Process of multistage hydrofomylation of c6-c24-olefins into aldehydes and/or alcohols

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to technology of production of higher aldehydes and alcohols via hydrofomylation of olefins. C6-C24-olefins are subjected to hydrofomylation on cobalt or rhodium catalyst to achieve degree of conversion 20 to 98%, whereupon catalyst is removed from the product, regenerated and returned to hydrofomylation reactor. Resulting liquid mixture is separated by distillation into low-boiling olefins- and paraffins-containing fraction and bottom fraction containing aldehydes or aldehydes/alcohols mixture. In the case of alcohols being desired product, product fraction is subjected to hydrogenation on hydrogenation catalyst including copper, nickel, chromium, zinc, molybdenum, or mixture thereof, after which hydrogenate is routed to distillation. Olefins contained in low-boiling fraction are subjected to hydrofomylation comprising above-indicated stages. Bottom fractions obtained in all process stages are processed together in common reaction product separation stage.

EFFECT: increased yield of desired product due to improved technology.

19 cl, 3 dwg, 2 tbl, 6 ex

 

Description

The present invention relates to a method for producing aldehydes from 7-25 carbon atoms through a multi-step catalyzed by cobalt or rhodium hydroformylation corresponding olefins.

Higher aldehydes, particularly those containing from 7 to 25 carbon atoms, can be obtained, as is known, the catalytic hydroformylation (technically often called the oxo-synthesis) olefins containing one carbon atom less. Aldehydes can be used, for example, as a preliminary step in the synthesis in the production of carboxylic acids and as fragrant substances. They are often technically translated by catalytic hydrogenation into the corresponding alcohols, which are used, along with others, as intermediates in obtaining the softeners (plasticizers and detergents.

How hydroformylating olefins are widely described in the literature. The choice of the catalytic system and the optimal reaction conditions for hydroformylation depends on the reactivity of the olefins used. Influence of structure used olefins on their reactivity in the process of hydroformylating described, for example, in J. FALBE, "New Syntheses with Carbon Monoxide", Springer Verlag, 1980, Berlin, Heidelberg, New York, page 95 ff.

As a rule, it is usually assumed that the reaction rate guide is formirovaniya at constant framework conditions decreases with increasing number of carbon atoms and with decrease in the degree of branching of the olefins. Thus, the reaction rate is linear olefins compared to branched isomers may be increased by the amount more than a tenth of a degree. Additionally decisive influence on the reactivity is the position of the double bonds of the olefin. Olefins with terminal double bonds react much faster than isomers with double bonds within the molecule. The different reactivity of isomeric octanol investigated, for example, B.L. HAYMORE, A. van HASSELT, R. BECK, Annals of the New York Acad. Sci., 1983, 415, 159-175; B. CORNILS, W. A. HERRMANN, Applied Homogeneous Catalysis with Organicmetallic Compounds", Vol. 1&2, VCH, Weinheim, New York,1996.

The technical mixture of olefins used as doctow for synthesis hydroformylation often contain olefinic isomers various patterns with various degrees of branching, different position of the unsaturated double bonds and olefins of different molecular weight. This is especially true for mixtures of olefins formed during di-, tri-oligomerization and oligomerization with a higher degree of olefins of 2-8 carbon atoms or other easily accessible higher olefins or mixtures of olefins formed during cooligomerization called olefins. As typical examples of mixtures of olefins, technically relevant hydroformylation, can be called three - and tetrapropenyl, as well as di-, tri - and atributary.

In addition to the adverse effect on the selectivity there are two other aspects against the joint of hydroformylation is of olefin mixtures in one step to achieve a high degree of conversion. According to one of the relatively long reaction time at a pre-specified bandwidth (or reactor power) requires a relatively large volume of the reactor. This adversely, especially because the methods of hydroformylation we are talking about processes taking place at high pressure, and investments in working under pressure reactors exponentially increase with their size. According to the second aspect is limited to the regulation of the production properties of aldehydes, for example, defined n/sootnosheniem (ratio of compounds a normal (unbranched) and isomeric structures).

Method two hydroformylating olefins are known. In the European patent applications EP 0562451 and EP 0646563 describes hydroformylation mixtures containing 1 - and 2-butenes, with the first stage carry out the conversion of 1-butene heterogeneous reaction, and in a multiphase system, possibly with the addition of the reagent phase transition or solvent, and the second stage impose homogeneous dissolved catalyst. According to the European patent application EP 0562451 on both stages using rhodium catalysts, while according to the European patent application EP 0646563 the first stage using rhodium catalysts, and the second stage uses balcomie catalysts. According to the European patent application EP 0562451 not affected by turning on the first stage of the olefin, predominantly 2-butene, hydroformylation at the second stage in a homogeneous phase and in the presence of rhodium as a catalyst. In European patent application EP 0646563 the nature of the process is specified that is not affected by turning on the first stage of the olefin is removed from the reactor in gaseous form together with carbon monoxide, hydrogen and formed during the hydrogenation of Bhutan. This gas may, after compression delivered to the second stage of hydroformylation. Methods according to these two publications are disadvantageous for use in hydroformylation higher olefins, i.e. containing more than five carbon atoms, so as not affected by the conversion of olefins due to their relatively high boiling point can not be removed in the gaseous state with the first stage with justifiable costs.

In the United Kingdom patent GB 1387657 describes a two-stage hydroformylation, in which the reaction product of the first stage is removed in the gaseous state and after separation by condensation of aldehydes or alcohols exhaust gas of the first stage, containing not affected by the conversion of olefins, partially return to the first step and the other part is sent to the second reactor. This concept of process suitable for hydroformylation volatile olefins containing not more than five carbon atoms, such as ethylene or propylene. For the transformation of higher olefins, such as in the previously mentioned methods, it is not appropriate, because the vapor pressure of the olefin (and aldehydes) is too small and therefore they must forcibly be processed in the liquid phase.

In the international application WO 95/08525 described two-step method of hydroformylation, in which the reaction mixture is removed from the first stage in the gaseous state. According to this method, be subjected to transformation should be able olefins containing from 2 to 20 carbon atoms, particularly from 2 to 8 carbon atoms. Hydroformylation catalyzed by rhodium, the catalyst is identical on both levels. In the example described, the propylene hydroformylation. Higher olefins containing more than five carbon atoms, do not allow technically advantageous to be subjected to transformation, as in the previously described methods, due to the relatively high boiling point doctow and products. Therefore, the transformation in the gas phase is energetically not favorable.

Another variant of the two-hydroformylation described in the German patent DE 3232557. On the first stage of olefins is subjected to hydroformylation in the use of the implement of the cobalt catalyst with a degree of conversion of 50-90%. Cobalt catalyst separated from the reaction mixture, and the formed aldehydes together with not subjected to conversion of the olefin is injected in the second stage of hydroformylation. Used modified ligands cobalt catalyst acts not only as a catalyst for subsequent hydroformylating olefins, but also as a catalyst for the hydrogenation of aldehydes to alcohols. In addition, formed on the first stage of aldehydes break the energy of the reaction conditions in the second stage. This leads to sequential reactions, especially reactions of condensation with the formation of high-boiling compounds.

Therefore, the objective of the invention is to provide a method for obtaining the highest oxalidales or the corresponding alcohols from olefins or mixtures of olefins, which combines a high degree of conversion with high selectivity, and, accordingly, fewer side products and/or consecutive reactions, and which, moreover, is characterized by high efficiency of use of space and time and offers more possibilities for controlling the properties of the product.

Therefore, an object of the present invention is a method of multi-step catalyzed by cobalt or rhodium hydroformylating olefins containing from 6 to 24 and the Ohm carbon, in alcohols and/or aldehydes, and olefins

a) are hydroformylating at the stage of hydroformylation to the degree of conversion of from 20 to 98 wt.%,

b) remove the catalyst thus obtained liquid product from the reactor,

C) share the thus obtained when hydroformylating liquid mixture of low-boiling fraction containing olefins and paraffins, and the fraction from the lower portion of the column containing aldehydes and/or alcohols,

g) contained in a low-boiling fraction olefins is subjected to conversion in the subsequent steps of the process comprising stages a), b) and C), and combine the fractions from the bottom of the column stage in all steps of the method.

Preferably the method according to the invention is carried out in such a way that the liquid product from the reactor stages of hydroformylating a) is a homogeneous liquid phase. Cobalt and rhodium catalysts are preferably used so that they are homogeneous dissolved in the liquid product release from the reactor stages of hydroformylating a).

The Department is not affected by the interaction of olefins formed from aldehydes is carried out after the separation is not used synthesis gas and catalyst in one or more stages of separation or distillation. Thus, the products of hydroformylation first stage of the method is not yet R is h are subjected to one or more subsequent stages of the favorable conditions of sequential reactions of hydroformylation.

The method according to the invention can be tailored to specific circumstances, preferably in two stages, periodically or continuously. When a continuous process various ways, which in the example is represented as a two-step process in figure 1-3. Subsequently, these types of the method are referred to as options 1, 2 and 3. It must be emphasized that the described variants of the method according to the meaning also suitable for methods with more than two degrees.

Obtained by means of the method according to the invention the crude aldehydes containing addition products of way - aldehyde and alcohol, formate, condensation products and other high-boiling compounds, is subjected to processing or distillation to separate the aldehyde, or first hydronaut, and then subjected to processing by distillation for the separation of alcohol.

Option 1

The method according to option 1 presented in the form of a flowchart in figure 1. In the first reactor for hydroformylating 1 serves olefinic mixture 3, the synthesis gas 2 (carbon monoxide and hydrogen), and the solution of the catalyst or catalyst precursor 4. Relieve pressure thus obtained in hydroformylation mixture 5, assign decompressional gas 7 (unused synthesis gas), and decompressional by the scientists at hydroformylating the mixture is freed from catalyst 4 during the first part of the catalyst 6, which is returned to the first reactor for hydroformylating 1, possibly after removal through the gateway a small part of the flow and recharge with fresh catalyst. Catalyst are referred to here as a preliminary stage (predecessors) education of catalysts, such as solutions of salts of divalent cobalt (II). Freed from catalyst obtained by hydroformylating the mixture is separated in a distillation column 9 on the low-boiling fraction 10, consisting in the overwhelming number of which have not undergone transformation aleinov and the crude aldehyde 11. Low-boiling fraction 10, synthesis gas 13 and the solution of the catalyst 16 is directed to the second reactor for hydroformylation 12. Hydroformylation on the second step of the method can be performed with the same catalytic system (both metal and ligand or the existing concentration) or with another catalytic system than on the first level. Obtained by hydroformylation mixture 14 from the second reactor to hydroformylation 12 is again subjected to decompression and assign decompression gas 17. Decompressional obtained by hydroformylation mixture 14 is released when the second part of the catalyst 15 from the catalyst 16, which is again sent to the second reactor for hydroformylation 12 may, after removal through a small gateway part II of the current and feeding fresh catalyst. Freed from catalyst obtained by hydroformylation mixture 18 is divided in the column 19 on the low-boiling fraction 20, comprising the vast amount of saturated hydrocarbons and crude aldehyde 21. If necessary, the portion of low-boiling fractions 20 may be returned to the reactor 12 (line 1 is not shown). Another implementation of this variant of the method is that, freed from catalyst obtained by hydroformylating a mixture of 18 without distillation in the column 19 is sent together with the crude aldehyde 11 in the hydrogenation of 22 (line 24). The crude aldehydes 11 and 21 or 11 and 24 hydronaut hydrogen in the reactor for hydrogenation of 22 with the formation of the crude alcohol 23, which may, by means not shown distillation process in pure alcohol. If the aldehyde is the base product, the hydrogenation unit 22 bypass and process the crude aldehyde (11 and 21 or 11 and 24) in the pure aldehyde, it is possible, by means not shown distillation.

In this form of the invention, each step of the way has its stage of hydroformylating a), the phase separation of the catalyst b) and stage distillation), provided that is separated in stage b), the catalyst directly or after processing returns to the step of hydroformylation and the same step of the way. Optional this VA is iant method can also be carried out so the last step of the way has no stage distillation).

Option 2

Block diagram of another embodiment of the method according to the invention are presented in figure 2. In the first reactor for hydroformylating 1 serves olefinic mixture 3, the synthesis gas 2 (carbon monoxide and hydrogen), and the catalyst 4 or its predecessor. Thus obtained when hydroformylating a mixture of 5 decompression, decompressional gas 7 (not used synthesis gas) assign and decompressional obtained by hydroformylation mixture is released when the first part of the catalyst 6 from catalyst 4, which may, after removal through the gateway a small part of the stream and feeding fresh catalyst is returned to the first reactor for hydroformylating 1. Freed from catalyst obtained by hydroformylation mixture 8 is directed to the distillation 9. There I share it together with freed from catalyst obtained by hydroformylation mixture 18 from the second reactor to hydroformylation 12 on the low-boiling fraction 10 that has not been subjected to the conversion of olefins and inert paraffins, and the crude aldehyde 19. After removal through the gateway part of the stream 11 for the separation of saturated hydrocarbons (paraffins) and other non-olefinic compounds of the low-boiling fraction 10 is sent together with the synthesis gas 13 and the catalysis of the torus 16 in the second reactor for hydroformylation 12. Thus obtained when hydroformylation mixture 14 decompression, assign decompressional gas 17, and decompressional obtained by hydroformylation mixture is released when the second part of the catalyst 15 from the catalyst 16, which returns to the second reactor for hydroformylation 12 may, after removal through the gateway a small part of the flow and recharge with fresh catalyst. Released from the second catalyst obtained by hydroformylation mixture 18 fuel obtained by hydroformylation mixture 8 of the first stage, as already mentioned, in the distillation column 9. The crude aldehyde 19 may be hydroformylating hydrogen in the hydrogenation unit 20 with the receipt of raw alcohol. This alcohol may again be processed into pure alcohol by means not shown in figure 1 distillation. If the target product is an aldehyde, the crude aldehyde 19 is converted into pure aldehyde by means not shown in figure 1 distillation bypass block hydrogenation.

The catalyst here are also called pre-stage (predecessors) preparation of catalysts, for example solutions of divalent cobalt (II). The second or any subsequent step of the method can be carried out with the same catalytic system (as with the metal and the ligand or the existing concentration) or with another system, than at the first stage of the method.

Remove through the gateway of saturated hydrocarbons instead of removal by separated flow 11 can also occur through processing of the divided stream is freed from catalyst obtained by hydroformylation product 18 (not illustrated). Technically this is feasible, for example by distillation separation of the flow on the low-boiling fraction is removed through the gateway, and aldehydes returned liberated from the catalyst obtained by hydroformylating a mixture of 18 or crude aldehyde 19.

This form of the invention has at each step of the way stage of hydroformylating a)and phase separation of the catalyst b), and the combined liquid obtained by hydroformylation mixture divided by the total stage distillation b) for low-boiling fraction and a fraction from the lower portion of the column, provided that is separated in stage b) of the catalyst returns to the stage of hydroformylating a) the same level of way either directly or after processing.

Option 3

The following variant of the method according to the invention are presented in figure 3. In the first reactor for hydroformylating 1 serves olefinic mixture 3, the synthesis gas 2 (carbon monoxide and hydrogen), and the solution of the catalyst or its precursor 4. Received this the way when hydroformylation mixture 5 together with those obtained by hydroformylation mixture 14 from the second reactor to hydroformylation 12 is subjected to decompression processing in a unified final product hydroformylation 15, and decompressional gas 7 assign. United final product hydroformylation released from the catalyst 16 in the separation of catalyst 6 and receive a mixture of 8 containing the formed aldehydes, alcohols, and is not affected by the conversion of olefins. The catalyst 16 is divided into two partial flow 4 and 17 may, after partial removal through the gateway and feeding fresh catalyst. Separated flow 4 return in the first reactor for hydroformylating 1 and otdeleniye 17 in the second reactor for hydroformylation 12. Freed from catalyst obtained by hydroformylating final product 8 are separated in a distillation column 9 on the low-boiling fraction 10 and the crude aldehyde 18. Low-boiling fraction 10 that has not been subjected to the conversion of olefins, possibly after removal through the gateway part number 11 (for the separation of saturated hydrocarbons or other non-olefinic compounds) are sent together with the synthesis gas 13 and the catalyst 17 in the second reactor for hydroformylation 12. The crude aldehyde 18 may be subjected to hydrogenation with hydrogen in the hydrogenation unit 19 with the formation of the crude alcohol 20. The latter can again be processed into pure alcohol by means not shown in figure 3 distillation. If the target product is an aldehyde, the unit Hydra is by 19 bypass and process the crude aldehyde 18 in the pure aldehyde by distillation (fig.z not shown).

In option 3, it is also possible to carry out removal through the gateway of saturated hydrocarbons by means of a separate processing stream obtained by hydroformylation mixture 14, for example by distillation separation of low-boiling fraction.

This form of the invention is characterized by the fact that the joint products release from the reactors at all stages of hydroformylation and pass only through a stage of separation of the catalyst b) and stage distillation), provided that separated at the stages of method b), the catalyst directly or after processing share and return on stage hydroformylation a) the individual steps of the method.

In this embodiment, the catalyst also includes the preceding stage (predecessors) of preparation of the catalyst, for example, solutions of salts of divalent cobalt (II).

In this variant of the method at all stages of hydroformylation, respectively, at all the steps of the method must be used the same catalyst, namely cobalt or rhodium as the active catalytic metal. However, it is possible to use different concentrations of the catalyst at various stages of the method, respectively, on their stages of hydroformylation.

In the method according to the invention may be partially or completely returned to the finishing process is slow unused synthesis gas. A particularly interesting possibility arises when the reactors for hydroformylation at different pressures. The gas exhaust from the reactor, operating at a higher pressure compared to the other reactors, can be separated at a pressure exceeding the working pressure in the other reactors, so that it can be used in other reactors without compression.

A common feature of the invention and, accordingly, variants 1 to 3 is hydroformylating olefins or olefin mixtures in several stages, preferably in two stages, with the first stage is subjected to transformation of the predominantly reactive olefins, and in subsequent stages - mostly inert olefins. Another important distinguishing feature of the invention is the separation contained in the low-boiling fractions are not affected by the conversion of olefins from liquid outlet products hydroformylation first stage after separation of the catalyst, mainly, by distillation. Significant differences between the individual variants consist of costs for recycling exhaust the reaction products. Thanks for separately circulating current circuit of the catalyst in option 1 creates the possibility of use in the reactor of different catalysts, different concentrate the walkie-talkies catalysts or different ligand systems. Option 1 is guaranteed the best Department in the process of dividing distillations paraffins, resulting as by-products of the reaction. However, it is possible to save at least one distillation and subjected to separation of the final product from different reactors for hydroformylation only one stage of distillation (option 2). Another reduction of the necessary machines is achieved when combining the circulation paths catalysts (option 3). Although you can no longer make use of various catalysts on the steps of the method, however, the concentration of catalyst in the reactor can be adjusted ratio when splitting the return flow of catalyst (separated streams 4 and 17 in two-stage method according to figure 3). The reaction conditions such as pressure, temperature and so forth, remain selectable independently of one another for each stage of hydroformylation.

Reactors in which the conduct hydroformylation, may be the same or different at all steps of the way. Examples of the types of reactors can be bubble columns, loop reactors, jet nozzle reactors, reactors with mixing device and tubular reactors, which can be partially implemented in the form of a cascade and/or installed.

Eductae way to show who I am the olefin or mixture of olefins with 6-24 carbon atoms, preferably 6-20 carbon atoms, in particular from 8 to 20 carbon atoms, and with terminal or internal unsaturated double bond C-C. the Mixture may consist of olefins with equal close (±2) or clearly different (more ±2) the number of carbon atoms. As olefins, which can be used as educt in pure form and in mixtures of isomers or in a mixture with other olefins with a different number of carbon atoms can be mentioned, for example, 1-, 2 - or 3-hexene, 1-hepten, linear Heptene with internal unsaturated double bond (2-hepten, 3-hepten and so on), a mixture of linear heptanol, 2 -, or Z-methyl-1-hexene, 1-octene, linear octanol with internal unsaturated double bond, mixture of linear octanol, 2 - or 3-methylheptane, 1 nonene, linear noneno with internal unsaturated double bond, mixtures of linear octanol, 2-, 3-or 4-methyloctane, 1-, 2-, 3-, 4 - or 5-mission 2-ethyl-1-octene, 1-dodecene, linear dodecanol with internal unsaturated double bond, mixtures of linear dodecanol, 1-tetradecene, linear tetradecanol with internal unsaturated double bond, mixtures of linear tetradecanol, 1-hexadecene, linear hexadecanol with internal unsaturated double bond, mixtures of linear hexadecanol. Suitable eductae in addition to this are, among others, obtained as a byproduct of productare dimerization of propene mixture of isomeric hexene (ditropan), obtained as by-products of the dimerization of butenes mixture of isomeric octanol (debute), obtained as a by-product of the trimerization of propanol mixture of isomeric noneno (tryprophan), obtained as a by-product of tetramerization of propene or tetramerization of butenes mixture of isomeric dodecanol (tetrapropyl or tribute), obtained as a by-product of tetramerization of butenes mixture of hexadecanol (terabyte), and olefin mixtures obtained by cooligomerization olefins with different numbers of carbon atoms (preferably from 2 to 4)may, after distillation into fractions with the same or closest number (±2) of carbon atoms. Further, there may be used the olefins or olefin mixtures obtained by Fischer-Tropsch synthesis. In addition can be used olefins obtained by olefination or other technological processes. The preferred eductae are a mixture of isomeric octanol, noneno-dodecanol or hexadecanol, i.e. oligomers of lower olefins, such as n-butenes, isobutene or propene. Other equally well suitable eductae are oligomers of olefins containing 5 carbon atoms.

For the oligomerization of butenes with obtaining mixtures containing mainly olefins with up to 8 carbon atoms, there Principia is Ino three variants of the method. Long known oligomerization in the presence of acidic catalysts, and technically used, for example, zeolites or phosphoric acid media. You get isomeric mixture of branched olefins, representing mainly dimethylhexane (international application WO 92/13818). Similarly, used worldwide method is to oligomerization in the presence of soluble Nickel complexes, known as the DIMERSOL-way (B. CORNILS, W. A. HERRMANN, Applied Homogeneous Catalysis with Organicmetallic Compounds", Vol. 1&2, VCH, Weinheim, New York, 1996). The third option is the oligomerization on the fixed layer of Nickel catalysts. The way entered the literature as OCTOL process (Hydrocarbon Process., Int. Ed. (1986) 65 (2. Sect.l) Siete 31-33).

To obtain according to the invention a mixture of alcohols with 9 carbon atoms, are suitable, in particular, as plasticizers used mainly a mixture of olefins with up to 8 carbon atoms, derived from remotemachine of butenes on OCTOL process.

Used for hydroformylation synthesis gas of carbon monoxide and hydrogen, in General, are in a molar ratio of from 1:4 to 4:1 and preferably in a stoichiometric ratio.

In the method according to the invention are cobalt or rhodium catalysts with complex-stabilizing additives, such as organic phosphines and ospiti, and without them. At all stages of hydroformylation possible to work both with rhodium catalysts and cobalt catalysts. In addition, it is possible to use as the first stage of the method at the stage of hydroformylating a) a cobalt catalyst (alternative: rhodium catalyst), and on the stages of hydroformylation subsequent stages - rhodium catalysts (alternative: cobalt catalysts). The advantage of the method according to the invention is the use of the separate stages of various catalysts, so when more than two levels in the way you can also work with various catalysts, such as cobalt/rhodium/cobalt.

The choice of catalyst and the reaction conditions (concentration of catalyst, temperature, pressure, residence time) depends, among other things, on the number of carbon atoms and the composition of the starting olefins. If the criterion of high quality product is the high content of hydroformylating on the ends of olefins, it is very good quality at a satisfactory product yield is achieved, for example, a mixture demonizovana n-butenes, known as di-n-butene, if in a two-stage method is used in both stages of unmodified cobalt catalysts. If you use the first stage unmodified cobalt ka is alistar, and in subsequent stages - unmodified rhodium catalyst, the product yield is improved, while the quality of the product is somewhat reduced. To further improve product yield and reduce the quality of the product occurs, if at all steps use unmodified rhodium catalysts. If the criterion of the high quality of the product is low hydroformylating on the ends of olefins, it is a good quality product at very high output is achieved, for example, a mixture demonizovana n-butenes, known as di-n-butenes, if the two-stage method on both stages use unmodified rhodium catalysts. Using modified ligands of the catalysts, particularly when using rhodium and phosphorus ligands, the contents hydroformylating at the ends or not at the ends of olefins, moreover, can influence the choice of ligands. The optimal number of steps of the method as well as the optimal catalysts in the individual stages of hydroformylation for this specific source of the olefin easy to determine the approximate test. The concentration of catalysts in separate steps may be the same or different.

Temperature and pressure during hydroformylation different stupine the method can vary within wide limits depending on the catalyst and olefin mixture. As the first stage preferably the reaction involves reactive olefins, at the stages of hydroformylation subsequent steps it is advisable to establish more stringent reaction conditions in respect of temperature, amount of catalyst, time-keeping and so on.

Optimal conditions may vary from case to case depending on the objectives. For example, the optimization criterion can be achieved in conjunction useful use of space and time, increasing the selectivity or the desired properties of the product. As a rule, are of critical importance olefin composition of the educt and the choice of catalyst system and/or reaction conditions that determine the possible forms of implementation of the method according to the invention, which is economically optimal.

In the method according to the invention the degree of conversion of olefins in the stages of hydroformylation individual steps of the method ranges from 20 to 98%, in particular from 40 to 80%, particularly preferably from 50 to 75% (by choice of suitable single value).

On the following after the first stage of the method stages of hydroformylation other subsequent steps of the method, the degree of conversion of olefins, depending on the specific case, can reach at least 50%, preferably from 55 to 98%.

In im is e according to the invention is useful, to the reactor for hydroformylation you can install different reaction conditions. This makes it possible to align the conditions of hydroformylation with reaction activity input olefinic mixture. To minimize subsequent products and side reactions might occur, for example, be subjected to the conversion in the first reactor reactive olefins under more mild conditions so that there is almost not formed and subsequent by-products. Next the reactor was then subjected to hydroformylation, possibly with more severe conditions remaining olefin mixture consisting mainly of reactive-passive olefins. Thus, through various reaction conditions in the reactor may affect the distribution of isomers in the formed aldehydes.

Catalyzed by rhodium and cobalt processes hydroformylation differ mainly in their work settings. However, the main difference is in a completely different Department and return catalysts. In subsequent separately describes both methods.

How hydroformylation catalyzed by cobalt

In catalyzed by cobalt ways of hydroformylation can be used unmodified and/or modified cat the catalysts, that at each step of the method may be the same or different. The process of hydroformylating at any step catalyzed by cobalt process can be carried out according to a single-stage process described in the German patent application DE 19654340. In this process, the original substance, the cobalt salt solution, the organic phase and the synthesis gas is simultaneously introduced into the reactor parallel to the bottom, mainly through the mixing nozzle.

As compounds of cobalt is preferably used cobalt salts, such as formate, acetate or salts of carboxylic acids which are water-soluble. Particularly useful was cobalt acetate, which is used in the form of an aqueous solution containing cobalt in the calculation of the metal from 0.5 to 3 wt.%, mainly from 1.0 to 2.0 wt.%.

The organic phase contains be hydroformylating olefin and possibly additional aldehyde and/or alcohol, and we are talking about the aldehyde or alcohol, mainly formed as the reaction product of hydroformylation.

Of particular importance in the way, catalyzed by cobalt, is attached to the dosing starting materials in the reactor. The metering device must provide good mixing of the phases and the achievement of the highest possible surface phase exchange. Therefore, when catalyzed by cobalt is th hydroformylating it is useful to divide the reactor space in the reactor for hydroformylation through the construction of a small number of perforated sheets (minimum number = 1), vertically arranged with respect to the direction of flow (movement) of flow of the reactants and products. Through the reactor cascading down mixing is largely reduced in comparison with a simple bubble column, and the nature of the flow tubular reactor is aligned. Such technological measures that lead to improved both the yield and selectivity of hydroformylation.

If according to the invention using the stage of hydroformylation with a cobalt catalyst, it is carried out at a temperature from 100 to 250°and a pressure of from 100 to 400 bar. Particularly useful was the temperature from 100 to 210°and the pressure of the synthesis gas from 200 to 300 bar. The volume ratio of carbon monoxide to hydrogen in the synthesis gas is, in General, in the range from 2:1 to 1:2, mainly it is 1:1. The synthesis gas is mainly used in excess, for example up to three times the number in relation to the stoichiometric quantity.

Hydroformylating olefins with cobalt catalyst in the first stage of the process, which carry out the transformation of reactive olefins, carried out at a temperature in the range from 140°With up to 195°mainly from 160°185°C. the Degree of conversion of olefins at this stage too is as committed to the value in the range of 20 to 90%, mostly from 50 to 80%.

After the release from the reactor of the first stage of the method or the first stage of hydroformylation final product decompression to pressure from 10 to 15 bar and direct to the stage of liberation from cobalt catalyst separation, 6 in figure 1). At the stage of removal of cobalt final product (organic phase) is released from the carbonyl complexes of cobalt in the presence of "process water" air or oxygen at a temperature of from 130 to 190°C. the removal of cobalt are well known and are described in detail in the literature, as, for example, J. FALBE, "New Syntheses with Carbon Monoxide", Springer Verlag, (1980), Berlin, Heidelberg, New York, page 158 ff.

The removal of cobalt is carried out mainly in the completed nozzle bodies, such as the ring process, the autoclave (pressure vessel), which achieved the highest possible surface phase exchange. Exempt from cobalt product organic phase separated from the aqueous phase in consistently located the separating tank. The aqueous phase is "process water"containing perestraivanie from the organic phase recovered cobalt in the form of acetate/formate, cobalt, return to the oxo reactor the same level the whole way, or after removal through the gateway of its small quantity and is used mainly as a source of nutrients is to obtain the "in situ" cobalt complex catalyst.

Pre-carbonyl extraction of the catalyst and the actual hydroformylation carried out in a reactor according to German patent DE 19654340. It is also possible these stages of the method apparatus to separate from each other.

Organic product from the reactor, containing not affected by the conversion of olefins, aldehydes, alcohols, ether formic acid and high boiling compounds, after the stage of hydroformylation and separation of the catalyst returns to the stage distillation. Here the product from the reactor, are exempt from the cobalt catalyst and is not used synthesis gas, divided by the distillation of crude aldehydes/alcohols (fraction bottom of the column) and low-boiling fraction, which depending on the method and conditions of stage hydroformylation consists mainly not affected by the transformation of weakly reactive olefins and/or paraffins formed when hydroformylating olefins.

Released at the stage distillation from valuable products not affected by the conversion of olefins immediately thereafter send to the stage of hydroformylation subsequent stage of the method.

Catalyzed by cobalt hydroformylation in the method according to the invention is performed on the following for the first stage of the subsequent stages of the method, respectively, the stage is hydroformylation, at a temperature of from 160 to 220°mainly from 175 to 195°C. the Degree of conversion of olefins here tends to the value of at least 50%, preferably in the range from 50 to 95%, particularly preferably in the range from 55 to 98%.

Multistage method according to the invention provides the ability to achieve the desired degree of conversion of the olefins in the first stage by creating the appropriate reaction conditions, for example by selecting low concentrations of cobalt. In subsequent stages, where the transformation is subjected to more slowly reacting olefins, the reaction conditions can then be tightened, for example, by increasing the concentration of catalyst.

The steps of the method according to the invention, which uses a cobalt catalyst, particularly suitable for hydroformylation mixtures of isomeric olefins obtained by the oligomerization of propene and butenes. Typical oligomerization, mainly used as the base raw material for hydroformylation, according to the new method include the di-, tri - and tetraploid, as well as di-, tri - and tetrabutyl.

Hydroformylation catalyzed by rhodium

When catalyzed by rhodium way of hydroformylation can be used, modified and/or unmodified catalysts, which are each catalyzed radiostudio of hydroformylation may be the same or different.

These rhodium catalysts may be introduced into the process in the form of their active complexes. However, as a rule, it is technologically easier to generate active catalysts "in situ" from stable, can easily be stored rhodium compounds. Suitable compounds of rhodium are, for example, salts of two(II)- and three(III)-valent rhodium, such as chloride, rhodium(III)nitrate, rhodium(III)sulfate, rhodium(III), potassium sulfate, mixed potassium sulfate and rhodium, the rhodium carboxylate(II) or rhodium(III)acetate, rhodium(II) or rhodium(III), octanoate rhodium(II), nonanoic rhodium(II)oxide, rhodium(III)acid salts of rhodium(III), Tris-ammoniacarbonate(III). Further, suitable complexes of rhodium, such as bicarbonateitric rhodium, acetylacetoneiminates(I). Particularly suitable rhodium acetate, octanoate rhodium and nonanoate rhodium.

In the General case, add approximately from 1 to 500 mol of ligand, mainly from 3 to 50 mol ligand per 1 mol of rhodium. Fresh ligand can be added to any intermediate reaction product in order to maintain a constant concentration of free ligands.

The concentration of rhodium in the reactor for hydroformylation is in the range from 1 part in 106parts to 500 parts in 106parts, mainly in the range of 5 parts in 106parts to 200 parts in 106parts.

The choice of ligands, before oznacenych for use in the method according to the invention, not limited, but depends on the olefin and the desired products. Preferred ligands are ligands containing nitrogen atoms, phosphorus, arsenic or antimony. Particularly preferred phosphate ligands. The ligands can be one or Mnogotochie. The chiral ligands can be used as the racemate and enantiomer or diastereoisomer. As phosphorus ligands especially include phosphines, phosphine oxides, phosphites, phosphonites and phosphinite. Examples of phosphines include triphenylphosphine, Tris(p-tolyl)phosphine, Tris(m-tolyl)phosphine, Tris(o-tolyl)phosphine, Tris(p-methoxyphenyl)phosphine, Tris(p-forfinal)-phosphine, Tris(p-chlorophenyl)phosphine, Tris(p-dimethylaminophenyl)phosphine, ethyldiphenylphosphine, propylpiperazine, treboltenerife, n-butyl-diphenylphosphine, n-hexylbiphenyl, o-hexylbiphenyl, dicyclohexylphenylphosphine, tricyclohexylphosphine, tricyclohexylphosphine, three-edelfosine, three(1-naphthyl)-phosphine three-2-furifosmin, tribenzylphosphine, benzylpiperazine, tri-n-butylphosphine, triisobutylene, three-trebutien, bis(2-methoxyphenyl)-phenylphosphine, neopentylene-phosphine, alkaline, alkaline earth, ammonium and other salts of sulfated triphenylphosphine, such as Tris(m-sulfanilyl)phosphine, (m-sulfonyl)diphenylphosphine; 1,2-bis(di-cyclohexylamino)ethane; bis(DICEC-logexit spine)methane, 1,2-bis(diethyl-phosphino)ethane, 1,2-bis(2,5-diethyl-phospholane)benzene [Et-DUPHOS], 1,2-bis(2,5-diethylphosphino)ethane [Et-BPE], 1,2-bis(dimethylphosphino)ethane, bis(dimethyl-phosphino)methane, 1,2-bis(2,5-dime-telesforo)benzene [Me-DUPHOS], 1,2-bis-(2,5-dimethylphosphino)ethane [IU-TIME], 1,2-bis(diphenylphosphino)benzene, 2,3 bis-(diphenylphosphino)-bi-cyclo[2.2.1]hept-5-ene [NORPHOS], 2,2'-bis(diphenyl-phosphino)-1,1′-binaphthyl [BINAP], 2,2′-bis(diphenylphosphino)-1,1′-biphenyl [BISBI], 2,3-bis(diphenyl-phosphino)butane, 1,4'-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)-ethane, bis(2-diphenylphosphinoethyl)phenylphosphine, 1,1′bis-(diphenylphosphino)-ferrocene, bis(diphenylphosphino)methane, 1,2-bis(diphenyl-phosphino)propane, 2,2'-bis(di-p-tolylphosphino)-1,1′-binaphthyl, o-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane [DIOP], 2-(diphenylphosphino)-2′-methoxy-1,1′-binaphthyl, 1-(2-diphenylphosphino-1-Naftali)isoquinoline, 1,1,1-Tris-(diphenyl-phosphino)ethane, Tris(hydroxypropyl)phosphine.

Especially preferred phosphine is triphenylphosphine.

Examples of phosphites are trimethylphosphite, triethylphosphite, tri-n-propyl-pofit, triisopropylphosphine, tri-n-butylphosphate, triisobutylene, three-tert. butylphosphine, Tris(2-ethylhexyl) FOSFA, triphenylphosphite, Tris(2,4-di-trebutien)FOSFA, Tris(2-trebuil-4-methoxyphenyl)FOSFA, Tris(2-trebuil-4-were)FOSFA, Tris(p-cresyl)FOSFA. In addition, aricescu employed fosfatnye ligands, such as are described, inter alia, in European patent application EP 155508, U.S. patent US 4668651, US 4748261, US 4769498, US 4774361, US 4835299, US 4885401, US 5059710, US 5113022, US 5179055, US 5260491, US 5264616, US 5288918, US 5360938, European patent applications EP 472071 and EP 518241 and in the international application WO 97/20795. Preferably use triphenylphosphite, substituted preferably in anthopology relative to the ether group phosphite choice of 1 - or 2-isopropyl and/or tert. boutelou group.

Examples of phosphonites are metaldetection, phenyldimethylsilane, phenylmethanesulfonyl, 6-phenoxy-6N-dibenz[C, e][1,2]oxaphosphorin and their derivatives in which the hydrogen atoms are completely or partially substituted by alkyl, aryl or halogen atoms and the ligands described in the international application WO 9843935, the Japan patent JP-09-268152 and German patent application DE 19810794 and German patent applications DE 19954721 and DE 19954510.

Suitable phosphinite ligands are described, inter alia, in U.S. patent US 5710344, in the international patent application WO 9506627, in U.S. patent US 5360938, in the Japan patent JP 07082281. Their examples are diphenyl(phenoxy)phosphine and its derivatives in which the hydrogen atoms are completely or partially substituted by alkyl, aryl or halogen atoms, di-phenyl(methoxy)phosphine, diphenyl(ethoxy)phosphine, and so on.

Catalyzed by the rhodium hydroformylation, as a rule, carried out at a pressure of 1 to 300 bar, mainly at a pressure of from 15 to 270 bar. Used pressure depends on the structure of the source olefins used rhodium catalyst and the desired effect. For example, α-olefins can be converted into the corresponding aldehydes at a pressure of less than 64 bar with a high degree of useful use of space and time. For olefins with internal unsaturated double bond, in particular for branched olefins, on the contrary, it is higher pressure.

Temperature catalyzed by rhodium processes hydroformylation, in General, is in the range from 40°to 180°C, preferably from 60°C to 135°C. Temperatures above 100°has the technical advantage that the possibility of using the waste heat of reaction to heat the steam.

After hydroformylating a large part of the synthesis gas is removed by means of pressure relief. From the liquid outlet of the reaction product is separated by distillation catalyst (catalyst separation, for example, 6 and 15 in figure 1). The catalyst and possibly added ligands, stabilizers and so forth remain in the residue / as residue from the distillation. Therefore, it is advantageous to introduce high-boiling (more storable than the product and educt) an inert solvent, which dissolves the catalyst. Dissolved in Wysocki the statutory solvent catalyst may then directly back to the reactor. Especially advantageous to introduce as a high-boiling solvent formed during high-boiling by-products. Other suitable solvent is a high boiling ester, such as 2,2,4-trimethylpentanediol-1,3-monoisobutyrate, commercially known as Texanol.

For the technological implementation of the distillation separation of the catalyst used in various ways. Preferred is the separation of the catalyst solution by evaporation apparatus with a falling film (with a downward flow of liquid), evaporator short-haul or thin-film evaporator, or by combinations of these devices. The advantage of this combination may, for example, consist in the fact that in the first stage separates the still dissolved synthesis gas, as well as part of the product and still have the original olefins (for example, in the evaporation apparatus with a falling film) to the second stage (for example, thin-film evaporation apparatus) to perform the final separation of the catalyst.

As oxo-conversion of olefins is an exothermic reaction, to maintain the temperature in the reactor within the specified limits must be removed from the reactor heat. Increasing temperature generally causes increased formation of by-products and the decontamination cat who lyst. Often also desirable, if possible, isothermal process, as the reaction temperature can directly affect the composition of the product (for example, the ratio of the compounds of normal and isomeric structure, n/ISO-value).

The heat dissipation is possible to carry out various technical measures, for example, through the wall of the reactor, via a built-in cooler and so on. Technically it is advantageous to reduce the cost of heat. However, due to the different speeds of reaction when using olefin mixtures may, in particular, at the first stage due to exterminate to receive considerable heat, because here in reaction mainly involves components that are easily subjected to transformation in the oxo reaction.

The method according to the invention creates in this way by choosing the appropriate reaction conditions, for example by means of a low concentration of catalyst or additive inert solvent, to maintain heat, primarily in the first stage of the method is technically simple feasible deterrent framework.

Processing obtained by hydroformylation mixtures containing no catalyst

Product from the reactor, freed from the catalyst and is not used synthesis gas, as shown in Fig.1-3, separately or sovmestimost distillation of crude aldehydes and low-boiling fraction. Low-boiling fraction consists, depending on the method and its steps, mainly from not subjected to the conversion of olefins or paraffins produced by the hydrogenation of olefins. The bottom product of the column contains in addition to aldehydes and alcohols and even high-boiling by-products such as formate, acetate, saturated and unsaturated simple ether, ester, carboxylic acid, and condensation products. Freed from the catalyst, the product from the stage of hydroformylation divided into low-boiling fraction and the crude aldehyde in one or more distillation stages (Option 1)or on the common stage distillation (Options 2 and 3). The conditions of distillation depends on the boiling point of the components and, therefore, mainly on the molecular weight olefins and aldehydes. They are chosen taking into account the fact that the distillation process was not formed large quantities of any products. As they are, mainly, by the reaction of aldehydes at elevated temperatures moving in the opposite state, the distillation can be conducted at reduced pressure and, thus, to support the column of low temperature. However, it is also possible to carry out the distillation under normal pressure.

If the reaction product from stage hydroformylation subjected to reprocessing the e separation by distillation (Option 1), the low-boiling fraction from the first stage of distillation is directed to the following stages of the method (in the General case, the low-boiling fraction one step guide to the next step), and low-boiling fraction of the last stage of distillation are removed through the gateway, it is also possible to partially return to their previous level of hydroformylation. If the reaction product with various steps of the method are processed together (Options 2 and 3), the appropriate part of the low-boiling fraction before entering on the last step of the way or in the processing part of the flow of product from the last step to remove through the gateway in order to support the content of paraffins in the circuit at an acceptable level.

Consequently, it is possible to completely or partially remove the paraffin from the at least one low-boiling fraction.

Along with these, are also given in the description of the Options from 1 to 3, removal of the process, low-boiling fractions and, in particular, paraffins, can be considered more. If the separation of the catalyst and possibly also the distillation is conducted under reduced pressure, the portion of low-boiling fraction and, of course, the products are removed from the process through the vacuum system. After condensation of this part may be dropped from sufficient for a (partial) refund to which icesta to return to the process. Through separated unused synthesis gas, depending on the operating conditions, also remove the portion of low-boiling fractions and products that can be separated (e.g., condensation) and, if necessary, to take back or recycle.

The crude aldehyde in that case, if they are the target product, on the steps of a separate or co-processed by distillation in products by known methods.

It serves to separate by distillation or processing aldehydes combined fractions of the lower parts of the column with stage distillation) or cancellation stage distillation) on the last step of the method is combined fractions of the lower parts of the columns and the product of the last stage of separation of the catalyst b) method.

If, on the contrary, the target products are alcohols, crude aldehydes hydronaut normally in gaseous or liquid phase.

You can gidrirovanii or combined fractions of the lower parts of the column with distillation stages), or the refusal stage distillation) on the last step of the method is combined fractions of the lower parts of the columns and the final product of the last stage of separation of the catalyst b) method.

For hydrogenation can be used, for example, catalysts: copper/Nickel, copper/chromium, copper/chromium/Nickel, zinc/chromium, Nickel/molybdenum. Catalysis is ora may not contain media, or catalytic hydrogenation of the active substance or its precursor may be supported on a carrier, such as silicon dioxide or aluminum dioxide.

Preferred hydrogenation catalysts obtained by hydroformylation mixtures contain the choice from 0.3 to 15 wt.% copper or Nickel, as well as activators of 0.05 to 3.5 wt.% chromium and preferably from 0.01 to 1.6 wt.%, mainly of 0.02 to 1.2 wt.% the alkaline component on the carrier, preferably of aluminum oxide and silicon dioxide. Quantitative figures are for the not yet recovered catalyst. The alkaline component is optional.

The catalysts preferably used in a form in which they are opposed by a small stream, for example in the form of granules, balls or molded products such as tablets, cylinders, strangalia extrudates or rings. Before use, they should be activated, for example, by heating in a stream of hydrogen.

Hydrogenation, preferably liquid-phase hydrogenation, in General, carried out at the total pressure of from 5 to 30 bar, in particular in the range from 15 to 25 bar. Hydrogenation in the gas phase can also be carried out at reduced pressure, accordingly, a large amount of gas. When using multiple reactors for hydrogenation of total pressure in the individual reactors may be dyakovym or different in these limits pressure values.

The reaction temperature in the hydrogenation in the liquid or gas phase, typically is in the range from 120 to 220°With, in particular from 140 to 180°C.

Examples of such gidrirovanii described in the German patent applications DE 19842369 and DE 19842370.

After hydrogenation of the thus obtained reaction mixture is processed by distillation. The selected olefins, if necessary, can be returned to the stage of hydroformylation.

The following examples serve the purpose of explaining the invention, but without limiting its scope of use, as defined in the claims.

Example 1

The conversion of octene in two stages with different catalyst ligands.

In a 1 l autoclave was subjected to conversion of 100 g of 1-octene (>98% GC) at 85°and the pressure of the synthesis gas 20 bar. The rhodium catalyst was obtained "in situ" from octanoate rhodium and ligand 1.

Ligand 1

As the inert high-boiling solvent to the reaction was added to 200 ml of Texanol (2,2,4-trimethylpentanediol-1,3-monoisobutyrate). Installed the concentration of rhodium 40 parts in 106parts (based on the total weight). The ratio of phosphorus to rhodium (P/Rh) was 20/1. The conversion of olefin was followed up by the amount of absorbed synthesis gas. After the degree of conversion reached about 90%, greatly have not been registered almost no gas absorption, and the test was stopped. According to GC analysis (GC analysis) the degree of conversion was 91%, the formed aldehyde was 95% of nonanal. Analysis of residual olefins showed only traces of 1-octene. The main components were 2-octene, 3-octene and 4-octene formed by isomerization of 1-octene.

The test was conducted 6 times. The obtained products were combined and subjected to distillation. When this was received 43 g of a mixture of octanol. It was dissolved in 100 ml of Texanol and again subjected to hydroformylation at 120°and the pressure of the synthesis gas 50 bar in the autoclave of 500 ml, the Concentration of rhodium was 40 parts in 106parts. As a ligand was added Tris(2,4-di-trebutien)fosfat (P/Rh 20/1). In the process of this transformation was achieved quantitative conversion of olefin (GC).

The example shows that the first stage of using the catalytic system has a high n/ISO-selectivity, but only minor activity in hydroformylation of octanol with internal double bond such as formed in the first stage by isomerization of used n-octanol (cf P.W.N.M. van Leuwen et al., Organometallics 1996, 15, 835-847). However, they can be subjected to metamorphosis on the second stage when other test conditions. On the one hand, is also achieved high selectivity for the desired remotemachine of nonanal, and on the other article the Rhone, the best overall output compared to the original substance.

Example 2

Hydroformylation di-n-butenes in two stages with different catalysts.

In a 3 l autoclave with a stirrer was previously placed about 1000 g containing cobalt acetate water (the content of cobalt is about 1 wt.% based on the metal). With stirring (1000 rpm) was injected mixture at a pressure of synthesis gas 280 bar and regulation established temperature 170°C. after 7 hours, cooled to 60°and reduced pressure up to 100 bar. Then there was added 600 g of di-n-butenes (main components: 14% octanol, 60% of methylheptane, 26% 3,4-dimethylhexane). After ten minutes of stirring (1000 rpm) and the mixture was left to stand for 15 minutes. Separated aqueous phase. The phase di-n-butenes contained CARBONYLS of cobalt in concentrations 0,019 wt.% based on cobalt. This solution was subjected to transformation in 170°and the pressure of the synthesis gas 280 bar. The degree of conversion was determined by the amount of absorbed synthesis gas. When the degree of conversion of 70%, the reaction was interrupted. After cooling to 80°and pressure relief from the reaction mixture was removed from the flask cobalt by adding 5 wt.% an aqueous solution of acetic acid in the presence of air. Not containing cobalt organic phase was separated into fractions of residual olefins / a small amount of paraffin, aldehyde /alcohol and high boiling components.

Residual olefins (175 g major components: about 4% of octanol, 52% of methylheptane, 44% 3,4-dimethylhexane) immediately thereafter subjected to the transformation catalyzed by rhodium reaction analogously to Example 1. As the inert solvent were added 200 g of Texanol (2,2,4-trimethylpentanediol-1,3-monoisobutyrate). The concentration of rhodium was set to 200 parts in 106parts of rhodium. The molar ratio of ligand (Tris(2,4-di-trebutien)FOSFA) to rhodium was 20/1. The pressure was maintained constant at 50 bar, a temperature - 130°C.

After 6 hours, the autoclave was cooled, dropped the pressure and the final product was separated by distillation into fractions of residual olefins / a small amount of paraffin, aldehydes/alcohols and high-boiling components. Combined fractions aldehyde/alcohol from both reactions was first made with Raney Nickel to form alcohols. Alcohol yield after both stages of hydroformylation and hydrogenation was 87%.

Thus, according to the invention in a two-stage method achieved higher output, as in the single-stage method (comparative Example 6).

Example 3 (Improving the degree of conversion, reduction of by-products)

The test was performed in a pilot plant consisting of a reactor bubble column, thin-film evaporation apparatus and on stellazine device, which are indicated in figure 1, respectively, numbers 1-8. With this experimental setup it was possible to explore the essential aspects of the two-stage behavior of the process under laboratory conditions. In the bubble column was injected from the bottom to be hydroformylating olefin together with the excess synthesis gas and the high-boiling solvent containing the catalyst. In the upper part of the reactor were separated not affected by the conversion of synthesis gas. Liquid components (residual olefin, aldehyde, by-products, high-boiling solvent, catalyst) were sent to the thin-film evaporating device operating at reduced pressure to separate the formed aldehyde together with not subjected to the conversion of olefins from high-boiling components, in which was dissolved catalyst. As a high-boiling solvent used dioctylphthalate, which was filed in the reactor with a concentration of 20 wt.%. The concentration of rhodium in the reactor was 100 parts in 106parts. As a ligand was added Tris(2,4-di-trebutien)FOSFA). The ratio of P/Rh was 20/1. Bubble column maintained at a constant temperature of 120°by double-shirts. Operating pressure of the synthesis gas was equal to 50 bar.

Under the above reaction conditions, the circulation of the olefin was installed 2 to the/h di-n-butenes. Bubble column had a volume of 2.1 liters After a steady level of transformation, after 100 hours, the flow of matter came into balance. Separated in thin-film evaporation apparatus, and the mixture was divided into not affected by the conversion of olefins and educated aldehydes. From 200 kg di-n-butenes received 156 kg of aldehydes and 77 kg of olefin, which corresponded to the average degree of conversion of 61.5%. Simultaneously formed 130 g of high-boiling by-products, which are concentrated in the circuit of the catalyst.

Olefins are not affected by turning on the first stage, were again subjected to transformation in the experimental setup at the second stage of hydroformylation. The reaction conditions correspond to the conditions of the first stage, but the circulation of the olefin was reduced to 1 kg/h To establish equilibrium chose the period and 77 hours, during which underwent transformation of 77 kg of the olefin from the equilibrium period of the first stage. Received 65 kg aldehydes. Simultaneously formed 310 g of high-boiling by-products.

If you combine the results of both equilibrium periods, the result for 177 hours of the workflow received 221 kg aldehydes. Thus formed 440 g of high-boiling by-products.

Example 4 (Comparative example, a single stage hydroformylation)

For cf is Vania with Example 3 in the experimental setup when the former is equal to the conditions of the tests were administered 200 kg di-n-butenes for 177 hours (1.13 kg of olefin/h). This just got 198 kg of aldehyde. Simultaneously formed 490 g of high-boiling by-products.

Comparison of Examples 3 and 4 shows that when hydroformylation of olefin in two stages of the same amount of olefin used for an equal period of time turned out to aldehydes to 23 kg more. From this it follows that when the unit response hydroformylation two notches receive the best beneficial use of space and time than with a single-stage reaction. At the same time found that when a two-stage process, despite a higher degree of conversion, designed for both stages, as a result, there is less high-boiling by-products. This is of particular importance, since the processing of mixtures oxo-transformation of the rhodium catalyst remains dissolved in high-boiling components. The more high-boiling components must be removed through the gateway, the more rhodium should be subsequently measured.

Example 5

Sonali received two hydroformylation di-n-butenes.

1st level

A 5 l autoclave high-pressure mixing device and electric heating was subjected to hydroformylation 2000 g of di-n-butenes (composition shown in Table 1, column 2) in the presence of cobalt can produce the RA at a temperature of 175° And pressure of the synthesis gas 280 bar for 2 hours. Received the catalyst, which 640 g of an aqueous solution of cobalt acetate with cobalt concentration 1 wt.% treated synthesis gas for 7 hours at 170°and a pressure of 280 bar. After cooling and pressure relief formed carbonyl cobalt translated extraction of 2000 g of di-n-butenes in the organic phase, which was separated from the aqueous phase. The concentration of the catalyst based on cobalt metal in di-n-butenes was at 0.020 wt.% by weight di-n-butenes.

After cooling to 80°and pressure relief obtained by hydroformylating the mixture was freed from cobalt processing 5 wt.% aqueous solution of acetic acid in the presence of air. Not containing cobalt obtained by hydroformylation mixture was separated from the aqueous phase.

The process was performed four times under the same conditions. Not containing cobalt obtained by hydroformylation mixture together. Got 9432 g obtained by hydroformylation mixture. The composition of the mixture according to GC analysis (GC analysis) are shown in Table 2, column 2. In accordance with this, the degree of transformation of di-n-butenes was 67,2%, and the selectivity valuable product - 93,8%. Accordingly, the yield of valuable products amounted to 63.1%. Under the valuable product here and in the following refers to nonanal, nonanol and produced is water.

2nd level

7500 g not containing cobalt obtained by hydroformylation mixture from the first stage was subjected to distillation through one column for recovery is not affected by the conversion of olefins. Olefins were obtained in the form of a head of a faction, and at the bottom of the column contained valuable products and high-boiling components. The distribution of isomers in recovered octinomos mixture are shown in Table 1, column 3. Compared with fresh di-n-butenes content of dimethylhexane 23 wt.% the recovered olefin content of 45 wt.% dimethylhexane contained significantly more of these reactive passive olefins.

2000 recovered mixture of hydrocarbons having 8 carbon atoms (91,75 wt.% olefins with up to 8 carbon atoms, 8.25 wt.% paraffins with 8 carbon atoms) were subjected to hydroformylating a 5 l autoclave of 1-St stage at 185°and the pressure of the synthesis gas 280 bar for 3 hours. Cobalt catalyst prepared as at 1st level, and translated in the olefin phase. Its concentration in the calculation of the metallic cobalt was 0,050 wt.% by weight of olefin.

Obtained by hydroformylating the mixture was cooled to 80°, dropped the pressure and removed from the cobalt, as described in the 1st stage. Got 2448 g not containing cobalt obtained by hydroformylation mixture, which according to GC-analysis is the study (GC analysis) re are shown in Table 2, column 3. The degree of conversion of the olefin was 91%, and the selectivity valuable product - 83,7%. Accordingly, the output of valuable product of 76.2%.

The total degree of conversion of the olefin on both levels reached 97.2% with a selectivity valuable product 90.7 percent. Accordingly, the overall yield of valuable products amounted to 88,2% in relation to the used di-n-butenes.

Example 6 (Comparative example, a single stage hydroformylation di-n-butenes)

A 5 l autoclave high pressure used in Example 5 were subjected to hydroformylation 2000 g of di-n-butenes (composition shown in Table 1, column 2) in the presence of a cobalt catalyst at 185°and the pressure of the synthesis gas 280 bar for 3 hours. The catalyst was obtained as in Example 5. The concentration of the catalyst di-n-butenes in the calculation of the metallic cobalt was 0,040 wt.% by weight di-n-butenes.

After cooling to 80°With dropped pressure obtained by hydroformylation mixture and freed her from cobalt processing 5 wt.%-tion aqueous solution of acetic acid and air. After separation from the aqueous phase obtained 2485 g not containing cobalt obtained by hydroformylation mixture, whose composition is defined by GC analysis (GC-analysis), are shown in Table 2, column 4. When this is achieved the degree of transformation of di-n-butenes 92% while selectivity is i.i.d. product 88,5%. Accordingly, the achieved yield valuable product of 81.4%.

In multi-stage method according to the invention (Example 5) clearly achieved the best degree of conversion, selectivity and outputs of the product in comparison with the single-stage method (Example 6).

Table 1
The distribution of isomers used in the olefin
OlefinsDi-n-butenes (educt in PR,stage 1 and PR), wt.%Artenova mixture of educt in PR, 2nd degree), wt.%
Dimethylhexane2345
3-methylheptane6250
N-octane155

Table 2
Composition not containing cobalt exhaust products hydroformylation (calculated as anhydrous product)
Example 5, stage 1,Example 5, 2-stage,Example 6,
wt.%wt.%Wt.%
C8-olefins27,86,76,4
C8-paraffins2,510,83,1
With9-aldehydes48,845,252,7
Noninformed2,2the 5.74,2
With9-alcohols17.422,926,9
Storable1,38,76,7
components

1. The way multi-step catalyzed by cobalt or rhodium hydroformylating olefins with 6-24 carbon atoms in the alcohols and/or aldehydes, characterized in that

a) olefins are hydroformylating to the degree of conversion of from 20 to 98%,

b) the catalyst is removed from hydroformylating liquid product from the reactor,

C) the liquid mixture is separated into a low-boiling fraction containing olefins and paraffins, and the fraction from the lower portion of the column containing the aldehyde or mixture of aldehydes and alcohols, which in the case of hydroformylation in alcohols in the quality of the final product is subjected to hydrogenation in a hydrogenation catalyst comprising copper, Nickel, chromium, zinc, molybdenum, or a mixture thereof, and then the hydrogenation product sent for distillation,

g) contained in a low-boiling fraction olefins is subjected to transformation in subsequent stages of pic is BA, which includes stages a, b and C,

and combine the fractions from the bottom of column stages in all steps of the method.

2. The method according to claim 1, characterized in that each step of the way has its stage of hydroformylating a), the phase separation of the catalyst b) and stage distillation), provided that is separated in stage b), the catalyst directly or after processing returns to the step of hydroformylating a) the same level.

3. The method according to claim 1, characterized in that each step of the way has its stage of hydroformylating a), the phase separation of the catalyst b) and to the last stage of the way one stage distillation), provided that is separated in stage b), the catalyst directly or after processing returns to the step of hydroformylating a) the same level.

4. The method according to claim 1, characterized in that each step of the way has its stage of hydroformylating a), the phase separation of the catalyst b), and the combined liquid obtained by hydroformylation mixture divided by the total stage distillation b) for low-boiling fraction and a fraction from the lower portion of the column, provided that separated at stages b) the catalyst directly or after processing returns to the step of hydroformylating a) the same level.

5. The method according to claim 1, characterized in that the joint products and the reactor with all stages of hydroformylating a) are only a stage of separation of the catalyst b) and stage distillation in) provided what separated in stage b) of the method, the catalyst directly or after processing to separate and return to the stage of hydroformylating a) the individual steps of the method.

6. The method according to one of claims 1, 2, 4, or 5, characterized in that the paraffins of at least one low-boiling fraction in whole or in part derive from the process.

7. The method according to one of claims 1, 2, 4, 5 or 6, characterized in that in the case of hydroformylation in alcohols in the quality of the final product combined fractions from the bottom of the column with distillation stages) is subjected to hydrogenation.

8. The method according to claim 1, 3 or 6, characterized in that in the case of hydroformylation in alcohols in the quality of the final product combined fractions from the bottom of the columns stages of distillation) or the product obtained from stage of separation of the catalyst (b) the last step of the method is subjected to hydrogenation.

9. The method according to one of claims 1, 2, 4, 5 or 6, characterized in that the separating by distillation the aldehydes contained in the combined fractions from the bottom of the columns stages of distillation).

10. The method according to one of claims 1, 3 or 6, characterized in that the separating by distillation the aldehydes contained in the combined fractions from the bottom of the columns stages of distillation and the resulting product from the stage of separation of the catalyst (b) the last stage of the method.

11. The method according to demo one of claims 1 to 10, characterized in that at each stage of hydroformylating a) use of cobalt catalysts.

12. The method according to one of claims 1 to 10, characterized in that at each stage of hydroformylating a) using rhodium catalysts.

13. The method according to one of claims 1 to 10, characterized in that at the stage of hydroformylating a) the first stage of the method using cobalt catalyst, and the stages of hydroformylation and subsequent steps of the method using rhodium catalyst.

14. The method according to one of claims 1 to 10, characterized in that at the stage of hydroformylating a) the first stage of the method using rhodium catalyst, and on the stages of hydroformylation and subsequent steps of the method using cobalt catalyst.

15. The method according to one of claims 1 to 14, characterized in that the liquid products from the reactor with the stage of hydroformylating a) represent a homogeneous liquid phase.

16. The method according to one of claims 1 to 15, characterized in that the cobalt or rhodium catalyst is homogeneous dissolved in the liquid products from the reactor with the stage of hydroformylating a).

17. The method according to one of claims 1 to 16, characterized in that the olefins in the stages of hydroformylation other steps of the method, following the first step of the method, is subjected to hydroformylation always to achieve the degree of transformation, at m is re, 50%.

18. The method according to 17, characterized in that the olefins in the stages of hydroformylation other steps of the method, following the first step of the method, is subjected to hydroformylation always to achieve the degree of conversion of from 55 to 98%.

19. The method according to one of claims 1 to 18, characterized in that it contains two steps.



 

Same patents:

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the hydroformylation process of olefins with using rhodium catalyst for preparing aldehydes comprising 3-21 carbon atoms. Reaction products from the hydroformylation reactor are separated for: (a) gaseous and liquid phase; (b) liquid phase is fractionated for a head fraction containing unreacted olefins and aldehydes and a vat fraction containing by-side products and rhodium catalyst, and (c) the vat fraction is cooled to temperature lower than the hydroformylation point into reactor, preferably, to 10-120°C. Then the vat fraction is saturated with carbon monoxide-containing gas under partial pressure of carbon monoxide 0.1-300 bars. The vat fraction containing catalyst and carbon monoxide are recovered completely or partially into the hydroformylation reactor. Invention provides prolonged working life of catalyst due to prevention of its inactivation in stages for isolation of the end product.

EFFECT: improved preparing method.

11 cl, 3 tbl, 3 dwg, 2 ex

FIELD: chemical technology.

SUBSTANCE: invention describes a method for realization of the multiphase reaction of hydroformylation of olefins in tube reactor wherein a catalyst is in the continuum liquid phase and at least one the parent product is in the dispersed phase. The hydroformylation reaction is carried out at the loading coefficient B 0.8 or above that is calculated as a quotient from the pressure fall PD length value and the static pressure PS value wherein PD = Cw x g/2 x w2/D and PS = (M/V) x g wherein Cw means a tube reactor resistance coefficient; D means diameter of tube reactor; W means a flow rate moving; S means a density value of flowing phase; M means a weight flow of all components in reactor; V means a volume flow; g = 9.81 m/c2.

EFFECT: improved method, enhanced output of process.

11 cl, 1 dwg, 9 ex

FIELD: processes catalyzed by metal-phosphoro-organic ligand complexes when target product may be selectively extracted and separated from liquid product.

SUBSTANCE: Specification gives description of methods of separation of one or several products of decomposition of phosphoro-organic ligand, one or several reaction byproducts and one or several products from liquid reaction product synthesized continuously and containing one or several non-consumed reagents, catalyst in form of complex of metal-phosphoro-organic ligands, not obligatory free phosphoro-organic ligand, one or several said decomposition products of phosphoro-organic ligand, one or several said reaction byproducts, one or several said products, one or several non-polar solvents and one or several polar solvents by separation of phases where (i) is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several products expressed by ratio of distribution coefficient Ef1 whose magnitudes exceeds about 2.5; (ii)is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several decomposition products expressed by ratio of distribution coefficients Ef2 whose magnitude exceeds proximately 2.5; and (iii) is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several reaction byproducts expressed by ratio of distribution coefficients Ef3 whose magnitude exceeds approximately 2.5 (versions). Description is also given of continuous methods of obtaining one or several products (versions) and reaction mixture containing one or several aldehyde products.

EFFECT: increased conversion of initial materials and selectivity by product; avoidance or exclusion of deactivation of catalyst.

20 cl, 2 tbl

FIELD: methods of production of 1.3 alkandiol.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to production of 1.3 alkandiol by hydrogenation of the raw material, containing 3-hydroxyaldehyde at presence of a catalyst and a source of hydrogen, where as a source of hydrogen use a synthesis gas, and the catalyst represents a heterogeneous catalyst containing copper on the carrier; and also to the method of production of 1.3-alkandiol by conversion of an oxide in the process including a hydroformylation and hydrogenation. At that it is not obligatory to realize the indicated phases simultaneously in one reaction vessel. The reached technical result consists in essential reduction of the fixed value of equipment and in bringing to a "single-phase" production of 1.3-propandiol (or a similar 3-alcandil) from ethylene oxide (or a corresponding oxide).

EFFECT: the invention ensures essential reduction of the fixed value of equipment and reduction to a "single-phase" process of the propandiol or alkandiol production.

9 cl, 2 tbl, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing concentrate of butyric aldehydes by oxonation. Method is carried out by the hydroformylation reaction of propylene with synthesis-gas in two in-line connected reactors at temperature 120-150°C, under pressure 250-300 kgf/cm2 and with heat removing by circulation of cooling agent through Field's tubes installed in hydroformylation reactors followed by separation of reaction products. The hydroformylation process in the first reactor is carried out in regimen when the ratio of volume consumptions of cooling agent circulating in Field's tubes and propylene feeding into reactor is (18-28):1. Invention provides enhancing yield of end products, improving energetic indices due to effective heat transfer in the hydroformylation reactor.

EFFECT: improved preparing method.

1 tbl, 4 ex

FIELD: improved processes catalyzed by complexes of a metal- organophosphorous ligand.

SUBSTANCE: the invention presents the improved processes catalyzed by complexes of metal-organophosphorous ligand. The method of extraction includes: feeding of the indicated liquid reactionary product in the zone of separation, stirring of the indicated liquid reactionary product with production by separation of phases of a polar phase containing one or several unreacted reactants, a complex catalyst metal- organophosphorous ligand, not obligatory free organophosphorous ligand and one or several polar dissolvents; and a nonpolar phase containing one or several products of decomposition of the organophosphorous ligand, one or several by-products of the reaction and one or several products. Further the method provides for the stages of withdrawal from the zone of separation and feeding into the reaction zone and-or into the zone of separation. In the given method selectivity of the polar phase for the organophosphorous ligand concerning one or several products is expressed by a ratio of distribution coefficients Efl, which has a value more than approximately 2.5; (ii) the selectivity of the polar phase for the organophosphorous ligand concerning one or several decomposition products of the organophosphorous ligand is expressed by a ratio of distribution coefficients Ef2, which has a value more than approximately 2.5; and (iii)the selectivity of the polar phase for the organophosphorous ligand concerning one or several by-products of reaction is expressed by a ratio of distribution coefficients Ef3, which value is more, than approximately 2.5. The method allows to reduce a negative effect on the process, for example, on prevention of a decrease of efficiency of the catalyst, conversion of the initial material and selectivity by a product.

EFFECT: the invention ensures reduction of a negative effect on the process, on efficiency of the catalyst, on conversion of the initial material and selectivity by a product.

20 cl, 2 tbl

The invention relates to an improved method of separating one or more products from the liquid reaction product containing the catalyst in the form of complex compounds of a metal with an organophosphorus ligand, optionally free organophosphorus ligand, a non-polar solvent, the polar solvent is selected from the group comprising NITRILES, lactones, pyrrolidone, formamide and sulfoxidov, and named one or more products, the method comprises (1) mixing named liquid reaction product to obtain phase separation a nonpolar phase containing the above catalyst, optionally free organophosphorus ligand and called nonpolar solvent and a polar phase, contains named one or more products and a polar solvent, and (2) the Department called the polar phase from the named non-polar phase, and named the organophosphorus ligand has a distribution coefficient between the nonpolar solvent and the polar solvent of greater than about 5, and named one or more products is the distribution coefficient between the polar solvent and the nonpolar rastvorimo of the reaction product, containing the catalyst in the form of complex compounds with metal-phosphorus metal, optionally free organophosphorus ligand, a non-polar solvent and one or more products, the method comprises (1) mixing named liquid reaction product with a polar solvent selected from the group comprising NITRILES, lactones, pyrrolidone, formamide and sulfoxidov, to obtain phase separation a nonpolar phase containing the above-mentioned catalyst, optionally free organophosphorus ligand and called nonpolar solvent and a polar phase containing named one or more products and a polar solvent, and (2) the Department called the polar phase from the named non-polar phase, and named the organophosphorus ligand and named one or more products have the distribution coefficient between the nonpolar solvent and the polar solvent of greater than about 5, and named one or more products is the distribution coefficient between the polar solvent and the nonpolar solvent of greater than about 0.5

The invention relates to new furifosmin formula I

< / BR>
where n denotes an integer of 1 or 2; R1denotes a hydrophilic group selected from the following groups: -SO2M, -SO3M, -CO2M, -PO3M, where M represents inorganic or organic cationic residue selected from a proton, cations, alkaline or alkaline earth metals, ammonium cations -- N(R)4where R denotes hydrogen or C1-C14alkyl, and the other cations are based on metals, salts with acids: fullsleeve, fullcarbon, fullsleeve or furylphosphonous soluble in water; m denotes an integer of 1; R2denotes a hydrophilic group,- SO2M, -SO3M, -CO2M, RHO3M, where M denotes hydrogen or an alkaline metal salt with the acid fullsleeve, fullcarbon, fullsleeve or fullfactorial soluble in water, R denotes an integer from 0 to 2

The invention relates to a mixture of branched primary alcohols from C11to C36and to mix them sulfates, alkoxylated, alkoxylates and carboxylates, which have high washing ability in cold water and good biological degradability
The invention relates to a method for producing alcohols from 7-18 carbon atoms by hydroformylation corresponding olefins with synthesis gas in the presence containing cobalt catalyst of the organic phase with 50 - 220oC and a pressure of 100 to 400 bar, with subsequent hydrogenation of the thus obtained aldehyde

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for oxidizing liquid hydrocarbons in barrier discharge carried out in the bubble reactor with mixtures of oxygen with helium, argon or nitrogen. Method involves using helium, argon and nitrogen taken in the amount 20-80%. The oxidation process is carried out in the presence of solid additives wherein aluminum, nickel, molybdenum, copper oxides or zeolite catalyst ZSM-5 comprising 1.2% of Fe is used. Method provides reducing energy consumptions for oxidation of the parent hydrocarbon in the barrier discharge.

EFFECT: improved oxidizing method.

3 cl, 2 tbl, 10 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of alcohol comprising synthesis of olefins by the Fischer-Tropsch process followed by the hydroformylation reaction and isolation of mixture of alcohols. Hydrocarbon fraction with the content of linear olefins 10-45 wt-% is separated from products reaction synthesized by the Fischer-Tropsch process with using cobalt catalyst by distillation followed by its hydroformylation with carbon monoxide and hydrogen taken in the molar ratio hydrogen to carbon monoxide = 1.0-5.0. The reaction of synthesis is carried out in the presence of cobalt-base catalyst and a substituted or unsubstituted monophosphocycloalkane ligand followed by steps of hydrogenation and distillation. Invention provides preparing a composition with the content of linear (C7-C12)-alcohols 60 wt.-%, not less, high rate of reaction and high selectivity of the process.

EFFECT: improved method of synthesis.

8 cl, 3 tbl, 4 ex

FIELD: industrial organic synthesis.

SUBSTANCE: process involves aldol condensation of n-butyric aldehyde in presence of 1-3% aqueous NaOH solution to form 2-ethyl-2-hexenal, which is washed out to remove alkali residues and distilled on steam stripping rectification column to separate high-boiling products, after which it is hydrogenised on copper-chromium catalyst to produce 2-ethylhexanol. 2-Ethyl-2-hexenal distillation bottom residue is treated for 15-60 min with aqueous NaOH solution at 100-120°C and aqueous NaOH solution-to-bottom residue volume ratio 1:(4-10). Alakali effluent produced in n-butyric aldehyde aldol condensation stage is evaporated to NaOH concentration 15-30% and then utilized to treat 2-ethyl-2-hexenal distillation bottom residue, while water steam obtained from evaporation is used as vaporizing agent in stripping rectification column.

EFFECT: reduced (by a factor of 20-50) volume of alkali effluent in aldol condensation stage.

2 tbl, 10 ex

FIELD: petrochemical processes.

SUBSTANCE: alcohols such as tert-pentanol or tert-butanol are obtained via liquid-phase hydration of alkenes contained in hydrocarbon feedstock in presence of solid high-acidity catalyst at elevated temperature in two consecutive stages followed by separation of unreacted hydrocarbons from reaction mixture withdrawn, preferably via rectification, from the second stage and containing synthesized alcohols. In the first reaction stage carried out at higher temperature, reaction zone(s) comprises two liquid phases, of which phase containing basically water, is in essential weight excess and phase mainly containing hydrocarbon(s) is in dispersed state. Withdrawn is only or mostly (i) liquid stream containing mainly hydrocarbon(s), synthesized alcohol(s), and dissolved water and optionally (ii) liquid stream containing basically water and alcohol(s). The latter, in the second stage, is fed through distribution device(s) into one or several in series arranged reaction zones, water being introduced into one or several reaction zones separately, and liquid in the second-step reaction zones, operated at lower temperature, is maintained in homogenous or heterogeneous state wherein one phase containing basically water and alcohol(s) is in dispersed state and its weight does not exceed 25% of the weight of phase basically containing hydrocarbons and alcohol(s).

EFFECT: increased conversion of feedstock and accelerated reaction.

12 cl, 1 dwg, 3 tbl, 6 ex

FIELD: organic chemistry, in particular production of high oxoalcohols.

SUBSTANCE: invention relates to method for production of high oxoalcohol from isomeric olefin mixture containing from 5 to 24 of carbon atoms. Claimed method includes hydroformylation in presence of catalyst at elevated temperature and elevated pressure. Hydroformylation in carried out in one step, and ones-through olefin conversion is limited in range of 40-90 %. Obtained reaction mixture after catalyst separation is preferably transferred to selective hydration carrying out at 120-220°C and pressure of 5-30 bar in presence of supported catalyst containing copper, nickel and chromium as active ingredients. Hydration product mixture is separated by distillation, and olefin fraction is recycled into hydroformylation step. As starting materials for hydroformylation mixtures of C8-, C9-, C12- or C16-olefins are used.

EFFECT: high olefin conversion ratio, selectivity, and capability.

15 cl, 1 dwg, 1 tbl, 2 ex

The invention relates to a method for producing aliphatic alcohols containing three or more carbon atoms, which are widely used as solvents, flotation agents, raw material for plasticizers, surface-active substances

The invention relates to a mixture of branched primary alcohols from C11to C36and to mix them sulfates, alkoxylated, alkoxylates and carboxylates, which have high washing ability in cold water and good biological degradability

The invention relates to an improved process for the preparation of isoamyl alcohol from fusel oil production of ethyl alcohol

The invention relates to the field of chemical technology, namely the improvement of the method of processing fusel oil

The invention relates to a method for production of 2-ethylhexanol - tonnage product of petrochemical synthesis

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of alcohol comprising synthesis of olefins by the Fischer-Tropsch process followed by the hydroformylation reaction and isolation of mixture of alcohols. Hydrocarbon fraction with the content of linear olefins 10-45 wt-% is separated from products reaction synthesized by the Fischer-Tropsch process with using cobalt catalyst by distillation followed by its hydroformylation with carbon monoxide and hydrogen taken in the molar ratio hydrogen to carbon monoxide = 1.0-5.0. The reaction of synthesis is carried out in the presence of cobalt-base catalyst and a substituted or unsubstituted monophosphocycloalkane ligand followed by steps of hydrogenation and distillation. Invention provides preparing a composition with the content of linear (C7-C12)-alcohols 60 wt.-%, not less, high rate of reaction and high selectivity of the process.

EFFECT: improved method of synthesis.

8 cl, 3 tbl, 4 ex

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