) setting a preset speed exhaust flow;

(b2) determining the speed of exhaust flow and determining the difference between the measured speed of the exhaust is about flow and constant speed exhaust flow; and

(b3) on the basis of the difference of the velocities of the exhaust stream, measured at the stage (b2), the speed control of the feed gas stream containing carbon monoxide, to align the measured speed exhaust flow, in fact, to a predetermined velocity exhaust stream.

In this preferred embodiment, as an alternative, stage of the process (A1) to (A3), inclusive, and the stage of the process (b1) to (b3), inclusive, all carried out to equalize the total pressure, in fact, up to a given total pressure and to align the measured speed of the exhaust flow, in fact, to a predetermined velocity exhaust stream.

In another aspect this invention is a novel device for the stabilization process of hydroformylation, including:

the reactor, containing a device for feeding one or more reactants; a device for feeding the synthesis gas; it is possible that the device for supplying a secondary source of carbon monoxide; a feeding device of a catalytic solution; a device for removing a reactive or inert gas; a device for extracting the reaction stream; a device for measuring the total gas pressure and a device for measuring the speed of the exhaust flow of the reaction and inert gases; the device further comprising, p is at least one of the following structural diagrams, chosen from:

Design:

(A1) a device for determining the difference between the desired total gas pressure and the measured total gas pressure;

(A2) a device for generating a signal corresponding to the pressure difference;

(A3) a device for receiving a signal from (A2) and to determine and send a feedback signal to control the flow rate of synthesis gas and/or secondary source of carbon monoxide to align the measured total pressure up to the specified total pressure; and

Design:

(b1) a device for determining the difference between the set speed exhaust flow and the measured speed of the exhaust flow;

(b2) a device for generating a signal corresponding to the difference of the velocities of the exhaust flow;

(b3) a device for receiving a signal from (b2) and to determine and send a feedback signal to control the flow rate of synthesis gas and/or secondary source of carbon monoxide for aligning a measured speed exhaust flow to a predetermined velocity exhaust stream.

In an alternative embodiment of the present invention, the device may include all objects constructive scheme with (A1) to (A3) inclusive and (b1) to (b3), inclusive, previously mentioned in the patent application. Specially the Ista in this area should pay attention to the standard references on the development of control systems for describing device generating signals corresponding to the difference of the parameters of the device, receiving signals, and a device that determines and outputs the signals to control the process parameters.

The method of the invention, described earlier in this patent application provides a method of stabilization, including the reduction or elimination of unexpected random, extreme changes in the process parameters and the reduction and regulation of the cycles of reaction parameters such as reaction speed hydroformylation, total pressure, velocity exhaust flow, the temperature of the reactor, or combination thereof, when the process in sensitive reversible area or region of negative order curve speed hydroformylation relative to carbon monoxide. In one preferred embodiment of the present invention to allow easier management of response and stability are achieved preferably at a constant preset speed exhaust flow regulation flow rate of carbon monoxide containing the incoming gas in order to maintain a given total pressure of the reaction. In another preferred embodiment, the control response and stability are achieved preferably at a constant predetermined total pressure by regulating the flow rate monoxide is gerada, containing the incoming gas in order to maintain the speed of exhaust flow. Accordingly, the method of the present invention allows the partial pressure of carbon monoxide to smoothly increase and decrease in response to deviations of the total pressure and/or velocity of the exhaust stream resulting from the speed deviation response of hydroformylation, thus stabilizing the process from random and unexpected extreme deviations of process parameters or their periodicity. Since in practice the method of the present invention is the manipulation of the gas flow and the total pressure, this method is not blocked by the slow reaction of the manipulation of the liquid phase or slow response determination of partial pressure characteristic of the gas component. Therefore, the reaction of this direct method is much faster than the reaction of methods already known in this technical field.

The process of hydroformylation of the present invention may be asymmetric or not asymmetric, it is preferable not asymmetric way; the process of hydroformylation can be done with any continuous or properities organization of the process; the process of hydroformylation, if desired, may include any conventional recycling kataliticheski the first liquid and/or gas and/or extraction. As mentioned in this patent application, it is assumed that the term "hydroformylation" includes all existing asymmetric and not asymmetric processes hydroformylation relating to the conversion of one or more substituted or unsubstituted olefinic compounds or reaction mixtures containing one or more olefinic compounds, usually in the presence of a catalyst of hydroformylation to one or more substituted or unsubstituted aldehyde or reaction mixtures containing one or more substituted or unsubstituted aldehyde. Any catalyst hydroformylation known in this field, can accordingly be used in the process of the present invention. Preferably, the catalyst hydroformylation contains a complex ORGANOMETALLIC catalyst containing organophosphorus ligand, where the ligand includes, for example, triorganotin, organophosphine ligand or a combination of both. More preferably, the catalyst hydroformylation contains a complex ORGANOMETALLIC catalyst containing organophosphine ligand. Visual complex ORGANOMETALLIC catalyst containing organophosphine ligand, kataliziruetsya processes hydroformylation that could be applied in this invention, VK is uchet, for example, the processes described in patents US№№ 4148830; 4593127; 4769498; 4717775; 4774361; 4885401; 5264616; 5288918; 5360938; 5364950 and 5491266; the disclosure of which is presented in this patent application by reference. Accordingly, the technological technique for performing hydroformylation used in this patent application may correspond to any technological methods known and described in the field. The preferred methods are those that include ways of hydroformylation recycle catalytic fluid, as described in patents US№№ 4668651, 4774361, 5102505, 5110990, 5288918, 5874639 and 6090987; and extracting methods hydroformylation, as described in patents US№№ 5932772, 5952530, 6294700, 6303829, 6303830, 6307109 and 6307110; the disclosure of which is presented in this patent application by reference.

In General, such catalyzed liquid ways of hydroformylation include getting aldehydes interaction of olefinic unsaturated compounds with carbon monoxide and hydrogen in the presence of a complex ORGANOMETALLIC catalyst containing organophosphorus ligand in the liquid phase, which may also contain an organic solvent for the catalyst and ligand. Preferably, the free organophosphorus ligand present in the liquid phase. Under "free phosphororganic is Kim ligand" refers to organophosphorus ligand, which is not bound in the complex formed a connection or bond) with a metal, for example, the atom of the metal complex catalyst. In General, the process of hydroformylation may include a method of recycling, in which part of the liquid reaction fluid containing a catalyst and aldehyde product is removed from the reactor hydroformylation (which may have one reaction zone or more reaction zones connected, for example, sequentially), either continuously or periodically; and aldehyde product is separated and released from this portion by using the techniques described in this field; and then, after separation, the residue containing the catalyst metal is returned to the reaction zone, as disclosed, for example, in US patent No. 5288918. (If you are using multiple reaction zones connected in series, interactive olefin can be sent only in the first reaction zone; while the catalytic solution, the carbon monoxide and hydrogen can be routed to any of the reaction zones.) It is assumed that the term "reactive flow" or "flow of the reaction product further in this document implies, but does not limit, the reaction mixture comprising (a) a complex ORGANOMETALLIC catalyst containing a ligand, preferably an integrated metalloorg the practical catalyst, containing organophosphorus ligand, (b) aldehyde product formed in the reaction, (c) optionally free ligand, (d) optionally, unreacted reagents, including olefin, (e) an organic solubilizer for the above-mentioned ORGANOMETALLIC complex catalyst containing ligand, and above the free ligand, and (f) optionally, one or more inhibitory or toxic phosphate by-products formed during hydrolysis in the reaction stream. It should be understood that the reaction stream hydroformylation may and usually will contain the minimum number of additional ingredients, such as those that were either deliberately added or formed in situ during the process. Examples of such additional ingredients include gases: carbon monoxide and hydrogen, and in situ formed products, such as saturated hydrocarbons and/or unreacted samaritane olefins corresponding to the source of olefinic products, and/or high-boiling liquid by-products of aldol condensation, as well as other inert auxiliary solvents or hydrocarbon additives, if used.

As previously established, the object of the invention is the discovery that the deactivation of a complex ORGANOMETALLIC catalyst containing organophosphorus ligand, caused by the action of inhibitory or toxic by-products, can be turned in the opposite direction or at least reduced by the process of hydroformylation in the reaction region, where the reaction rate of hydroformylation has a negative or inverse order in carbon monoxide; and moreover, unexpected accidental changes or cyclical responsiveness hydroformylation, total pressure, velocity exhaust flow, temperature, or combinations thereof in the negative region or reverse curve, the response speed can be prevented and/or reduced smooth alignment of partial pressure to maintain a specified amount of the total pressure, or a preset speed exhaust flow, or both parameters.

The selection of the current target pressure is an important aspect of the present invention. In this regard, the option may influence the design of the reactor. It is preferable to use a reactor design, which provides a stationary work during data collection. The design of the reactor liquid hydroformylation continuous element recycling are presented in figure 3. Preferably, such a reactor equipped with a paddle stirrer (1), the axis of the stirrer (2), line feed olefin and mouth what Euston for flow control (3), line feed synthesis gas and a device for flow control (4), suction line and a device for controlling suction flow (5), General pressure sensor (6), the output line of the solution of the reaction products from the reactor (7) and the input line for supplying the recovered catalyst back to the reactor (8). Line feed synthesis gas usually ends bubbling device. It is possible that the reactor had one or more baffles (not shown in the figure), which divide the internal chamber of the reactor at several reaction zones. Typically, each partition is attached to the inner wall of the reactor and is located in the reactor perpendicular to the axis of the agitator; and each partition has a hole of sufficient size for the passage of the axis of the stirrer, and the reaction flux and gases. Usually each chamber or zone in a reactor formed by such walls, contains a stirrer, and bubbling device for gas circulation and mixing reaction flow in this chamber or zone.

To illustrate, the choice of working a given total pressure is discussed with reference to figure 2, using the device, designed as in figure 3. First you choose a number of process parameters, including special unsaturated olefinic compound or mixture of olefinic compounds, specialeducational of hydroformylation, preferably, the ORGANOMETALLIC complex catalyst containing organophosphorus ligand, any excess ligand, solvent, reaction temperature, the feed rate of the olefin and the molar ratio in the synthesis gas H₂CO. The initial feed rate of the synthesis gas is selected so that she stoichiometric ratio was less than the feed rate of the olefin, preferably less than 1/2 stoichiometric feed speed relative to the speed of the feed olefin. Also select the speed of the gas exhaust flow reactor. Usually all parameters are fixed except for the flow rate of the incoming synthesis gas and the total pressure.

On the basis of figure 2, the feed stream of synthesis gas, and after the reaction reaches a stationary regime is determined and recorded the total pressure. In the initial phase of this evaluation there is an excess of olefinic feedstock, and the reaction system is limited by the speed substochiometric feed synthesis gas. Thus, as the flow of incoming synthesis gas is increased at a fixed feed rate of the olefin (and because it is usually the initial reaction has a positive order monoxide), the total system pressure gradually decreases, because more carbon monoxide and hydrogen is available for saturation stech is hometree reaction hydroformylation. The total pressure continues to decrease until, until a point is reached in which the partial pressure of carbon monoxide is high enough to go into negative order curve speed. When reaching this point, the total pressure is suddenly and rapidly increasing, because each increase in the partial pressure of the added carbon monoxide slows down or inhibits the speed of hydroformylation. Desirable given total pressure selected from the range of values of total pressure, measured in negative order curve (figure 2, dramatically increasing positive slope with increasing flow of incoming synthesis gas and the partial pressure of CO).

After you select a given total pressure, as described above in this patent application, then in one embodiment of the present invention the actual process pressure of hydroformylation periodically or preferably continuously measured using a standard device for determining pressure and calculates the difference between the desired total pressure and the actual total pressure. After this, the stability of the reaction is achieved by regulating the flow rate of the incoming gas of carbon monoxide either up or down, to restore the measured pressure to a specified General is Alenia, preferably, to maintain the preset speed exhaust flow. (Definition given speed exhaust flow is described later in this patent application.) Thus, if the actual pressure is higher than specified, which implies a slight speed hydroformylation, the flow rate of the gas containing carbon monoxide, sharply down. If the measured pressure is lower than the preset pressure, which implies an unacceptably high rate of hydroformylation, the flow rate of the gas containing carbon monoxide increases.

The total pressure respectively measured by any traditional definition of pressure, which can be located on the supply line source synthesis gas immediately before entering the synthesis gas in the reactor or, alternatively, is located directly in the reactor, or on the suction line coming out of the reactor. The gas containing carbon monoxide, can be fed into the reactor in any way that meets the conditions under which the reaction is carried out in the field, namely, negative order in carbon monoxide and in which the total pressure is kept constant by regulating the flow rate of the gas containing carbon monoxide, preferably at a predetermined speed exhaust the sweat is CA. In one embodiment of the present invention, shown in figure 4, to control the pressure in the reactor is changed, the initial flow of the incoming synthesis gas (4). Especially desirable results are obtained by using the minimum of the initial gas stream containing carbon monoxide (i.e. synthesis gas) (4), and then align the total pressure to a predetermined pressure with the secondary feed gas containing carbon monoxide (9). In the above method works other process parameters such as feed rate of the reagent (for example, olefin), the composition of the reactants entering the reactor, the composition of the synthesis gas into the reactor, the liquid level, the mixing rate, the removal rate of the reaction stream, the speed of recycling of the catalyst solution, the temperature and velocity of exhaust flow, more preferably, to put on, in fact, constant values.

Another way, which uses primary and secondary incoming flows of carbon monoxide can be illustrated in figure 4, using the information obtained from the data shown in figure 2. In this way a given total pressure is chosen along the sharply increasing slope of the curve speed (e.g., figure 2, point 3). After that we select the minimum flow rate original is a high gas containing carbon monoxide, such as, approximately, the minimum flow rate of the incoming carbon monoxide corresponding to a given total pressure (figure 2, point 1, first crossing the curve of the total pressure with a straight line of a given total pressure). It is preferable to use a higher speed of the incoming stream of synthesis gas or carbon monoxide, to ensure that the system is not stabilized in the field of positive order of a speed curve. While working with the appropriate minimum speed of the initial stream of carbon monoxide, where the total pressure is less than the desired set pressure, secondary, usually increasing, the gas stream containing carbon monoxide (figure 4 (9)), fed into the reactor for smoothing the total pressure to the specified value. With the addition of carbon monoxide coming from the secondary flow, the total pressure will move even slower until, until it reaches the minimum point, as shown in figure 2. After the minimum, the reaction is in the range of a sharp slope, which has a negative order in carbon monoxide; however, the secondary stream of carbon monoxide, as shown in the structural diagram 4 (9), will act as a weakening agent in this area, thus providing a fast and thin the Board of the reaction. Thus, as the amount of carbon monoxide and increases the reaction rate, it is necessary to add additional carbon monoxide to lock and stabilize the reaction. Thus, as shown in figure 4, the feed of carbon monoxide and partial pressure are not permanent options, and smoothly change up and down to keep the total pressure as close as possible to the value of the specified total pressure. As shown in figure 2 (point 2), it is preferable that the maximum speed of the initial gas stream containing carbon monoxide, can be selected in the second point of intersection of the curve of the total pressure of the reactor with specified total pressure.

Preferably, the synthesis gas was used to provide the primary source of feed gas containing carbon monoxide. (See 4 (4).) A separate stream of pure carbon monoxide or gas containing carbon monoxide, for example, synthesis gas, can provide a secondary source of gas, debilitating reaction. (See 4 (9) or Fig (12).) Suitable gases containing carbon monoxide, include mixtures of carbon monoxide with hydrogen, synthesis gas, nitrogen, helium, argon and/or methane and their mixtures. A separate device to control the flow of gas can be provided for primary and secondary p the currents, in either case, when the secondary thread uses the synthesis gas as a gas containing carbon monoxide, a single flow meter may be used with appropriate control devices process.

In the above embodiment, regulating the amount of gas containing carbon monoxide, is fed into the reactor from a secondary source of carbon monoxide to control the total pressure at a predetermined specified value. Exhaust flow reactor can maintain constant, but measured and controlled independently, for example, through the flow aperture, a flow sensing devices for control, namely, a valve governing the flow rate through the flow meter diaphragm gas exhaust stream. The term "valve" should be attributed to any of the many devices by which the flow of gas, you can start to submit, stop, or regulate, usually using a movable part that opens, shuts, or partially overlaps one or more holes or passages, including, but not limited to, ball valve, valve with valve, needle valve type, a tapered valve (gate valve, throttle valve (butterfly valve), Poppet valve and Bolotnikova valve.

When the process as disclosed is of this patent application, to the extent that the ratio of hydrogen to incoming monoxide different from the stoichiometry of hydroformylation side and hydrogenation of olefins, excess gas and gaseous side products should be given to maintain the performance of the process. Otherwise, when a predetermined total pressure of the process, increasing the percentage of the total pressure of the process to be entirely undesirable or less desirable components. Quite similarly, impurities in the synthesis gas, including methane, carbon dioxide, nitrogen or other inert gases or inert gaseous components in the olefinic feedstock can accumulate and reduce the efficiency of the process. Such inclusion must also be removed through the exhaust line.

Thus, in another preferred embodiment of the present invention the stability of the reaction can be controlled using the device speed control exhaust flow (Fig). In this embodiment of the present invention the flow rate of the gas containing carbon monoxide entering the reactor (Fig (14)), is used to align the speed of exhaust flow reactor to a predetermined speed exhaust flow, preferably, while maintaining a given total pressure. Given shresthasexvideo flow is determined by means of flow control, coming out of the reactor (Fig(11)), and speed exhaust flow, to maximize the release of inert components such as hydrogen and gaseous impurities and minimizes the release of reactive olefin and possibly the synthesis gas. The standard technique of gas chromatography can be used successfully for the analysis of exhaust flow. Minimum of a given exhaust velocity is the speed at which remove the excess hydrogen and gaseous impurities, essentially at the speed at which they are introduced, certainly given that some inert gases, such as saturated hydrocarbons formed by the hydrogenation of olefin, or inert components included in the reactor with the olefin, there may also be dissolved in the catalyst solution. Set exhaust velocity is higher than the minimum speed, is also valid, but at the cost of reducing the effectiveness of the process. In accordance with the present invention, when the measured speed exhaust flow deviates from the specified speed exhaust flow, then varies the flow of incoming gas containing carbon monoxide, in order to align the measured speed exhaust flow back to the desired value of velocity exhaust stream. In practice the ICA, increase the speed of exhaust flow above the set speed exhaust flow leads to a reduction in the rate of feed gas containing carbon monoxide and the reduction of velocity of the exhaust flow below set speed exhaust flow leads to an increase in the rate of feed gas containing carbon monoxide. In this preferred embodiment, the present invention is preferable to be installed virtually constant values of other process parameters such as feed rate of the reagent (for example, olefin), the composition of the incoming reagent composition of the incoming synthesis gas, liquid level, the mixing rate, the removal rate of the reaction fluid, the speed of recycling of the catalyst solution, the temperature and total pressure.

Both the first and second preferred implementation of the present invention have several aspects in common. The minimum flow of incoming gas containing carbon monoxide is typically managed through the use of the original source of carbon monoxide and the use of pre-defined operating parameters, taken from the plot of total pressure on the rate of flow of the synthesis gas (figure 2). Total pressure (adjustable parameter 1) and the speed kazootoys the th flow reactor (adjustable option 2) individually or jointly operated at constant predetermined set values (2 adjustable parameter). Usually feature two devices to control (or equivalents; e.g., valves), one device in the supply line of the secondary gas containing carbon monoxide, and the other device on the suction line reactor (2 processed parameter). The main difference between the two variants of implementation of the present invention is that the first design is measured by the total pressure, while the second design is measured velocity exhaust stream. Either measurement is transmitted through the corresponding signalling device in the supply line of carbon monoxide, preferably, the supply line of the secondary monoxide, to align the total pressure to a predetermined value of pressure, or for leveling speed exhaust flow to a predetermined value of the speed of exhaust flow. Preferably, the adjustments are as close as possible to the specified pressure value and the set speed exhaust flow within the constraints of the design.

In the third preferred embodiment of the present invention combines aspects of the first and second preferred embodiments of the present invention. The total pressure and velocity exhaust flow reactor (2 controllable parameter) both are controlled by pre-defined is specified, when using two devices to control (namely, valves or equivalent), one device on the line feed gas containing carbon monoxide, and the device on the suction line reactor (2 manipulated parameter). Accordingly, the combined measurements are transmitted through the corresponding signalling device in the supply line of carbon monoxide, preferably, the secondary line of feed of carbon monoxide and lines exhaust flow reactor for smoothing the total pressure to a predetermined value of pressure and alignment speed exhaust flow to a predetermined velocity exhaust stream.

When the process of hydroformylation is carried out in a number of continuously operating the vessel-type reactor mixing, connected in series, the speed of exhaust flow and/or pressure in the reactor of one or more consecutive reactors can be used to determine the total velocity exhaust flow and/or pressure in the entire series of sequential reactors, and measurement(I) can then be transferred to the line of the incoming gas containing carbon monoxide (e.g., synthesis gas)in the first reactor or any other or combination of reactors to align the total pressure and/or velocity of the exhaust flow to the total number of reactors to a predetermined led the ranks the total pressure or the predetermined speed exhaust stream, or combinations thereof.

As another option, the portion of the total amount of gases being expelled from the reactor, with or without further separation and purification, can be returned back to the reactor as raw materials.

It was surprising that with the help of the method of this invention by the process of hydroformylation can be simply, economically and effectively manage in a negative region or reverse speed curve for carbon monoxide, where the ratio is highly desirable normal isomers to branched isomers and stability of ligands/catalysts improves, but where, on the contrary, until this discovery management process was challenging. Moreover, devices of the present invention it is possible to choose and to work in the field of optimal partial pressure of carbon monoxide in the field of reverse reaction curve speed. Preferably, the partial pressure of carbon monoxide are selected so as to achieve a reaction rate of hydroformylation at the maximum, or within 50 percent of the maximum (peak) speed of reaction, more preferably, 30% or within 30 percent of the maximum reaction rate and most preferably at 10% or within 10% of the peak reaction rate, as defined by the graph of the dependence of the reaction rate of hydroformylation from parts the social pressure of carbon monoxide.

About appropriate process conditions of hydroformylation, indicative of a complex ORGANOMETALLIC catalysts containing ligands employed in the process of hydroformylation of the present invention, as well as methods for their preparation are well known in this area and include those disclosed in the above reference patents. In General, such catalysts can be pre-formed or obtained in situ and to contain, in fact, the metal in complex combination, usually with organophosphorus ligand, preferably organophosphine ligand. I believe that carbon monoxide is also present and is linked in complex with the metal in the active samples, which may also contain hydrogen, and is directly connected with the metal.

Valid metals form ORGANOMETALLIC complexes with ligand, are the metals of groups 8, 9 and 10, selected from rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), Nickel (Ni), palladium (Pd), platinum (Pt), osmium (Os) and mixtures thereof, the preferred metals are rhodium, cobalt, iridium and ruthenium, more preferred is rhodium, cobalt and ruthenium, and the most preferred is rhodium. Other acceptable metals include the metals of groups 6, selected from chromium (Cr), molybdenum (Mo), tungsten (W) and mixtures thereof. Mixtures of metals GRU is p 6, 8, 9 and 10 can also be used in the present invention.

Preferred organophosphine ligands, which form an ORGANOMETALLIC complex with organophosphine ligand and free organophosphine ligand include mono-, di-, tri - and higher organophosphine ligands. Mixture of such ligands can be used, as needed, in comprehensive ORGANOMETALLIC catalyst containing organophosphine ligand and/or free ligand, and such mixtures may be the same or different.

The term "complex"as used in this patent application and in the claims, means a coordinated compound formed by combining one or more electron-rich molecules or atoms with one or more poor electrons by molecules or atoms. For example, organophosphine ligands used in this invention have two or more donor atoms of phosphorus, each of which has one available or unshared pair of electrons, which, in turn, can form a coordinated covalent bond independently or possibly in combination (e.g., via chelation) with the metal. Carbon monoxide may also be present and form a complex with the metal. The basic composition of a comprehensive rolled ATOR may also contain additional ligand, for example, hydrogen or an anion, satisfying focal points or nuclear charge of the metal. Illustrative additional ligands include, for example, halogen (Cl, Br, I), alkyl, aryl, substituted aryl, acyl, CF₃C₂F₅CN, (R₂)PO and RP(O)(OH)O (in which each R is the same or different and represents a substituted or unsubstituted hydrocarbon radical, for example alkyl or aryl), acetate, acetylacetonate, SO₄PF₄PF₆, NO₂, NO₃CH₃O, CH₂=CHCH₂CH₃CH=CHCH₂C₂H₅CN, CH₃CN, NH₃, pyridine, (C₂H₅)₃N, monoolefinic, diolefine and triolein, tetrahydrofuran, etc.

The number of available focal points on such metals are well known in this area. Thus, the catalyst samples can include a complex mixture of catalysts, in their Monomeric, dimeric form or shape with a large number of cores, which are preferably characterized by the fact that at least one molecule containing organophosphorus fragment forms a complex with one molecule of metal, such as rhodium. For example, it is assumed that the samples are the preferred catalysts, operating in response hydroformylation, can form a complex with carbon monoxide and hydrogen in addition to the organophosphorus ligand (is gandam) with regard to the use of carbon monoxide and hydrogen in the reaction of hydroformylation.

Preferred organophosphate, which can serve as a ligand of a complex ORGANOMETALLIC catalyst with organophosphine ligand and/or free ligand processes hydroformylation, and the fluid reaction products of the present invention may be achiral (optically inactive) or chiral (optically active) and is well known in this area. Preferred are the achiral organophosphate. Typical organophosphate contain two or more tertiary (trivalent) phosphorus atoms, and may include those that have the formula:

in which X is substituted or unsubstituted n-valent organic linking radical containing from 2 to 40 carbon atoms, each R¹is the same or different and denotes a bivalent organic radical containing from 4 to 40 carbon atoms, each R²is the same or different and denotes a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 24 carbon atoms, a and b may be the same or different, and each has a value from 0 to 6, provided that the sum a+b is equal to from 2 to 6 and n equals a+b. Of course it should be understood that when a has a value of 2 or more, each R¹the organic radical can be the same or different,and when b has a value of 1 or more, each R²the organic radical can be the same or different.

Typical n-valent (preferably bivalent) hydrocarbon linking radicals denoted by X, and typical bivalent organic radicals denoted by R¹earlier in the patent application, include both acyclic radicals and aromatic radicals, such as alkylene, alkylene-Q_m-alkylen, cycloalkyl, Allen, bizarre, arrenaline, Allen-(CH₂)_y-Q_m-(CH₂)_y-aralen radicals, etc. in which each y is the same or different and is 0 or 1. Q represents a bivalent linking group selected from-C(R³)₂-, -O-, -S-, -NR⁴-, -Si(R⁵)₂- and-CO-, in which each R³is the same or different and denotes hydrogen, an alkyl radical having from 1 to 12 carbon atoms, phenyl, tolyl and anisyl, R⁴denotes hydrogen or a substituted or unsubstituted monovalent hydrocarbon radical, e.g. alkyl radical having from 1 to 4 carbon atoms; each R⁵is the same or different and denotes a hydrogen or alkyl radical, and m has a value of 0 or 1. More preferred acyclic radicals denoted by X and R¹earlier in the patent application, are bivalent alkionovymi radicals, while more preferred is an aromatic radicals, denoted by X and R¹earlier in the patent application, are bivalent allenbyi and Basilashvili radicals, such as is presented in more detail in patents, for example, US№№ 4769498, 4774361, 4885401, 5179055, 5113022, 5202297, 5235113, 5264616, 5364950, 5874640, 5892119, 6090987 and 6294700 etc. which are included in the present patent application by reference. Typical preferred monovalent hydrocarbon radicals, marked each R²radical earlier in this patent application include alkyl and aromatic radicals.

Illustrative preferred organophosphate may include bisphosphate represented by the following formulas (II)to(IV):

in which each R¹, R²and X of formulas (II)-(IV) are as defined above in the text of the patent application for formula (I). Preferably each R¹and X denotes a bivalent hydrocarbon radical selected from alkylene, arylene, arylene-alkylene-arylene and bizarely, while R²radical denotes a monovalent hydrocarbon radical selected from alkyl or aryl radicals. Organophosphine ligands such formulas (II)-(IV) can be found described, for example, in US patents№№ 4668651, 4748261, 4769498, 4774361, 4885401, 5113022, 5179055, 5202297, 5235113, 5264616, 532996, 5364950 and 5391801, the consideration of which is included in the present patent application by reference.

Typical representatives of the more preferred classes of organobentonites are those represented by the formulas (V)to(VII):

in which Q, R¹, R², X, m and y are as defined above in the text of the patent application, and each Ar is the same or different and represents a substituted or unsubstituted aryl radical. More preferably X denotes a bivalent aryl-(CH₂)_y)-(Q)_m-(CH₂)_y-aryl radical, where each y individually has a value of 0 or 1, m is 0 or 1 and Q is-O-, -S - or-C(R³)₂in which each R³is the same or different and denotes hydrogen or a methyl radical. More preferably, each alkyl radical videopreteen R²groups can contain from 1 to 24 carbon atoms and each aryl radical videopreteen Ar, X, R¹and R²groups of the above formulas (V)-(VII) can contain from 6 to 18 carbon atoms, these radicals can be the same or different, while the preferred alkylene radicals X may contain from 2 to 18 carbon atoms, and preferably is e alkylene radicals R ¹can contain from 5 to 18 carbon atoms. In addition, it is preferable that the bivalent Ar bivalent radicals and aryl radicals X of the above formula were phenylanaline radicals, in which the linking group denoted by -(CH₂)_y-(Q)_m-(CH₂)_y-formed connection with the above phenylanaline radicals in ortho-position to the oxygen atoms of these formulas, to in turn connect phenylenebis radicals with their phosphorus atom in the formula. It is also preferable to any alternative radical, when present in such filinovich radicals, formed a link in the para and/or ortho-position filinovich radicals relative to the oxygen atom to bind this substituted phenylenebis radical with its phosphorus atom.

Moreover, if necessary, any given organoplastic in the above formulas (I)to(VII) may be ion postitem, which may contain one or more ionic components selected from the group consisting of: -SO₃M, in which M represents inorganic or organic cation, -PO₃M, in which M represents inorganic or organic cation, N(R⁶)₃X¹in which each R⁶is the same or different and is a hydrocarbon radical containing from 1 to 30 carbon atoms, for example, alkyl is hydrated, aryl, alkalinty, Aracely and cycloalkenyl radicals, and X¹denotes an inorganic or organic anion, -CO₂M, in which M represents inorganic or organic cation, as described, for example, in US patents No. 5059710, 5113022, 5114473 and 5449653, the consideration of which is included in the present patent application by reference. Thus, if necessary, such organophosphine ligands can contain from 1 to 3 such ionic components, although it is preferable that only one ion component was replaced on any given aryl component in organophosphites the ligand when the ligand contains more than one ion component. As the available counterions, M and X¹for anionic component of the ionic organophosphites, there can be mentioned hydrogen (a proton), the cations of alkali and alkaline earth metals such as lithium, sodium, potassium, cesium, rubidium, calcium, barium, magnesium and strontium, ammonium cation and Quaternary ammonium cations, cations of phosphonium, cations Arcania and cations imine. Suitable radicals anions include, for example, sulfate, carbonate, phosphate, chloride, acetate, oxalate, etc.

Of course, any of the radicals R¹, R², X, Q and Ar such non-ionic and ionic organophosphites the above formulas (I)to(VII) can be substituted, if desired, any approaching is named Deputy containing from 1 to 30 carbon atoms, which does not harm the desired result of the process of the present invention. The substituents that may be on the above radicals, in addition, of course, to the corresponding hydrocarbon radicals such as alkyl, aryl, Uralkaliy, alkalinty and tsiklogeksilnogo substituents may include for example silyl radicals such as -- Si(R⁷)₃, amino radicals such as-N(R⁷)₂, phosphine radicals such as-P(R⁷)₂, acyl radicals such as-C(O)R⁷acyloxy radicals, such as-OC(O)R⁷, amido radicals such as -- CON(R⁷)₂and-N(R⁷)COR⁷, sulfonic radicals, such as-SO₂R⁷, alkoxy radicals, such as-OR⁷, sulfanilamide radicals, such as-SOR⁷, sulfanilamide radicals, such as-SR⁷, Vospominanie radicals such as -- P(O)(R⁷)₂as well as halogen, nitro, cyano, trifluoromethyl, hydroxy radicals, etc. in which each R⁷radical individually represents the same or different monovalent hydrocarbon radical having from 1 to 18 carbon atoms (for example, alkyl, aryl, Uralkaliy, alkalinty and tsiklogeksilnogo radicals), with the proviso that in amino substituents such as -- N(R⁷)₂each R⁷taken together, can also seat the th bivalent linking group, which forms a heterocyclic radical with the nitrogen atom, and the amide substituents such as-C(O)N(R⁷)₂and-N(R⁷)COR⁷each R⁷associated with N can also be hydrogen. Of course, it should be understood that any of the groups, substituted or unsubstituted hydrocarbon radicals, which form organoplastic may be the same or different.

More precisely illustrated substituents include primary, secondary and tertiary alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, tert-butyl, neo-pentyl, n-hexyl, amyl, sec-amyl, tert-amyl, isooctyl, decyl, octadecyl etc.; aryl radicals such as phenyl, naphthyl, etc.; arylalkyl radicals, such as benzyl, phenylethyl, triphenylmethyl etc.; alkaline radicals, such as tolyl, xylyl etc.; alicyclic radicals such as cyclopentyl, cyclohexyl, 1-methylcyclohexyl, cyclooctyl, cyclohexylethyl etc.; CNS radicals, such as methoxy, ethoxy, propoxy, tert-butoxy, -OCH₂CH₂OCH₃, -O(CH₂CH₂)₂OCH₃, -O(CH₂CH₂)₃OCH₃etc.; azlocillin radicals, such as phenoxy etc; as well as silyl radicals such as -- Si(CH₃)₃, -Si(OCH₃)₃, -Si(C₃H₇)₃etc.; amino radicals such as-NH₂,-N(CH ₃)₂, -NHCH₃, -NH(C₂H₅and so on; arylphosphine radicals such as-P(C₆H₅)₂and the like; acyl radicals such as-C(O)CH₃, -C(O)C₂H₅, -C(O)C₆H₅etc.; carbonyloxy radicals such as-C(O)OCH₃etc.; oxycarbonyl radicals, such as-O(CO)C₆H₅etc.; amido radicals such as CONH₂, -CON(CH₃)₂, NHC(O)CH₃and so, sulfonylurea radicals, such as-S(O)₂C₂H₅etc.; sulfanilamide radicals, such as-S(O)CH₃etc.; sulfanilimide radicals, such as-SCH₃, -SC₂H₅, -SC₆H₅etc.; postonline radicals such as -- P(O)(C₆H₅)₂, -P(O)(CH₃)₂, -P(O)(C₂H₅)₂, -P(O)(C₃H₇)₂, -P(O)(C₄H₉)₂, -P(O)(C₆H₁₃)₂, -P(O)CH₃(C₆H₅), -P(O)(H)(C₆H₅and so on

Special examples of such organobentonite ligands include the following:

6,6'-[[4,4'-bis(1,1-dimethylethyl)-[1,1'-binaphthyl]-2,2'-diyl]bis(oxy)]bis-dibenzo[d,f][1,3,2]dioxaphosphinan having the formula:

6,6'-[[3,3'-bis(1,1-dimethylethyl)-5,5'-dimethoxy-[1,1'-biphenyl]-2,2'-diyl]bis(oxy)]bis-dibenzo[d,f][1,3,2]dioxaphosphinan having the formula:

6,6'-[[3,3',5,5'-tetrakis(1,1-dimethylpropyl)-[1,1'-biphenyl],2'-diyl]bis(oxy)]bis-dibenzo[d,f][1,3,2]dioxaphosphinan, having the formula:

6,6'-[[3,3',5,5'-tetrakis(1,1-dimethylethyl)-[1,1'-biphenyl]-2,2'-diyl]bis(oxy)]bis-dibenzo[d,f][1,3,2]dioxaphosphinan having the formula:

(2R,4R)-di[2,2'-(3,3',5,5'-tetrakis-tert-amyl-1,1'-biphenyl)]-2,4-pentylbiphenyl having the formula:

(2R,4R)-di[2,2'-(3,3',5,5'-tetrakis-tert-butyl-1,1'-biphenyl)]-2,4-pentylbiphenyl having the formula:

(2R,4R)-di[2,2'-(3,3'-di-amyl-5,5'-dimethoxy-1,1'-biphenyl)]-2,4-pentylbiphenyl having the formula:

(2R,4R)-di[2,2'-(3,3'-di-tert-butyl-5,5'-dimethyl-1,1'-biphenyl)]-2,4-pentylbiphenyl having the formula:

(2R,4R)-di[2,2'-(3,3'-di-tert-butyl-5,5'-diethoxy-1,1'-biphenyl)]-2,4-pentylbiphenyl having the formula:

(2R,4R)-di[2,2'-(3,3'-di-tert-butyl-5,5'-diethyl-1,1'-biphenyl)]-2,4-pentylbiphenyl having the formula:

(2R,4R)-di[2,2'-(3,3'-di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl)]-2,4-pentylbiphenyl having the formula:

6-[[2'-[(4,6-bis(1,1-dimethylethyl)-1,3,2-benzodioxaphosphorin-2-yl)oxy]-3,3'-bis(1,1-dimethylethyl)-5,5'-dimethoxy[1,1'-biphenyl]-2-yl]oxy]-4,8-bis(1,1-dimethylethyl)-2,10-dimethoxybenzo [d,f][1,3,2]dioxaphosphinan having the formula:

6-[[2'-[1,3,2-benzodioxaphosphorin the-2-yl)oxy]-3,3'-bis(1,1-dimethylethyl)-5,5'-dimethoxy[1,1'-biphenyl]-2-yl]oxy]-4,8-bis(1,1-dimethylethyl)-2,10-dimethoxybenzo[d,f][1,3,2]dioxaphosphinan, having the formula:

6-[[2'-[(5,5-dimethyl-1,3,2-dioxaphosphinan-2-yl)oxy]-3,3'-bis(1,1-dimethylethyl)-5,5'-dimethoxy[1,1'-biphenyl]-2-yl]oxy]-4,8-bis(1,1-dimethylethyl)-2,10-dimethoxybenzo[d,f][1,3,2]dioxaphosphinan having the formula:

2'-[[4,8-bis(1,1-dimethylethyl)-2,10-dimethoxybenzo[d,f][1,3,2]-dioxaphosphinan-6-yl]oxy]-3,3'-bis(1,1-dimethylethyl)-5,5'-dimethoxy[1,1'-biphenyl]-2-yl-bis(4-hexylphenyl)ester of phosphorous acid having the formula:

2-[[2-[[4,8-bis(1,1-dimethylethyl)-2,10-dimethoxybenzo[d,f] [1,3,2]-dioxaphosphinan-6-yl]oxy]-3-(1,1-dimethylethyl)-5-methoxyphenyl]methyl]-4-methoxy-6-(1,1-dimethylethyl)phenyl diphenyl ester of phosphorous acid having the formula:

3-methoxy-1,3-cyclohexanedimethanol[3,6-bis(1,1-dimethylethyl)-2-naphthalenyl]the ester of phosphorous acid having the formula:

2,5-bis(1,1-dimethylethyl)-1,4-penilesecrets[2,4-bis(1,1-dimethylethyl)phenyl]ester of phosphorous acid having the formula:

Methylenedi-2,1-penilesecrets[2,4-bis(1,1-dimethylethyl)phenyl]ester of phosphorous acid having the formula:

[1,1'-biphenyl]-2,2'-dieletric[2-(1,1-dimethylethyl)-4-methoxyphenyl]the ester of phosphorous acid having the formula:

The number of complex ORGANOMETALLIC catalyst containing ligand present in the reaction fluid process hydroformylation of the present invention should be minimal, such that it was sufficient only to provide necessary given the concentration of the metal and for the catalysis of the selected method hydroformylation. In General, the concentration of the metal, such as rhodium, in the range from about 10 parts per million to about 1000 parts per million, calculated as free metal in the fluid reaction hydroformylation, should be sufficient for most processes, while in General it is preferable to use a concentration of from 10 to 500 parts per million of metal, and more preferably from 25 to 350 parts per million of metal.

In addition to the ORGANOMETALLIC complex catalyst containing a ligand in a fluid reaction hydroformylation may be present in the free ligand (i.e., ligand that is not bound in a complex with the metal). The free ligand may correspond to any of the above organophosphorus ligands. How hydroformylation of the present invention may include from about 0.1 moles or less to 100 moles or more of free ligand per mole of metal is in the reaction of hydroformylation. Preferably, when the process of hydroformylation of the present invention is performed in the presence of ligand in an amount of from about 1 to about 50 moles, and more preferably, from 1.1 to about 4 moles of ligand per mole of metal present in the reaction medium; the above amount of the ligand, which is the sum of both the amount of ligand that is bound in a complex with present metal, and the amount present of free (not bound in the complex) ligand. You can add a compensating or additional ligand to the reaction fluid process hydroformylation at any time and in any suitable way, for example, to maintain a predetermined level of free ligand in the reaction fluid.

Substituted or unsubstituted unsaturated olefinic compound, which can be used in the method of hydroformylating the present invention includes optically active (probiralsya and chiral and optically inactive (achiral) olefinic unsaturated compounds containing from 2 to 40, preferably from 3 to 20, carbon atoms. Such olefinic unsaturated compounds may be unsaturated at the ends of the connection or inside and can have a direct (normal) chain hydrocarbons, to be branched is whether to have a cyclic structure, as well as mixtures of olefins, such as obtained by oligomerization of propene, butene, isobutene etc. (such as the so-called dimeric, trimeric or four-dimensional propylene, etc. as disclosed, for example, in US patents No. 4518809 and 4528403 entered into this patent application by reference). Moreover, such olefinic compounds may further contain one or more ethylene unsaturated groups and, of course, possible to use a mixture of two or more different olefinic unsaturated compounds. A typical mixture of olefinic feedstock, which can be used in reactions of hydroformylation include, for example, a mixture of butenes. In addition, such olefinic unsaturated compounds and the corresponding aldehyde products derived from them, may also contain one or more groups or substituents which do not affect the process of hydroformylation or method of the present invention in an inappropriate manner, as described, for example, in US patents No. 3527809, 4769498 etc. entered into this patent application by reference.

Most preferably, the objects of the invention have been particularly effective for obtaining optically inactive aldehydes, using achiral alpha-olefins, participating in hydroformylating containing from 2 to 30, preferably from 3 to 20, carbon atoms, is achiral internal olefins, containing from 4 to 20 carbon atoms, as well as the original mixture of such alpha olefins and internal olefins.

Typical alpha and internal olefins include, for example, ethylene, propylene, 1-butene, 1-penten, 1-hexene, 1-hepten, 1-octene, 1-none, 1-mission 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecane, 1-hexadecene, 1-heptadecene, 1 octadecene, 1-nonadecane, 1 achozen, 2-butene, 2-methylpropene (isobutylene), 2-methylbutane, 2-penten, 2-hexene, 3-hexane, 2-hepten, 2-octene, cyclohexene, propylene-dimer, propylene-trimer, propylene-tetramer, butadiene, piperylene, isoprene, 2-ethyl-1-hexene, steren, 4-methylstyrene, 4-isopropylthio, 4-tert-butylstyrene, alpha methylstyrene, 4-tert-butyl-alpha-methylstyrene, 1,3-diisopropenylbenzene, 3-phenyl-1-propene, 1,4-hexadiene, 1,7-octadiene, 3-cyclohexyl-1-butene and the like, as well as 1,3-diene, butadiene, alkylalcohol, for example, methylpentanoate, alkenylamine, alkenylacyl, alkanol, for example, pentanol, alkanal, for example, pentenal etc. such as allyl alcohol, allylmalonate, Gex-1-EN-4-ol, Oct-1-EN-4-ol, acetate, ZIOC scientists, 3-butylacetat, finalproject, arylpropionate, methyl methacrylate, unilateraly ether, vinylmations ether, arelatively ether, n-propyl-7-octanone, 3-butenonitrile, 5-hexanamide, eugenol, isoeugenol, safrole, Isosafrole, anethole, 4-allylanisole, inden, limonene, beta-pinene, Dicyclopentadiene is h, cyclooctadiene, camphene, linalool, etc.

Typical suitable substituted and unsubstituted olefinic starting materials include olefin compounds described in Kirk-Othmer, Encyclopedia of Chemical Technology, Fourth Edition, 1996, part of which is related to the method introduced in this patent application by reference.

Reaction conditions of the process of hydroformylating covered by this invention, can vary in a wide range of values. For example, the molar ratio of H₂:CO gaseous hydrogen to carbon monoxide may range from about 1:10 to 100:1 or higher, more preferred is a molar ratio of hydrogen to carbon monoxide is from 1:10 to about 10:1. In General, the process of hydroformylation can be carried out at the reaction temperature greater than -25°C., more preferably greater than 50°C. the Process hydroformylation can be carried out at the reaction temperature less than 200°C, preferably less than 120°C. Specified total pressure will be selected, as described above in this patent application. The minimum total pressure is limited primarily by the amount of carbon monoxide, necessary to conduct the reaction in the negative region or reverse curve speed, which will depend on the particular form of fosfororganicheskikh and catalyst hydroformylation. In General, the total pressure of a gas containing hydrogen, carbon monoxide and olefinic original connection may be in the range from about 1 pound per square inch (6.8 kPa) to about 10000 psi (68,9 MPa). In General, however, it is preferable that the process was carried out at the total pressure of a gas containing hydrogen, carbon monoxide and olefinic original connection is less than approximately 2000 psi (6895 kPa) and more preferably less than about 500 psi (34,5 kPa). In more detail, the partial pressure of carbon monoxide method hydroformylation of the present invention can vary from 1 pound per square inch (6.8 kPa) to about 1000 psi (6800 kPa), and more preferably from 3 psi (20.7 kPa) to about 800 psi (5516 kPa), most preferably, from 15 psi (103,4 kPa) to about 100 psi (689 kPa), at the same time, it is preferable that the partial pressure of hydrogen was from 5 psi (34,5 kPa) to about 500 psi (3450 kPa) and more preferably from 10 psi (68,0 kPa) to about 300 psi (2070 kPa).

The speed of the incoming stream of synthesis gas can be any current flow rate sufficient to vypolnyaemogo process hydroformylation. Typically, the feed rate of flow of the synthesis gas may vary widely and may depend on the particular form of the catalyst, the feed rate of flow of the olefin and other process conditions. Similarly, the speed of the exhaust flow can be any current flow rate sufficient to perform the desired process hydroformylation. The speed of exhaust flow usually depends on the size of the reactor and purity of the incoming reagent and synthesis gas. Suitable feed rate of flow of the synthesis gas and the speed of exhaust flow as described in the following reference: “Process Economics Program Report 21D: Oxo Alcohols 21d,SRI Consulting, Menlo Park, California, Published December 1999, included in the present patent application by reference. As defined by the experts in this field, other flow rate of the synthesis gas and exhaust flow can meet the requirements, depending on the design scheme of the process.

The invention will be further clarified by considering the following examples, which are intended for a full description of the use cases of the present invention. Other embodiments of the present invention will be obvious to specialists in this area from consideration of this description or application of this invention disclosed in this patent application.

In the reamers, later in the patent application to describe the velocity of the gas streams used unit of measure - normal liters per hour (NLC). The reaction rate of hydroformylation described as the rate of consumption of carbon monoxide in gram-mole of carbon monoxide used per liter of the volume of catalyst solution per hour (gmol/l/h). The purity of all components: propylene, carbon monoxide and synthesis gas was more than 99.8 per cent.

Example 1

This example demonstrates the method of the present invention for determining the flow rate of the initial amount of synthesis gas to work in reverse order on the partial pressure of carbon monoxide in the process. The reactor was designed in accordance with figure 3. A reactor equipped with a paddle stirrer (1), the axis of the stirrer (2), line feed of propylene and device flow control feed (3), line feed synthesis gas and a device for controlling the speed of the stream (4), a supply line, ending bubbling device in the reactor; a gas exhaust line flow and the control device exhaust stream (5), General pressure sensor (6), the output line of the solution containing the products/catalyst system for the extraction of products (7), and a supply line for returning catalyst from the product recovery (8). When conducting the experimental is the feed rate of propylene stream and the speed of exhaust flow reactor was maintained constant under the current restrictions. In order to maintain a constant level of catalytic liquid and reach the stationary part of the reaction solution was continuously removed from the reactor and passed through the extraction system of the product, to remove a portion of the product of hydroformylation and by-products. The treated solution containing the catalyst was recovered and returned back to the reactor in continuous mode. Synthesis gas filed via the control unit 4 into the reactor, starting at substochiometric feed speed relative to the speed of feed of propylene. Reaction conditions were maintained until such time has not been reached stationary mode of operation, which showed a constant total pressure of the reactor and continuing the reaction rate of hydroformylation. In stationary mode, the measured total pressure of the reactor, the reaction rate of hydroformylation, the speed of exhaust flow and composition, and other reaction conditions. After the run, the feed rate of the synthesis gas was regulated to determine another point stationary data.

The reactor contained 1 liter of the catalyst solution, containing 70 ppm of rhodium and 1.5±0.5 equivalent (rhodium) 6,6'-[[3,3',5,5'-tetrakis(1,1-dimethylethyl)-[1,1'-biphenyl]-2,2'-diyl]bis(oxy)]bis-dibenzo[d,f][1,3,2]dioxaphosphinan (the above-mentioned ligand D)dissolved in a mixture of Butyraldehyde, Butyraldehyde dimers, trimer is in (and above), together with propylene and propane, dissolved in solution. During the experiment the feed rate of propylene was kept constant and equal to 304 grams/hour. The internal temperature of the reactor was maintained constant and equal to 75°C. the Ratio of N₂:CO in the synthesis gas was kept constant and equal to 1.04 million. Therefore, the speed of exhaust flow 32,67 NLC, or more, was sufficient for the removal of inert components and by-products from the reactor to reach a stationary work. The following parameters were measured as a function of the flow velocity of the incoming synthesis gas: the total pressure of the reactor, the partial pressure of CO, partial pressure of H₂, the partial pressure of propylene, the speed of exhaust flow reactor and the reaction rate of hydroformylation, as shown in table 1.

According to the data from table 1, we plot in figure 2, based on the total pressure of the reactor velocity of the incoming synthesis gas. In figure 2 the area of negative order WITH speed curve corresponds to the region of sharply increasing total pressure. The last two coordinates of table 1 show the response of the reaction system on transitions in the partial pressure of carbon monoxide from the field of positive order curve speed (when 215,77 NLC flow rate of the incoming synthesis the Aza from 7.11 psi partial pressure of carbon monoxide) in the area of negative order curve speed (when 220,60 NLC flow rate of the incoming synthesis gas with 115,5 psi partial pressure of carbon monoxide). Next, figure 2 shows the coordinate at which the total pressure of the reactor increases sharply at the transition from the field of positive order in the area of negative order.

Given the total pressure was chosen because of the pressures within the region, a sharp increase (positive slope) figure 2 (negative order of a speed curve). For the selected specified total pressure in this area of negative order, minimum and maximum initial speed of flow of the incoming synthesis gas was chosen as the first (1) and second point (2) of intersection, respectively, of the curve plotted data with a straight line drawn parallel to the coordinate axes of the feed stream of synthesis gas at a given total pressure. (It should be noted that we can meet some variations in the maximum flow synthesis gas (2) depending on the slope of a line that is installed with the latest reference coordinates, which usually may not be in a stationary state). For this example, and based on table 1, it was concluded that when the total pressure of the reactor, for example, 120 psi in the back area of the partial pressure of the carbon monoxide, the minimum flow rate of the incoming synthesis gas should be set higher than 157,80 NLC, but less is eaten 215,77 NLC. Accordingly, the following examples were chosen so that the initial flow rate of the incoming synthesis gas was 202 NLC. On the basis of the examples that follow, it should be noted that the partial pressure of carbon monoxide in the range from 15 to 35 psi (103-241 kPa) lies in the negative or reverse field response curve speed.

Example 2

Example 2 demonstrates stable operation of the process hydroformylation in the field of negative order curve speed hydroformylation in accordance with the invention. The reactor was designed in accordance with figure 4, which was identical to the design of the reactor in figure 3 except that the device for controlling the incoming synthesis gas is supplied by a valve control device initial (4) and secondary (9) thread. Operating parameters managed in the same manner as in example 1. The initial amount of synthesis gas filed into the reactor through the device for controlling the speed of the initial stream of synthesis gas (4). In response to deviations of the measured total pressure from the target pressure 120 psi (827 kPa), the additional amount of synthesis gas filed via the secondary pressure regulator pressure (9)to equalize the total pressure of the reactor to a specified pressure. Reaction conditions were maintained until, until it was dost the bend stationary mode of operation, that showed a constant total pressure of the reactor is constant and the reaction rate of hydroformylation. Then determined the total pressure of the reactor, the reaction rate of hydroformylation, the speed of exhaust flow and composition, and other reaction conditions. Stationary mode of operation was demonstrated for more than 10 hours, as summarized later in a patent application.

The reaction was conducted under the following process parameters: flow propylene 229 grams/hour; the temperature of the catalyst at 75°C; ratio of incoming synthesis gas (H₂:) 1,06; the flow rate of the initial incoming synthesis gas 202 NLC; the total pressure of the reactor 120 psi (827 kPa) (using the pressure regulator incoming synthesis gas (9)); and the speed of exhaust flow reactor 38 NLC. When the experiment was determined that the average speed of flow of the incoming synthesis gas through the pressure regulator secondary incoming synthesis gas (9) is 27 NLC. Average total feed rate of the synthesis gas in the reactor included the speed of the initial stream 202 NLC plus the average velocity of the secondary flow through the pressure regulator pressure 27 NLC that gave the whole 229 NLC. Data were plotted as shown in figure 5 (a dependency of the reaction rate of hydroformylation by length of service) and 6 (dependence of parcia inogo pressure on the duration of the work). It is evident from Fig. 5 and 6 shows that a stable operation in the field of negative order curve speed reached through to 10.8 hours.

Comparative experiment 1

Comparative experiment 1 shows that stable operation can not be saved as a result of management total pressure of the reactor through a gas exhaust line and the sensor control exhaust gas discharge. After demonstrating stable operation over to 10.8 hours, as shown in example 2, the reactor design was quickly changed (<1 minute during operation), as shown in Fig.7. All items were identical to that shown in figure 3, including only device to control the flow of incoming synthesis gas (4), except that the pressure of the reactor was controlled using a back-pressure control on the suction line (10), and not controlling the pressure of the reactor with increasing the flow of incoming synthesis gas. The speed of exhaust flow reactor was measured (but not controls), using the speed sensor exhaust flow (11). Reaction conditions were the same as in example 2 with a feed rate of propylene 299 grams/hour; the temperature of the catalyst within the reactor at 75°C; ratio in the synthesis gas (H₂:) 1,06 with initial total velocity of the incoming stream 232 NLC; the reactor pressure 120 psi, using a back pressure regulator, gazoo the conductive flow reactor. The results are presented on Fig (the dependence of the reaction rate of hydroformylation by length of service) and Fig.9 (the dependence of the rate of exhaust flow reactor from the duration of the operation).

As can be seen from Fig. 8 and 9, even at the beginning of the reactor operation in a stable mode in the field of reverse order monoxide curve speed change control pressure in the reactor and control the flow rate of the incoming synthesis gas from the construction of the invention of example 2 (figure 4) to traditional designs (7), leads to a rapid, uncontrollable change of reaction conditions, including reducing the speed of reaction, speed increase exhaust flow and, consequently, increasing the partial pressure of carbon monoxide and hydrogen.

After 1.25 hours the flow rate of the incoming synthesis gas was reduced to 180 NLC, which immediately led to a reduction in the rate of exhaust flow reactor 193 NLC to 10 NLC to 1,38 hour of work. In this operating mode, the response is passed back into the realm of positive order curve speed hydroformylation, as shown previously in figure 2. Based on figure 10, through 1.42 hour feed rate of the synthesis gas was increased to 204 NLC and watched the parameters in a stationary mode. With increasing partial pressure of carbon monoxide is and the system again becomes unstable, when the speed of the feed synthesis gas reached approximately 238 NLC, and the partial pressure of carbon monoxide has reached the negative side of the curve speed hydroformylation. Figure 10 (the dependence of the rate of hydroformylation velocity of the incoming synthesis gas) shows that when the system has moved from a positive order in the area of negative order, in response to the condition in the reactor became unstable again (with a 7.85 on 9,35 including hours of operation), since the reaction rate of hydroformylation fell from 4.7 gmol/l/h to 2.4 gmol/l/H. a Similar instability, not shown in graphical form, found in the partial pressure of carbon monoxide, propylene and hydrogen and in the speed of the exhaust flow reactor. The experiment again demonstrates that when reaching negative, causing a reaction in the system, a slight throttling of the incoming synthesis gas (<1%) can lead to a significant and uncontrollable changes in operating parameters.

Example 3

This example shows the possibility of achieving stable operation of the reaction system in a comparative experiment 1. From the end of the conditions described in comparative experiment 1, the total flow rate of the incoming synthesis gas was reduced to 180 NLC, and the timer invoice the wheelie back to 0. Subsequently, through 0,20 hours overall speed of the exhaust flow reactor dropped below 17 NLC, and at this point quickly changed the design of the reactor (<1 minute during operation) back to the design shown in figure 4. The feed rate of the initial synthesis gas was set at 202 NLC (same flow rate of example 2). Given the total pressure was set to 120 pounds per square inch (834 kPa) and any deviation of the actual pressure of the reactor from specified pressure regulated through the control device of the secondary feed stream of synthesis gas (figure 4, part 9). Without any further changes, the reaction system was quickly returned to the desired initial stable mode of operation similar to that in example 2. Supported the following operating parameters: feed rate of propylene 299 gmol/h; the temperature of the catalyst within the reactor at 75°C; ratio of gases in the incoming synthesis gas (H₂:) Of 1.06, with the initial speed of the incoming stream 202 NLC; the total pressure of the reactor 120 psi (using the pressure regulator incoming synthesis gas); and the speed of exhaust flow reactor 44 NLC. The speed of exhaust flow reactor 44 NLC was sufficient for the removal of inert components and by-products from the reactor to achieve stationary. Raza is taty outlines figure 11 (a dependency of the reaction rate of hydroformylation by length of service) and Fig (the dependence of the values of the partial pressure of the duration of the work), which show the stability of the reaction rate of hydroformylation and partial pressures of the components in the reactor. Despite the lack of illustrative graphs, similar stability was observed for the speed of exhaust flow reactor as a function of time. This example demonstrates that a stable work in the field is desirable negative order curve speed hydroformylation quickly returned to its original state using the redesign of the reaction system to the structural specifications of the present invention.

Example 4

Example 4 demonstrates stable operation of the process hydroformylation in the field of negative order curve speed through the use of a secondary flow of pure carbon monoxide. The reactor was designed as shown in Fig, he has the same components as the reactor in figure 4, except that the device for controlling the flow of incoming synthesis gas contains the initial valve control device (4), while the secondary control device includes a device to control the flow of incoming net monoxide (12). The operating parameters in other respects were the same as in example 2. The initial amount of synthesis gas filed into the reactor to control the speed of the original is the material flow synthesis gas. In response to deviations of the measured total pressure from the target pressure 113 psi (880 kPa), some amount of carbon monoxide filed via the secondary pressure regulator pressure to align the total pressure of the reactor to a specified pressure. Reaction conditions were maintained until such time has not been reached stationary regime, which reflects a constant total pressure of the reactor and a constant reaction rate of hydroformylation. Then determined the total pressure of the reactor, the reaction rate of hydroformylation, the speed of exhaust flow and composition, and other reaction conditions. Stationary mode of operation was demonstrated for more than 12 hours.

The reaction was carried out under the following process parameters: flow rate of the incoming propylene 327 grams/hour; the temperature of the catalyst at 75°C, the ratio of the incoming synthesis gas (H₂:) 1,23; the flow rate of the initial incoming synthesis gas 213 NLC; the total pressure of the reactor 113 psi (880 kPa) (using the pressure regulator of the incoming carbon monoxide (4)) and the speed of exhaust flow reactor 38,5 NLC. Compared with the previous experiment, the speed of the incoming initial synthesis gas was adjusted higher to compensate for the reduced concentration of carbon monoxide in the original thread of synthetic ha is and to comply with the requirement to supply the stoichiometric amount of hydrogen in the reactor. However, when 213 NLC initial supply of synthesis gas was in the preferred range and is close to the maximum, derived from figure 2. During the experiment found that the average speed of flow of the incoming carbon monoxide through the pressure regulator incoming secondary stream of carbon monoxide (12) is 14.7 NLC. Data collected and graphically depicted as shown in Fig (the dependence of the reaction rate of hydroformylation by length of service) and Fig (the dependence of the partial pressure of the duration of the work). The graphs demonstrate stable operation of the reactor in the field of reverse order monoxide speed curve using operating modes, including constant speed exhaust flow, a constant feed rate initial synthesis gas and varying the feed rate of carbon monoxide to control the total pressure of the reactor.

Comparative experiment 2

Comparative experiment 2 shows that stable operation can not be maintained in the field of reverse curve speed due to the use of constant flow rate entering the initial synthesis gas, in combination with a constant flow rate of the incoming secondary monoxide. After demonstrating stable R the bots during the entire 12,25 hours as described in example 4, quickly changed the configuration of the reactor (<1 minute during operation), as shown in Fig, and the timer is put back to zero. All the parts were identical to those used on pig, except that utilized the device control constant incoming stream of carbon monoxide (4) and (13), and the total pressure in the reactor operated back pressure regulator (10) of the exhaust line of the reactor. The speed of exhaust flow measured (but not controls), using the speed sensor exhaust flow (11).

Reaction conditions were the same as in example 4: the feed rate of propylene 327 grams/hour; the temperature of the catalyst within the reactor at 75°C, the ratio of gases in the incoming synthesis gas (H₂:) 1,23 with the flow velocity of the initial incoming synthesis gas 213 NLC; constant flow rate of the incoming carbon monoxide 14,7 NLC; the set pressure of the reactor 109 psi, using a back-pressure control exhaust flow reactor (when the pressure in the reactor was less than the threshold, the speed of exhaust flow reactor was equal to zero). Data are presented on Fig (the dependence of the reaction rate of hydroformylation by length of service) and Fig (the dependence of the partial pressure of the length R of the bots).

Initially, the change in pressure resulted in rapid, unwanted and uncontrollable drop in total pressure in the reactor, reaching minimum values of 68 psi for approximately 0.3 hours. Until the pressure in the reactor was below the set pressure 109 psi, gas, expelled from the system, was not available for analysis and, therefore, the partial pressure of the reactor and the rate of hydroformylation could not be calculated. Through 2.65 an hour, when a value of the gas exhaust stream reset again from the reactor, it became obvious that for at least some time previous work pressure of carbon monoxide corresponded to approximately 2 pounds per square inch or less, which led to work in an unwanted region of positive order kinetic curve. Through 2.95 hour speed exhaust flow reactor quickly and unmanaged increased to approximately 170 NLC. Eventually this led to another undesirable mode of operation, namely, a significantly higher partial pressure of carbon monoxide and hydrogen, a lower reaction rate of hydroformylation and significantly higher velocity exhaust flow reactor. This experiment demonstrates that even at the beginning of the reactor operation in a hundred is safe mode in the field of reverse order monoxide speed curve, but changing the way that the control pressure in the reactor from the construction of the invention on Fig traditional design on pig can happen fast unmanaged changes in the reaction conditions.

Example 5

This example demonstrates the ability to restore stability unstable comparative experiment 2. At the end of the comparative experiment 2 quickly changed the configuration of the reactor (<1 minute during operation) back to the design shown in Fig; the feed rate of the synthesis gas was reduced to 97 NLC; the regulator pressure of carbon monoxide was set up to 109 psi and the timer resets. Subsequently, the feed rate of the synthesis gas incrementally increased, eventually reaching 211 NLC for 0.3 hour. Through 0.37 hours regulator pressure of the carbon monoxide control device WITH secondary stream (12) has increased from 109 psi to 113 psi. Without any further changes of the reaction system quickly regained required stable working conditions, similar to those found in example 4. Supported the following operating mode: feed rate of propylene 327 gmol/h; the temperature of the catalyst within the reactor at 75°C; ratio of incoming synthesis gas (H₂:) 1,23 with the initial speed of the incoming stream 211 is CL; the total pressure of the reactor 113 psi (880 kPa) (using the pressure regulator incoming synthesis gas (12)) and the speed of exhaust flow reactor 41,3 NLC. The speed of exhaust flow reactor 41,3 NLC was sufficient for the removal of inert components and by-products from the reactor to reach a stationary work for 12 hours.

Example 6

Variant implementation of the present invention is illustrated by the design of the reactor shown in Fig, in which the rate of exhaust flow reactor is maintained with the help of the device Manager variable speed of the incoming synthesis gas [(14), combined with (4)]to control the rate of exhaust flow through the back pressure regulator (10), used to keep the total pressure of the reactor. Note that the component 11 on Fig is a sensor exhaust flow reactor. First catalytic composition, process parameters and the design of the reactor is used as shown in figure 3 and in example 1 to determine the desired specified total pressure of the reactor and the flow rate of the initially incoming synthesis gas. The minimum speed of the exhaust flow is determined based on the purity of the incoming reactants, speed, sufficient for removal of inert components and by-products the comrade from the reactor to achieve steady-state operation. After establishing these parameters are entered, the reaction conditions and the flow velocity of the incoming reagents are the same as in example 2. During the experiment, the flow rate of the incoming propylene (3) and the speed of exhaust flow reactor is regulated so continuously, to the extent practicable. In order to maintain a constant level of catalytic liquid and reach the stationary regime, the solution of the catalyst is continuously removed from the reactor (7) and passed through the extraction system product removal products hydroformylation and by-products. The solution of the catalyst is recovered and returned back to the reactor continuously (8). The initial amount of the synthesis gas fed into the reactor to control the flow rate of the incoming synthesis gas (4). Changing the amount of synthesis gas is regulated through a valve control device of the secondary stream (14), thereby regulating the speed of exhaust flow reactor. The total pressure of the reactor is controlled by a back pressure regulator on the gas exhaust line reactor (10). Reaction conditions are saved and achieved steady-state mode, which reflects a constant total pressure of the reactor and a constant reaction rate of hydroformylation.

Example 7

This example illustrates the obtaining of a speed curve of hydroformylation the tion, as a function of partial pressure of carbon monoxide, as in the positive field and the negative of the order of a speed curve. Without using the method of the present invention, would have difficulty in achieving different values of the reaction rate in the region of negative order of a speed curve.

Propylene was subjected to reaction hydroformylation using synthesis gas (CO+H₂in the presence of a rhodium catalyst, prepared from 1.5±0.5 equivalent (rhodium) 6,6'-[[3,3',5,5'-tetrakis(1,1-dimethylethyl)-[1,1'-biphenyl]-2,2'-diyl]bis(oxy)]bis-dibenzo[d,f][1,3,2]dioxaphosphinan (the above-mentioned ligand (D). Reference is made to Fig. For the first three points in the field of positive order of a speed curve used traditional reactor (1 liter), having the structure 7. For the remaining base points in the negative order of a speed curve reactor designed in accordance with figure 4, using the method of the present invention to stabilize the process parameters. The internal temperature of the reactor was maintained constant at 75°C. the process Parameters and the initial reaction rate of hydroformylation below in table 2.

As each datum in table 2 is slightly varied in the values of the partial pressures of propylene and conc is of rhodium, the original speed hydroformylation regulated to standardized partial pressure of propylene at 50 psi (345 kPa) and the concentration of rhodium 70 ppm. Adjusted the speed is also brought forth in table 2.

Adjusted reaction rate of hydroformylation depicted on the graph as a function of partial pressure of CO, as shown in Fig, confirming theoretical graph presented in figure 1. Data are based on a method of selecting values FROM the partial pressure close to the maximum velocity of the reaction in the negative order of a speed curve, mostly, so that the reaction rate and the ratio of the isomeric products were maximal, and the formation of alkanes is minimal. In a similar way, like the graphics and the limits of partial pressures can be obtained for any ligand that is selected for use in the reaction, thus providing the operating parameters, leading to maximum speed and the maximum ratio of normal to branched isomer with minimal formation of alkanes.

1. The method of stabilization process hydroformylation, including the interaction of one or more reactants, carbon monoxide and hydrogen in the presence of a catalyst of hydroformylation to get gatitude the third stream and the stream of reaction product, containing one or more products in which the above method is carried out with the high partial pressure of carbon monoxide, the reaction rate increases with decreasing partial pressure of carbon monoxide and decreases with increasing partial pressure of carbon monoxide; and hosts the following stage of the process for the stabilization of the reaction rate, total pressure, velocity exhaust stream, the reaction temperature, or a combination of, the stage of the process, including at least one of the following schemes management process selected from:
Scheme A:
(A1) setting a given total pressure;
(A2) determining the total pressure and determining the difference between the measured total pressure and a specified total pressure; and
(A3) based on the pressure difference, measured in stage (A2), the manipulation of the flow of incoming gas, including carbon monoxide, to align the measured total pressure in fact, up to a given total pressure; and
Diagram:
(b1) establishing a preset speed exhaust flow;
(b2) determining the speed of exhaust flow and determining the difference between the measured speed of the exhaust flow and the set speed exhaust flow; and
(b3) on the basis of the difference in the speeds of the exhaust stream, measured on the Tadei (b2), manipulating the flow rate of incoming gas, including carbon monoxide, to align a certain speed exhaust flow effectively to the target speed of the gas exhaust stream.

2. The method according to claim 1, wherein one or more olefins in contact with carbon monoxide and hydrogen to obtain one or more aldehydes.

3. The method according to claim 2, in which the olefin contains from 3 to 20 carbon atoms.

4. The method according to claim 1, in which the catalyst hydroformylation includes a comprehensive ORGANOMETALLIC catalyst containing organophosphorus ligand.

5. The method according to claim 4, in which the catalyst hydroformylation includes a comprehensive ORGANOMETALLIC catalyst containing organophosphine ligand.

6. The method according to claim 5, in which the catalyst hydroformylation includes a rhodium complex catalyst containing organophosphine ligand.

7. The method according to claim 1, in which a given total pressure selected from the range of values of pressure in the area of sharpest positive slope of the plot of total pressure on the velocity of the incoming stream of carbon monoxide and hydrogen as shown in figure 2.

8. The method according to claim 1, in which the minimum set speed exhaust flow is selected as the speed of exhaust flow equal to input the mu stoichiometric excess of hydrogen and inert components.

9. The method according to claim 1, in which the initial source of carbon monoxide is introduced into the process in order, essentially, to satisfy the stoichiometric requirements of the process hydroformylation, and the measured total pressure is adjusted to a given total pressure by means of a secondary source of gas containing carbon monoxide.

10. The method according to claim 9, in which the initial source of carbon monoxide includes the primary supply of carbon monoxide and hydrogen in the reactor, and, optionally, in which the secondary source of gas containing carbon monoxide, includes synthesis gas, or pure carbon monoxide or carbon monoxide and an inert gas into the reactor.

11. The method according to claim 1, in which the total pressure is controlled by regulating the flow rate of the incoming gas, containing carbon monoxide, while the speed of the exhaust stream removed from the reactor, maintained at a constant flow rate.

12. The method according to claim 1, in which the speed of the exhaust stream removed from the reactor, is controlled by regulating the flow rate of the gas containing carbon monoxide is supplied to the reactor until a given total pressure.

13. The method according to claim 1, in which the process of hydroformylation is carried out in a number of continuously operating reactors mixing with the United sequentially, in which the total pressure is determined using the measuring device located in one or several reactors in order to regulate the total pressure in the entire series of reactors to a specified pressure.

14. The method according to claim 1, in which the process of hydroformylation is carried out in a number of continuously operating reactors mixing, connected in series, in which the rate of exhaust flow is determined using a measuring device that is located on the suction line of one or more sequential reactors, and the signal is transmitted to the line input of carbon monoxide in order to adjust the speed of the exhaust flow around the number of reactors to a predetermined velocity exhaust stream.

15. The method according to claim 1, in which the process of hydroformylation is carried out in a number of continuously operating reactors mixing, connected in series, in which the total pressure is determined using a measuring device located at one or several reactors in order to regulate the total pressure in the entire series of reactors to a specified pressure, and in which the speed of the exhaust flow is determined using a measuring device that is located on the suction line of one or more placentas is positive reactors and the signal is transmitted to the line input of carbon monoxide in order to adjust the speed of the exhaust flow around the number of reactors to a predetermined velocity exhaust stream.

16. The method according to claim 1, in which the partial pressure of carbon monoxide is selected in the field of reverse curve speed hydroformylation, the corresponding reaction rate of hydroformylation maximum or within 50% of the maximum speed that is set according to the schedule of dependence of the reaction rate of hydroformylation from the partial pressure of carbon monoxide as shown in Fig.

17. The method of stabilization process hydroformylation, including interaction in the reaction zone one or more olefinic compounds with carbon monoxide and hydrogen in the presence of a complex ORGANOMETALLIC catalyst containing organophosphorus ligand and, optionally, free organophosphine ligand to receive exhaust flow and the flow of the reaction product containing one or more aldehydes, and split into at least one separation zone one or more aldehydes from a complex ORGANOMETALLIC catalyst containing organophosphorus ligand, optional free organophosphine ligand, the improvement Zack is udaetsya in the process of hydroformylation with the high partial pressure of carbon monoxide, that the reaction rate increases with decreasing partial pressure of carbon monoxide and decreases with increasing partial pressure of carbon monoxide; and hosts the following stage of the process for a smooth change in the partial pressure of carbon monoxide in order to stabilize the reaction rate, total pressure, velocity exhaust stream, the reaction temperature, or a combination, stage of the process, including at least one of the following schemes management process selected from:
Scheme A:
(A1) setting a given total pressure;
(A2) determining the total pressure and determining the difference between the measured total pressure and a specified total pressure; and
(A3) based on the pressure difference, measured in stage (A2), the manipulation of the flow of incoming gas, including carbon monoxide, to align the measured total pressure in fact, up to a given total pressure; and
Diagram:
(b1) establishing a preset speed exhaust flow;
(b2) determining the speed of exhaust flow and determining the difference between the measured speed of the exhaust flow and the set speed exhaust flow; and
(b3) on the basis of the difference in the speeds of the exhaust stream, measured at the stage (b2), manipulating the flow rate of the incoming g is for, including carbon monoxide, to align a certain speed exhaust flow effectively to the target speed of the gas exhaust stream.

18. The method according to 17, in which the olefin contains from 3 to 20 carbon atoms.

19. The method according to 17, in which the metal complex ORGANOMETALLIC catalyst containing organophosphine ligand is rhodium plated.

20. The method according to 17, in which the partial pressure of carbon monoxide is in the range from 1 pound per square inch (6.8 kPa) to 1000 psi (6800 kPa).

21. The device for stabilization of hydroformylation according to claims 1-20, includes a reactor comprising a device for feeding one or more reactants; a device for feeding the synthesis gas; optionally, a device for supplying a secondary source of carbon monoxide; a feeding device of a solution of the catalyst;
the output device is reactive and inert gases; a device for removing the reaction fluid; a device for measuring the total gas pressure and the device for changing the speed of the gas exhaust flow of reactive and inert gases; the device further includes at least one of the following schemes, chosen from:
Circuit design:
(A1) a device for determining the difference between the desired total gas pressure and the measured total is m gas pressure;
(A2) a device for generating a signal corresponding to the pressure difference;
(A3) a device for receiving a signal from (A2) and to determine and send a feedback signal to manipulate the flow rate of synthesis gas and/or secondary source of carbon monoxide to align the measured total pressure up to the specified total pressure; and
The design of the schema:
(b1) a device for determining the difference between the set speed exhaust flow and the measured speed of the exhaust flow;
(b2) a device for generating a signal corresponding to the difference of the velocities of the exhaust flow;
(b3) a device for receiving a signal from (b2) and to determine and send a feedback signal to manipulate the flow rate of synthesis gas and/or secondary source of carbon monoxide for aligning a measured speed exhaust flow to a predetermined velocity exhaust stream.

22. The device according to item 21, which includes all the details of the constructive scheme with (A1) to (A3) including details of the constructive scheme with (b1) to (b3), inclusive.

23. The method according to claim 1, wherein the process is conducted at a temperature greater than 50°and less than 120°C.

24. The method according to claim 1, in which the catalyst hydroformylation includes rhodium and organophosphine ligand so that the rhodium is used in concentric and from 10 to 500 ppm of metal, calculated as the free metal in the fluid reaction hydroformylation.

25. The method according to claim 1, in which the catalyst hydroformylation includes metal and organophosphine ligand in such a way that the ligand is used in an amount of from 1.1 to 4 moles of ligand per mole of metal present in the reaction fluid, and above the amount of ligand is the sum of both the free ligand and the ligand, formed a complex with the metal in the reaction fluid.

26. The method according to claim 1, in which the partial pressure of carbon monoxide is in the range from 15 psi (103,4 kPa) to 100 psi (689 kPa).