Method for continuous preparation of 3-(methylthio)propanal

 

(57) Abstract:

The method is carried out by contacting a liquid reaction medium containing 3-(methylthio)propanal with a source stream of gaseous acrolein and interaction methylmercaptan with acrolein in the presence of a catalyst in the contact zone of the gas/liquid, and the reaction medium containing 3-(methylthio) propanal, methyl mercaptan and a catalyst for interaction methylmercaptan and acrolein, the specified source stream of gaseous acrolein includes a pair of acrolein and non-condensable gas and not more than about 8% by volume of water vapor, whereby acrolein is transferred from the source stream into the reaction environment and interacts in this environment with the mercaptan to form a liquid reaction product containing 3-(methylthio)propanal, non-condensable gas separated from the liquid reaction product, separate the reaction product at a fraction of the target product and a circulating fraction and a circulating fraction is recycled to the contact zone of the gas/liquid. 25 C.p. f-crystals, 5 tab., 5 Il.

The present invention relates to the production of 3-(methylthio)propanal, and more particularly, to a continuous method for direct production of 3-(methylthio)propanesulfonyl product to obtain as d-methionine, and 2-hydroxy-4-(methylthio)butane acid (HMBC). Methionine is an essential amino acid, which is usually insufficient nutrient mixtures for animals. GMC provides a source of methionine and is widely used as an additive methionine in feed mixtures for animals. ICC, almost not containing impurities, it is usually necessary for the production of GMBC or methionine.

The ICC is obtained by the interaction of acrolein with methylmercaptan. In accordance with a known method of obtaining ICC liquid acrolein and methyl mercaptan is introduced into a reactor containing a liquid phase of the ICC-product. The reaction proceeds in the liquid phase. To get the ICC desired quality, in this way using purified acrolein and/or ICC distilled before using it in production GMBC or methionine.

Acrolein is highly toxic and combustible material. It is usually produced by a vapor-phase oxidation of propylene over a solid-phase catalyst, receiving technical gaseous reaction product, which contains water vapor, acrylic acid, acetaldehyde, and other such organic products. Typically, the gas is treated for removal of acrylic acid, and then it is introduced into contact with klaeden is on and other organic components. Technical acrolein is then cleaned to remove low-boiling impurities, such as acetaldehyde, receiving the purified liquid acrolein. Purified liquid acrolein then stored for further use in the production of the ICC.

Storage of liquid acrolein entails the risk of infection, risk of fire and explosion. To ensure safe working with this substance requires a large capital and operational costs. The cost of working with acrolein can be significantly reduced if acrolein in the gas phase feeding continuously and directly after receiving it in the reactor for the production of the ICC, bypassing the stage of storing or condensation. However, since the conventional industrial methods of obtaining the ICC include reactions in the liquid phase, the need for condensing gaseous acrolein is inevitable. Moreover, as in the usual process is commonly used reaction system of periodic action, the stage of condensation and storage of liquid acrolein in the process is necessary as a protective buffer between operations of the process of obtaining acrolein and the flow in the reactor of the ICC.

In U.S. patent 4225516 described continuous method to polyosoma gas is first treated to remove acrylic acid and then cooled to condense water vapor. To reduce the water vapor content to a level acceptable for the reaction of obtaining the ICC, the final condensation temperature is from 0 to -5oC. Processed and chilled gaseous stream acrolein in contact with the flow of liquid ICC in counterflow absorption tower that leads to the absorption of acrolein ICC. Liquid stream ICC containing dissolved acrolein, circulates in the direction of the reactor ICC where add mercaptan. The process consists in the interaction of the mercaptan with the ICC with the formation of hammerkops ICC and semimarkovian in turn reacts with acrolein in liquid phase to obtain additional quantities of the ICC. Thus, this process requires up to 1% by weight of hammerkops in the reaction mixture. The ICC is removed from the system at a speed equivalent to receipt by the ICC in the reactor, while the bulk flow of the ICC recycle to the absorber acrolein.

To ensure quantitative absorption acrolein ICC, as described in U.S. patent 4225516, circulating cooling is required the ICC to a temperature of from 0 to -15oC before entering the absorber. Cooling required to condense water vapor at the temperature th and operational costs in the process, described in U.S. patent 4225516. Moreover, since the reaction proceeds through the formation of hammerkops, the reaction conversion proceeds very slowly, resulting in less than desired performance, the cost of the process increases even more.

Although the absorbance at zero temperature increases the secretion of acrolein at equilibrium system, it also increases the absorption of impurities, such as acetaldehyde, 3-(methylthio)propanal. Moreover, since the scrubber is separated from the reactor, acrolein, absorbed in the scrubber, is not consumed immediately in the zone of absorption. As a consequence there is a tendency to accumulate acrolein in the liquid phase, which reduces flag mesopredator. A high concentration of acrolein in liquid ICC also increases the possibility of formation of by-products in reactions between acrolein and ICC.

Among the several purposes of the present invention is the creation of an improved method for obtaining the ICC, the creation of such a method which can be performed continuously, the creation of such a method which provides high performance, the creation of such a method which can be accomplished with the use of technical acrolein is of such a method, which eliminates the need for storage of liquid acrolein, in particular, the establishment of such a method which can be implemented using a feed gas acrolein, obtained by continuous oxidation of propylene, without intermediate condensation liquid acrolein, and the creation of such a method which can produce high-quality ICC for immediate use upon receipt of methionine or HMBC without further purification.

In short we can say that the present invention relates to a method for continuous preparation of 3-(methylthio)propanal. The method consists of contacting a liquid reaction medium with a gaseous feed flow acrolein in the contact zone of the gas/liquid. The reaction medium containing 3-(methylthio)propanal, methyl mercaptan and a catalyst of the reaction between the mercaptan and acrolein. The feed flow of gaseous acrolein contains a pair of acrolein and non-condensable gas. Acrolein transition from the feed stream in the reaction medium and reacts with the mercaptan in this environment to form a liquid reaction product containing 3-(methylthio)propanal. Academservice gas is separated from the train. ercolina fraction is recycled to the contact zone of the gas/liquid.

Other objects and features of the invention are described in more detail below.

In Fig. 1 shows a schematic diagram of the process according to the invention, illustrating a continuous ICC technical gaseous acrolein obtained with the continuous catalytic oxidation of propylene, and Fig. 2 presents a schematic representation of a preferred method according to the invention, when the ICC receives from methylmercaptan and acrolein in a turbulent reactor with gas lift; Fig. 3 presents a schematic representation of a reactor with gas lift, adapted to work with low pressure drop; Fig. 4 presents a schematic representation of a reactor with a gas lift and the suction pipe adapted to operate at low differential pressures, and Fig. 5 shows a schematic representation of column trays for the conversion of mercaptan and acrolein in ICC.

According to the present invention the ICC obtained from methylmercaptan and gaseous acrolein in the reaction system, the gas/liquid containing liquid ICC. In the contact zone of the gas/liquid liquid phase containing the ICC and produce which goes from the gas phase into the liquid phase and reacts directly with the mercaptan in the liquid phase with the formation of additional quantities of the ICC. The heat of the exothermic reaction is transferred to the liquid coolant flowing through the device for heat exchange, for example, a shirt or a coil in contact with the contact zone of the gas/liquid.

In the contact zone of the gas/liquid are provided with a high coefficient of mass transfer due to the close contact of the gas/liquid, and the driving force for mass transfer is preferably brought to a maximum value by maintaining almost the cork flow in the gas phase. Close contact gas/liquid can be obtained by operating in the turbulent flow regime, which can be characterized, for example, a relatively high superficial velocities of gas and liquid in the bubble stream mode, where the bubbles are actively coalescent and destroyed as a result of turbulence. Such turbulent conditions also contribute to the high rates of heat transfer from the contact area of the gas/liquid to the jacket or coil in heat exchange with the contact zone. An alternative to this, the contact of the gas/liquid can be implemented with a counter-current movement of gas and liquid in the contact zone. In the latter case, the reaction heat is mainly transmitted coolant in the external heat exchanger, in keterkaitan and acrolein in the reaction zone, possible practically to avoid the formation of emotioanlly ICC. As a consequence, methyl mercaptan and acrolein react directly with the formation of the ICC. Since in this case the reaction takes place much faster than the reaction that proceeds through the formation of emotioanlly, the reaction rate is 3 - 10 times higher than that achieved in the way of this type, which is described in U.S. patent 4225516. At such speeds the reaction, the conversion speed is limited by the rate of mass transfer of acrolein from the gas phase into the liquid phase. However, it was found that the high mass transfer coefficients are achieved when, in accordance with a preferred variant implementation of the invention is supported turbulent regime. Moreover, due to rapid directional reaction between acrolein and mercaptan in the liquid phase, acrolein, arriving in the liquid phase, is consumed immediately, thereby increasing the driving force for misoperate. Thus, the marginal rate of mass transfer are high. Joint action aimed reactions and high speed mesopelagic leads to high performance in the reaction system according to the invention.

As shown in Fig. 1, Acro the different technical gaseous acrolein, leaving the reactor contain from about 4 to about 10 vol.% acrolein, from about 0.4 to about 1.0 vol.% acrylic acid, up to about 0.6% by propylene, up to about 0.6% by propane, up to about 0.5 vol.% propionic aldehyde, from about 0.1 to about 0.2 vol% acetic aldehyde and from about 40 to about 50 vol.% water vapor and from about 40 to about 50 vol.% ecodensity substances, including oxygen, nitrogen, carbon monoxide and carbon dioxide. Received technical gas is cooled in the outdoor heat exchanger 3, which causes condensation of acrylic acid and water from industrial gaseous product and provides education cooled gaseous source stream acrolein containing from about 5 to about 25 vol.%, usually from about 7 to about 15 vol.% acrolein, up to about 0.1 vol.% acrylic acid, up to about 1.0 vol.% propylene, up to about 1 vol.% propane, up to about 1 vol.% propionic aldehyde, up to about 0.5 vol.% acetic aldehyde, from about 2 to about 8 vol.% water vapor and from about 60 to about 80 about. % ecodensity substances. Technical gaseous acrolein optional you first delete the acrylic acid by contacting the gas with the usual absorbate then cooled for condensation of water vapor by passing the gas through the outdoor heat exchanger discharge stream from the absorber.

Stream source of cooled gaseous acrolein then injected into the reaction medium, which represents a recirculating flow of the ICC, flow-through reactor 5 continuous action. The reactor 5 is supplied with cooling water jacket 7. Circulating the ICC contains a catalyst for the reaction of the mercaptan with acrolein. Methyl mercaptan is introduced into the circulating stream of the ICC at any convenient point, but it is preferable to introduce it together with acrolein or slightly upstream of the insertion point acrolein. Thus, receive a two-phase mixture of reagents, in which acrolein is distributed between the liquid phase containing the ICC and the catalyst, and a gas phase containing non-condensable substances. The mercaptan may also be distributed between two phases, however, as follows from the observations, it basically is dissolved in the liquid phase. The catalyst is usually a salt of organic acid and amine. In the contact zone of the gas/fluid that travels downstream flow from the point of introduction of acrolein, acrolein is increasingly transferred from the gas phase into the liquid phase and reacts to purposefully and continuously with the mercaptan in the liquid phase with the formation of the ICC. To the extent that metelli with acrolein.

Conditions of turbulent flow are supported in the contact zone of the gas/liquid preferably, by setting the speed of two-phase flow in the turbulent regime, as defined above. The reaction proceeds rapidly with the formation of two-phase mixture of the reaction product constituting the liquid phase containing the ICC and the catalyst, and a gas phase containing non-condensable products. The reaction product leaving the reactor, is introduced into the separator 9, where the separation of the gas phase and the liquid phase. The gas phase, which contains propane, propylene, propionic aldehyde, acetaldehyde and water vapor, is removed from the separator to the device to control the eye-catching products, such as muffle furnace. The final product - the ICC is removed from the separator through the outlet 10 for the product, while the bulk of the ICC is recycled from the separator to the reactor. Received the ICC contains almost no methylmercaptan, acrolein and impurities contained in the source gas acroleine. Without further purification the obtained ICC can be used as an intermediate product in the production of GMBC.

The reaction can be performed at a temperature of from about 30 to CA is about 1 and about 2 atmospheres. Methyl mercaptan and acrolein is introduced into the reaction medium at a molar ratio of from about 0.95 to about 1.2, but most preferably from about 1.00 to about 1,02. As already noted, the original acrolein contained in an amount of from about 5 to about 25 vol.%, usually from about 7.0 to about 15 vol.%. Most preferably, the source flux vapor acrolein contain from about 10 to about 15 vol.% acrolein.

When the temperature of the reaction below about 50oC a favorable balance of acrolein between liquid and gas phases creates a particularly effective driving force for mass transfer in the liquid phase, but at temperatures significantly below the 40oC may be necessary liquid cooled refrigerant, and the kinetics of the reaction can begin to limit performance. Moreover, at lower temperatures the reaction equilibrium distribution of acetaldehyde between the gas and liquid phases becomes unfavorable, which leads to an increased concentration of acetaldehyde in the product coming out of the separator. Especially preferred reaction temperature is between about 40 and about 45oC. In this interval the temperature of the reaction can easily regulirebisa through shirt surrounding the zone of contact between the gas/liquid. As the reaction consumes dissolved acrolein, more acrolein increasingly transferred from the gas phase into the liquid to compensate for the unbalanced condition caused by the consumption of acrolein. Accordingly, in many embodiments, the execution of the invention is neither required nor desirable cooling or temperature control of the reaction or to accelerate the transition of acrolein from the gas phase into the liquid.

Although high blood pressure also contributes to misoperation, fast massoperedacha is achieved at atmospheric or close to it the pressure in the turbulent zone of contact between the gas/liquid, so that the use of reaction vessels high pressure is not necessary. Moreover, while maintaining moderate values of the pressure in the reactor pressure prevailing in the reactor for the oxidation of propylene, may be sufficient for introducing the resulting gaseous acrolein in the reactor ICC without the need for mechanical compression of the gas.

Although you can work with the source gas stream containing acrolein between about 5 and about 25 vol.%, the rate of mass transfer increases if fed gets to exceed the absorptive capacity of the contact area of the gas/liquid and have an adverse effect on the allocation of acrolein from the gas phase, and output ICC per acrolein. Given the combination of the required characteristics of the process and factors that affect conventional reactor for the production of acrolein, the optimal concentration of acrolein in the feed gas is from about 10 to about 15 vol.%.

By creating a very small excess of mercaptan in the reaction mixture reached a maximum conversion acrolein and virtually eliminates the need to remove unreacted acrolein. When the molar ratio of the reactants is maintained between about 1.00 and about of 1.02 mol of mercaptan per mole of acrolein directed reaction between the mercaptan and acrolein flows mainly in the direction of formation of the main product, and not in the direction of formation of the intermediate Hemi(methylthio)acetal of the ICC. As a consequence, achieve a high reaction rate in combination with high performance and relatively low capital and current expenditure on the operation of the reactor. The ratio of reactants can be adjusted by various means known from the prior art. Preferably periodically review the circulating flow of the ICC by gas chromatography in tulinovka relative flow rates acrolein and methylmercaptan, in order to maintain the desired excess of mercaptan and to avoid the formation of hemithoraces. For this purpose you can use located directly in the line of flow of the analyzer. In addition to the stage of the start method is carried out in a continuous steady recirculation mode. Accordingly, the attitude of the input mercaptan to acrolein can be set almost equal to 1.0, as soon as conditions are achieved steady state.

For the reaction, you can use conventional catalysts and in normal concentrations. Such catalysts include a wide variety of organic amines, such as, for example, pyridine, hexamethylenetetramine or triethylamine. For ingibirovaniya polymerization acrolein usually injected organic acids. When a catalyst is used, for example, pyridineacetic, support concentration between about 0.2 and about 1.0%, preferably between about 0.35 and about 0.5% by continuous or periodic addition of the catalyst in the liquid phase.

The circulation rate of the ICC is the largest, at least on order of magnitude greater than the receive rate of the ICC, preferably about 20 to 50 times, so that the reverse Boy of two-phase reactor, for example, a column with irrigated wall, reactor piping, a tank with a stirrer, a bubble cap column, Packed column or disc column. To accelerate the mass transfer of the gas phase is in plug flow mode. In plug flow mode in the gas phase is set to the concentration gradient of acrolein, and it is supported along the path of the flow in the contact zone of the gas/liquid, thereby creating an integrated average driving force for mass transfer substantially greater than the force that prevails in a reverse mixing of the gas phase. Particularly preferred reactor with gas lift, as it can work in corkboard mode gas phase so as to accelerate the circulation of the liquid phase of the ICC and to achieve thorough mixing of the liquid in the reactor can be used a significant amount of non-condensable substances in the feed stream of gaseous acrolein. Thus, eliminating the need for mechanical moving elements, such as pumps or agitators. In addition to this advantage is the use of column trays, especially in cases when there is a need to minimize the pressure drop in the zone of contact between the gas/liquids is illyustrirovano its use in the combined process, according to which technical gaseous acrolein is cooled and injected directly into the reactor of the ICC. In the combined process, as shown, propylene is mixed with air and injected together with steam-diluent and/or non-condensable gases in the reactor 101, containing a catalyst for the oxidation of propylene to acrolein. Stream is introduced into the reactor, prepared by mixing of air and propylene with diluents, as indicated, and the mixture is pre-heated in the external heat exchanger 111 by the transfer of heat from a technical gaseous acrolein. In counterflow tower absorber 113 with a nozzle partially cooled produced gas in contact with a liquid absorption medium for removing from the gas stream of acrylic acid. The gas leaving the absorber is passed through another external heat exchanger 103 for further cooling the product gas and condensation of the contained vapor of acrylic acid and water. Optimally, it is preferable to remove a pair of acrylic acid and the excess water is just condensation, thereby eliminating the need for the absorber for acrylic acid and does not require the pressure drop required for the passage of gas through the absorber. Chilled gotoblas the flow (upper knee"), fitted jacket 107, which can circulate the coolant. In addition, the reactor contains a pipe 119 downdraft ("lower knee"), which communicates with the upper knee through the lower bypass pipe 121, where flows the fluid flow. In the upper knee 117 is the zone of contact between the gas/liquid. Between the upper ends of the two tribes is the separator 109, through which, as through both knees, flows through the fluid flow. In an industrial setting, the desired performance can be achieved through the use of multiple bypass piping reactor in combination with one separator. Upper knee 117 contains the inlet opening 123 for gas at the lower end for introduction of a gaseous source of acrolein, and the lower knee 119 contains the inlet opening 125 for fluid introduction mercaptan vapor or liquid mercaptan. An alternative to this, the mercaptan can be entered at the point of introduction of the source gas acrolein or near this point. At the top of the knee is the zone of contact between the gas/liquid, and it has such a size that the two-phase flow is in bubble mode, when the gas is dispersed in the form of discrete bubbles within the continuous whom I fluid is caused by the difference in the height (head) of the liquid, resulting from lower density two-phase fluid at the top of the knee, compared with the liquid in the lower knee. To create favorable conditions of flow of the gas flow rate per cross sectional area of flow at the top of the knee is set to about 0.1 - 0.5 m/s this combination of gas flow and the height of the reactor, the gas trapping in the upper bend is from about 5 to about 20%, and the flow rate per unit cross section of flow in the upper bend of approximately 0.3 to 3.0 m/s To provide the desired speed of the circulation loop height gas lift preferably approximately 20 to 30 feet (6.1 to 9.1 m), for which the required pressure of gas in the inlet opening for gaseous acrolein the rector should be approximately 10 - 15 pounds/inch2, i.e., about 67 - 100 kPa (gauge pressure). You can also lower bypass pipe 121 to place the pump to facilitate circulation and reduce the desired height of the top knee 117.

To start the reactor, is shown in Fig. 2, the bypass pipe is almost all filled by the ICC, then immediately you can start the introduction of the original gaseous acrolein and methylmercaptan. Even when komnata raises the temperature of the reaction mixture to the preferred size 40oC, which is achieved sustainable working conditions.

Using a reactor with gas lift, the method according to the invention can achieve the degree of utilization of acrolein equal to at least 98%, conversion, equal to at least 97%, and output acrolein equal to at least 95%. Utilization is defined as the ratio of acrolein coming in the feed gas, the value that goes into the liquid phase; the conversion is defined as the ratio entering the reactor acrolein to a value that is consumed in the reaction; and the output is defined as the ratio of acrolein in the feed gas to the value, which is transformed into the final product - the ICC.

When the method according to the invention is carried out in conjunction with the stage of obtaining acrolein by catalytic oxidation of propylene, does not increase the formation of by-products or decomposition products of the ICC in the presence of impurities, such as propylene, propane, acetaldehyde, propionic aldehyde, oxygen, carbon monoxide, carbon dioxide, supplied in a gaseous acrolein. Thus, the method can be advantageous from an economic point of view, combined with the receiving node of acrolein to avoi is i.i.d. suitable for use in combination with the process of obtaining acrolein, which technical gaseous acrolein contains a mixture of vapor acrolein and inert gases, including small amounts of water vapor and organic impurities.

When using a reactor with a gas lift and bypass pipe, the back pressure resulting from the pressure drop at the top of the knee can lead to increased pressure in the reactor to obtain acrolein to levels above the optimum. This back pressure at least partially offset by the absence of the absorber acrolein used to obtain a purified liquid acrolein. The pressure drop in the absorber causes a back pressure in the reactor in a known method of producing acrolein. Moreover, the undesirable consequences of the pressure drop in the reactor with the gas lift can be avoided by using any known technique. For example, a moderate negative pressure can be created in the separator 109 by placing the compressor on the line blowing gas from the separator. As indicated above, the required height of the contact area of the gas/liquid can be reduced by mechanical circulation of the reaction medium of the ICC.

In Fig. 3 shows another reaction system with gas lift, what about acrolein in the zone of the lower part of the upper knee as shown in Fig. 2, the original stream of gaseous acrolein enter through the inlet opening 221 in the lower knee 219. Circulation in the bypass pipeline reactor gas is initiated at start-up by introducing the source gas through the inlet opening 224 in the upper knee 217. The height of the inlet is at least slightly less than the height, on which is located the inlet hole 221, but both of these holes may be located at such a height in the bypass pipeline to the pressure of fluid in the bypass circuit did not create excessive back pressure at the point of introduction of gas. To start the reactor can be used as the source of gaseous acrolein, and inert gas. As soon as the circulation of the reaction medium ICC, you can start typing the original gaseous acrolein through the inlet 221 and the input gas finish as soon as the two-phase flow is distributed from the inlet 221 to the inlet 224 or higher. The zone of contact between the gas/liquid covers the lower part of the knee 219 below the inlet 221 plus all the upper knee 217. Because the plot of the mushy zone in the knee 217 longer than the corresponding section in the knee 219, downward flow of Didcot, determined by the head of liquid above the inlet 221. Under moderate pressure of the liquid pressure drop is minimized. If the restriction of the differential pressure permissible pressure difference of the fluid cause the flow rate per unit cross-section of flow is less than optimal for efficient mass transfer, it is possible to compensate by increasing the size of the vertical segment below the point of gas injection to increase the residence time of the reagents in the device for mass transfer.

According to another variant, it is possible to use a reactor with gas lift and thrust tube, where the source of gaseous acrolein is injected into the conveyor pipe. Such a system is shown in Fig. 4. The reactor 305 includes traction tube 319, located in the center in a cylindrical reaction vessel 320 and containing the lower knee of the reactor system with gas/Elevator. The annular area between the thrust tube 319 and the inner wall of the reaction vessel contains upper knee 317, which, together with the thrust tube and the annular area forms a path for the circulation of the ICC. The flow of the source gas acrolein injected through the inlet 321 of the immersion tube into the conveyor pipe 319. Circulation in the bypass loop reactor with gaslift 317. Although the diagram shows the immersion tube with a single outlet opening, the inlet opening 324 preferably is a bubbler ring-type around the traction tube, with the output holes located on the periphery. Similarly, the reactor according to Fig. 3, the height of the inlet is at least slightly less than the height of the inlet 321, and both openings can be located at such a height, which is necessary for minimizing back pressure. Circulation start the same way as described above regarding Fig. 3, after which you can start typing the flow of the source gas acrolein through the inlet 321 and the input gas to start closing as soon as the two-phase flow is distributed from the inlet 321 to the inlet 324. More extensive two-phase zone in the annular knee 317 supports downward flow of two-phase reaction mixture in pulling the pipe. The reactor then continues to work with the differential pressure of the fluid determined by the head of liquid above the inlet 321. Without exerting a significant influence on the pressure drop of gas, the value of the vertical dimension of the draw-tube digestvalue residence time of reagents for mass transfer. The heat of reaction can be removed from the reactor according to Fig. 3 through the jacket surrounding the reactor 305, or coil, or other heat transfer surface located inside the reactor. In addition to the liquid flow rate per cross sectional area of flow and residence time of the reactants in cases where the differential pressure of the fluid is minimized to avoid excessive pressure in the reactor acrolein, the preferred operating conditions of the reactor according to Fig. 3 almost coincide with the operating conditions of the reactor according to Fig. 2.

Another preferred embodiment of the invention shown in Fig. 5. According to this variant, the reaction is carried out in tray column 405. The liquid reaction medium ICC is injected through the inlet opening 406 for fluid in the upper part of the column and a gaseous source acrolein is injected through the inlet opening 421 for gas in the lower part of the column. Methyl mercaptan is also injected at the point in the lower part of the column or near the bottom of the column, preferably through the same inlet 421. Inside the column is the zone of contact between the gas/liquid in which the gaseous and liquid phases are mixed in countercurrent with respect to each other, and massoperedacha from the gas in the liquid phase happens the AMI and the receiver at the bottom of the column. As the gas flows up the column, acrolein quickly transformed into a liquid phase, so that the gas discharged from the upper part of the column, contains practically no acrolein and is discharged through the muffle furnace.

Unlike virtually isothermal reactors with gas lift, shown in Fig. 2 to 4, plate column itself works mainly in the adiabatic regime. The liquid mixture of reaction products out of the lower part of the column and is separated into a fraction of the target product, which is withdrawn from the process, and return the fraction that is cooled and returned to the column. Pump 430 creates a coercive force for recycling. The heat of reaction is removed by passing the water cooling of the column in the external heat exchanger 407. To ensure complete absorption of acrolein in the liquid phase recirculation ICC emerging from the heat exchanger 407, preferably passed through the second external heat exchanger 408, where the recycle stream is cooled to about 10oC or lower temperature, preferably to about 0 to 10oC by heat transfer to the chilled brine. Part of the faction of the ICC emerging from the cooling heat exchanger 407, may not necessarily be returned to the Windows of the loop to the bottom of the column changes the temperature profile of the column, the reaction proceeds along the length of the column as in this embodiment and in the embodiment in which all of the circulating reaction medium ICC is returned in the upper part of the column.

Because of the almost adiabatic mode of operation prevails inside the column temperature gradient. The liquid flow inside the column is heated from a temperature of from about 0 to about 10oC in the upper part of the column to a temperature of from about 50 to about 60oC in the lower part of the column. As the gas emerging from the column is in contact with the ICC at a low temperature, prevailing favorable balance, and can be achieved recycling rates of acrolein more than 99%. As gas pressure drop occurs only when the passage of the gas through the liquid held by the plates can be constructed of plate column, providing very little back pressure on the reactor to obtain acrolein.

In the system depicted in Fig. 4, the use of nozzles instead of the plates can lead to the creation of tools to accelerate the mass transfer between gaseous and liquid phases. However, the disc column preferred, because the reaction proceeds in the liquid phase, and the column of raticate to completion in the contact zone of the gas/liquid. If the reaction is not fully completed, the equilibrium distribution of acrolein between phases can lead to loss of acrolein in the outgoing gas.

According to another variant of the system shown in Fig. 4, can be operated as a bubble column. However, the pressure drop in bubble column is significantly greater than in plate column or a column with a nozzle. In cases where acceptable fairly significant pressure drop, the preferred reactor with gas lift due to turbulence created in the upper knee of the reactor.

The invention is further illustrated with examples.

Example 1. The ICC is produced by interaction of methylmercaptan and acrolein in the reactor with a gas lift type shown in Fig. 2. The height of the reactor is equal to 3 feet (0,914 m), the inner diameter of the top knee is equal to 0.5 inch (1.27 cm). The separator 109 gas/liquid contains a cylinder with a hole for discharging the resulting ICC, the connection below the liquid surface for returning the circulating ICC in the lower knee of the bypass pipe reactor and the outlet at the top for a conclusion of non-condensable gases. Prior to the introduction of reagents bypass pipeline reactor fill the ICC, containing at sbryzgivaem air through the hole 1/16 inch (1.52 mm) inlet 123 for supplying the source gas acrolein. During the spraying air to start the circulation of the ICC through shirt 107 miss hot water to bring the temperature of the circulating ICC to the 41oC.

For filing prepare for a stream of synthetic technical acrolein having the composition shown in table. 1. This stream is introduced into the reactor through the spray at the entrance of the channel 123. A pair of mercaptan is injected through the same hole. Acrolein and methyl mercaptan is injected through the sprinkler in a molar ratio of about 1.0:1.0 in. The absolute speed of flow of the reactants are shown below in table. 1. In table. 1 shows the gas flow rate per cross sectional area of flow at the top of the knee, the volume of liquid in the reactor, the residence time in the reactor liquid product, the degree of utilization of the supplied reagents, the product yield in the reactor, the duration of a continuous cycle, the average feed rate of the added catalyst and the average speed of water in the original gaseous acrolein.

The sprinkler inlet 123 disperses two streams of reactants in the liquid at the top of the knee and creates an air column for this tribe. As a consequence, the liquid in neurinoma lower knee forcibly moves dispergirovaniya gases in the upper knee.

Inside the top of the knee contains two phases, starting from the spray gas in the lower part toward the separator in the upper part, there is formed a mixture of reagents, which includes the liquid phase containing the ICC, methyl mercaptan and a catalyst, and a gas phase containing acrolein. Acrolein and methyl mercaptan quickly absorbed in the liquid phase, and both absorbed reagent react with each other with the formation of the ICC. The reaction rate is very high, but it is the rate limiting process. Between acrolein and the mercaptan is also limited reaction in the vapor phase. The temperature in the contact zone of the gas/liquid in the upper knee of the reactor is maintained at approximately 41oC by removal of exothermic heat of reaction by cooling water circulating in the jacket 107.

Thanks to a high-turbulence and well dispersible two-phase flow produced in a simple system with gas lift without mechanical mixing or pump for recirculation, in a single reactor with a bypass pipeline is more than 95% utilization of all of the supplied reagents (i.e. acrolein and methylmercaptan), and virtually all of the used reagents preseruing leaving gas is also provided in table. 1.

Despite the higher than usual, the content of impurities in the feedstock (propylene, propane, acetaldehyde, propionic aldehyde and water) contained in the flow of the source gas acrolein, is not observed at all or there is a slight formation of by-products or decomposition products in the presence of these impurities. In particular, this and other experiments show that the reaction system is able to prevent the content as an impurity of the water more than 3 vol.% in the original stream of gaseous acrolein and reaching a water content of more than 6 wt.% in the circulating fluid during steady mode.

As a result of intensive mixing, provide a turbulent flow in the contact zone of the gas/liquid and rapid circulation of the reaction medium of the ICC, it is possible to avoid areas of overheating or non-equilibrium concentrations. This in turn prevents the formation of undesirable by-products.

The results of the experiment and material balances (to the table.1)

The average temperature of the reactor 41,0oC

The initial molar ratio, acrolein/MeSH - 0,99

The volume of liquid in the reactor - 650 ml

The residence time of the liquid/BR> The weight of the aldehyde/weight supplied acrolein + MeSH - 94,88%

Mol aldehyde/mol fed acrolein - 94,35%

Mol aldehyde/mol supplied MeSH 94,35%

The average feed rate of the catalyst - 0,0102 g/min

Examples 2 to 23. Using the apparatus depicted in Fig. 2, carry out the interaction of acrolein with methylmercaptan with obtaining the ICC. The process is carried out by the method described in General terms in example 1, but changing the value of the operating temperature, molar ratio of acrolein to the mercaptan in the feedstock fed to the reactor, the total volumetric gas flow rate and the concentration of acrolein in the source gas mixture. These process conditions and the values of the outputs in the experiments in examples 2 to 23 shown in table. 2.

Measurement or determination of conduct for gas flow per unit cross-section of flow, the concentration of introduced acrolein, reaction temperature, concentration of catalyst, the residence time of the reactants in the installation and initial relationship acrolein to the mercaptan. Conduct statistical analysis to determine the effect of the last operating parameters on the performance, utilization of acrolein, output per acrolein, the concentration of acrolein in the liquid phase and the concentration of IPA, as is shown in Fig. 2, conduct a 50-hour continuous cycle using the original gaseous acrolein obtained by catalytic oxidation of propylene in a laboratory reactor. During experiment the temperature in the loop gas is maintained at approximately 40oC, and the ratio of supplied acrolein to the mercaptan constantly adjust using the method of discrete gas chromatography, analyzing a sample of fluid from the reactor every half hour. The final aldehyde has the following composition, wt.%:

Acetaldehyde - 0,11

The mercaptan - 0,88

Acrolein - 0,07

Allyl alcohol - 0,29

Acetic acid - 0,35

Acrylic acid - 0,52

- hydroxypropionate aldehyde - 0,27

Pyridine - 0,19

ICC - 89,02

A by-product with the molecular weight = 190 - 0,18

Water - 7,00

When carrying out the process on an industrial scale, when the water content is adjusted to a more normal level, i.e., 2%, output ICC will be more than 94%. A relatively high content-hydroxypropionate aldehyde is a consequence of the presence of water in much larger quantities than that achieved by cooling the source of gaseous acrolein in the implementation of industrial spy in the reactor with irrigated wall and the reactor with a horizontal bypass pipeline. In these experiments use synthetic source of gaseous acrolein. During steady mode samples of liquid product analyzed by gas chromatography to determine the amount of aldehyde, residual acrolein, methylmercaptan and impurity-products. On the basis of this analysis, calculations were made to determine the degree of utilization of acrolein, product yield and material balance in each experiment. The average rate of mass transfer and kinetic constants of the reaction rate obtained using the experimental data for the model of two-phase reactor. Delay gas and the rate of recirculation of the liquid were measured and correlated.

The physical dimensions of the reactor are given in table. 4 along with the temperature, the velocity of the gas and liquid velocity in each experiment. Comparison of reaction conditions, flow rates, and average mass transfer coefficients are given in table. 5.

Example 26. In accordance with the method, which is shown in Fig. 5, the reaction medium containing the ICC and the mercaptan, is in contact with the stream of vapor acrolein in tray column containing 20 plates. ICC reaction will crepuscule through the cooler 308 and return in the upper part of the column. The flow of vapor acrolein injected into the lower part of the column with the speed 663,4 lb-mol/h, it contains 15% by volume of acrolein, 0,28% by volume of acetaldehyde, 17% by volume of water vapor and 83% by volume of non-condensable substances. Methyl mercaptan is introduced into the lower part of the column at a rate of 100 lb-mol/h

Reaction medium ICC is introduced into the upper part of the column at a rate of approximately 600 lb-mol/h of the Flow received by the ICC containing 97,3% by weight of the ICC, is removed from the process in the column at a rate of approximately 110,4 lb-mol/h

1 1. Method for continuous preparation of 3-(methylthio)propanal, comprising contacting a liquid reaction medium containing 3-(methylthio)propanal, with a source stream of gaseous acrolein and interaction of methylmercaptan with acrolein in the presence of a catalyst to obtain a reaction product, wherein the liquid reaction medium communicates with a source stream of gaseous acrolein in the contact zone of the gas/liquid, and the reaction medium containing 3-(methylthio)propanal, methyl mercaptan and a catalyst for interaction methylmercaptan and acrolein, the specified source stream of gaseous acrolein includes a pair of acrolein and non-condensable gas and not more than ISPs and interact in this environment with the mercaptan to form a liquid reaction product, containing 3-(methylthio)propanal, non-condensable gas separated from the liquid reaction product, separate the reaction product at a fraction of the target product and a circulating fraction and a circulating fraction is recycled to the contact zone of the gas/liquid. 2 2. The method according to p. 1, characterized in that the flow of gaseous acrolein, methylmercaptan and reaction medium are mixed to prepare a heterogeneous mixture of reagents, in which acrolein is distributed between the liquid and gaseous phases, and the liquid phase contains 3-(methylthio)propanal, methyl mercaptan and a catalyst, and the gas phase contains non-condensable gas, a heterogeneous mixture of reactants is passed through the zone of contact between the gas/liquid at a temperature effective for implementation of targeted reaction between the mercaptan and acrolein with 3-(methylthio)propanal, you get a heterogeneous mixture of reaction products, containing a liquid 3-(methylthio)propanal and non-condensable gas, non-condensable gas separated from 3-(methylthio)propanal in the mixture of the reaction product, 3-(methylthio)propanal contained in the mixture of reaction products, divided into the fraction of the target product and a circulating fraction and a circulating fraction is returned to the contact zone g is quantum in turbulence. 2 4. The method according to p. 2, characterized in that the mercaptan and acrolein continuously injected into the reaction medium in a molar ratio close to 1, so that 3-(methylthio)propanal get directed reaction between the mercaptan and acrolein almost without education Hemi(methylthio)acetal of 3-(methylthio)propanal. 2 5. The method according to p. 4, characterized in that the mixture of reagents contain virtually no Hemi(methylthio)acetal of 3-(methylthio)propanal. 2 6. The method according to p. 2, characterized in that the mercaptan and acrolein continuously injected into the reaction mixture in a molar ratio of mercaptan to acrolein about 0,95 - 1,2. 2 7. The method according to p. 6, wherein the mercaptan and acrolein continuously injected into the reaction mixture in a molar ratio of mercaptan to acrolein about 1,0 - 1,02. 2 8. The method according to p. 2, characterized in that the feed stream of the gaseous source of acrolein represents the flow of processed gas obtained by the catalytic oxidation of propylene, and the treatment consists in the removal of acrylic acid from a stream of technical gas produced during the oxidation. 2 9. The method according to p. 8, characterized in that the processing is a cooling flow of technical gas for conden the initial gaseous acrolein contains from about 5 to about 25 vol.% acrolein, from about 2 to about 8 vol.% water vapor, up to about 0.5 vol.% acetaldehyde, up to about 0.1 vol.% acrylic acid, up to about 1 vol.% propylene, up to about 1 vol.% propane, up to about 1 vol.% propionic aldehyde and from about 60 to about 80 vol.% non-condensable substances. 2 11. The method according to p. 2, characterized in that the reaction is performed in the reactor with the gas, and the reactor gas contains a pipe with upward flow, which is the zone of contact between the gas/liquid pipeline downdraft, reported its lower end with the lower end of the pipe with upward flow through the fluid flow, and the separation zone gas - liquid between the upper ends of the pipe with upward flow and pipeline downdraft, communicating through the fluid flow, and the flow of the source acrolein injected into the pipe with upward flow at the point located on its lower end or close to it, non-condensable gas separated from the resulting reaction mixture in the separation zone and a circulating fraction is returned to the contact zone of the gas/liquid by passing through a pipeline downdraft. 2 12. The method according to p. 11, characterized in that the contact zone of the gas/liquid cooled for poacha gas/liquid is cooled to maintain a reaction temperature from about 40 to about 50C. 2 14. The method according to p. 12, characterized in that the total pressure in the contact zone of the gas/liquid ranges from about atmospheric to about 2 ATM. 2 15. The method according to p. 11, characterized in that in the contact zone of the gas/liquid gas phase dispersed in a continuous liquid phase. 2 16. The method according to p. 11, characterized in that the flow regime in the pipe with upward flow is a bubble or bag. 2 17. The method according to p. 16, characterized in that the gas flow rate per unit cross section of flow in the pipe with upward flow ranges from approximately 0.1 to approximately 0.5 m/s and the flow rate per unit cross section of flow in the pipe with upward flow is from about 0.3 to about 3.0 m/s 2 18. The method according to p. 16, characterized in that the gas phase is almost in the mode of cork flow through the zone of contact between the gas/liquid and liquid phase mainly mixed in the opposite direction around the reactor. 2 19. The method according to p. 11, wherein the mercaptan and the flow of the source gas acrolein together are introduced into the reactor mainly at the lower end of the pipe with upward flow. 2 20. The method according to p. 11, wherein the source of gaseous acrolein is introduced into the reactor mainly at the lower end of the Tr is the AI in the pipeline downdraft. 2 21. The method according to p. 1, characterized in that the catalyst is chosen from the group consisting of organic amines and mixtures of organic amines and organic acids. 2 22. The method according to p. 1, characterized in that the flow of the source gas acrolein and the reaction medium is passed in countercurrent through the zone of contact between the gas/liquid. 2 23. The method according to p. 22, characterized in that the flow of the source gas acrolein and the reaction medium is passed in countercurrent flow through a vertical column containing a device to accelerate the mass transfer between the gas and liquid phases, and non-condensable gas away from the upper part of the column and the liquid reaction product discharged from the bottom of the column. 2 24. The method according to p. 23, characterized in that the recirculating stream is cooled by means of the external heat transfer to remove the exothermic heat of reaction from the reaction environment. 2 25. The method according to p. 24, characterized in that the circulating stream is cooled to a temperature not exceeding about 10C, to accelerate the absorption of acrolein the reaction medium in the upper part of the column. 2 26. The method according to p. 23, characterized in that the device for accelerating the mass transfer is a plate column trays, where Kon is

 

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