Method for preparing linear primary monoalcohols

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

 

This invention relates to a method for producing a composition of the alcohol(s), more specifically to a method for producing the composition of the alcohol(s), with a high degree of linearity.

Obtaining oxaspiro known in the art. One of the typical methods for obtaining such oxaspiro is hydroformylation of olefin in oxalicacid with subsequent hydrogenation of the obtained oxalicacid in oxopent. Hydroformylation usually carried out in the presence of a homogeneous catalyst, which is based on the source of the transition metal, usually metal of group 8 (iron, ruthenium or osmium), 9 (cobalt, rhodium or iridium) or 10 (Nickel, palladium or platinum) of the Periodic Table of Elements. In a catalytically active form, these metals can be used with the carbonyl ligands, but they can also be used in combination with other ligands, for example containing phosphorus ligands. Such catalysts usually referred to as phosphine and/or phosphatodilcoline catalysts hydroformylation.

Subsequent reaction, for example, hydrogenation of oxalicacid in the appropriate oxopent, occurs simultaneously with the reaction of hydroformylation. Some of homogeneous catalysts hydroformylation quite active for hydrogenation in situ obtained oxalicacid in the desired oxaspiro is. Sometimes, however, there is a separate final stage hydrogenation to improve the quality of the final oxaspiro from the point of view of the content of aldehyde.

Otsopirtti widely used as softeners or detergents. Typically, the plasticizer, based on the alcohols contain from 7 to 11 carbon atoms, and detergent-based alcohols contain from 12 to 15 carbon atoms. An important element in determining a plasticizer and detergent properties of the final oxaspiro is the linearity of the product. In this description under the linearity of alcohol refers to the weight ratio of linear primary monospitovo to the total number of alcohols. In General, the usual ecoprocess give alcohols having linearity from 50 to 60 wt.%.

The amount of olefin, downloadable for hydroformylation, is an important factor for the final properties of the resulting alcohol. In particular, is an important factor in the number of linear monoolefins in relation to the total amount of olefins present in the feedstock.

In one aspect, the invention aims to provide olefinic feedstock optimal number.

In the international application number WO 97/01521 described a method of obtaining products oxygenlive, usually aldehydes and alcohols, of saturated olefin feedstock, where the method includes the interaction,at the stage of hydroformylation, olefin product obtained by the reaction of the Fischer-Tropsch process, with carbon monoxide and hydrogen in the presence of a catalytically effective amount of catalyst hydroformylation and under the reaction conditions of hydroformylation, produce oxygenlive containing aldehydes and/or alcohols. Rich olefin feedstock typically contains from 35 to 100 wt.% olefins, of which from 50 to 100 wt.% olefins are linear a-olefins, from 0 to 60 wt.% - monomethionine branched a-olefins and from 0 to 10 wt.% - linear internal olefins. The minimum content of olefins in the raw materials used in the working examples, 50 wt.% (examples 9 and 10). Olefinic product obtained by the reaction of the Fischer-Tropsch process is a product obtained by processing the synthesis gas containing carbon monoxide and hydrogen under the reaction conditions of the Fischer-Tropsch catalyst Fischer-Tropsch based on iron, cobalt or iron/cobalt. A clear preference is given to catalysts of the Fischer-Tropsch iron-based, as evidenced by the fact that in all the working examples, which describe hydroformylation, the feedstock for hydroformylation based on the reaction product of a Fischer-Tropsch process, in which use rich iron catalyst.

In the method described in international application No. WO97/01521, the feedstock for the reaction of hydroformylation is a rich olefins feedstock, which is obtained by the interaction of carbon monoxide and hydrogen by reaction of the Fischer-Tropsch process with subsequent processing of the reaction product of a Fischer-Tropsch via distillation. Such distillation is required to produce a hydrocarbon fractions, which have a minimum olefin content of 35 wt.%.

However, the method according to WO-A-97/01521 leaves much to be desired in regard to the combination of the selectivity of alcohol when hydroformylating and linearity of the resulting alcohol. First of all, this is illustrated in the working examples of WO-A-97/01521: all, except one, the examples that used the original raw Fischer-Tropsch, linearity has typical values, while the selectivity for alcohol is not optimal. In a single example, which shows very high linearity 84% (example 5), the selectivity for alcohol is only 64%, which implies the formation of relatively large amounts of by-products. The degree of conversion of the olefin in this example is also relatively low: only 68%. Secondly, it was found that when using a long iron catalyst obtained olefin stream has a relatively high content of branched olefins. This is not favorable the La high linearity of the obtained alcohol in combination with high selectivity for alcohol. Finally, the high content of olefins in the feedstock to hydroformylation, which is a prerequisite according to WO-A-97/01521 implies that requires distillation of the reaction product of a Fischer-Tropsch in tough conditions.

The purpose of this invention is to overcome these shortcomings. More specifically, the present invention presents a method of obtaining oxaspiro hydroformylation of the reaction product of a Fischer-Tropsch that gives wysokowydajny alcohols in combination with high selectivity for alcohol at the stage of hydroformylation, thus limiting the quantity of generated by-products. The term "selectivity" in this description refers to the percentage ratio of the resulting alcohol products to the total number of products derived from converting olefins:

Further, in the method in accordance with this invention are achieved very high rate of conversion of the olefin, although this is not necessarily the use of raw materials for hydroformylation containing 35 wt.% or more olefins.

It has been unexpectedly discovered that by selecting certain types of catalysts at both stages of the reaction of the Fischer-Tropsch and hydroformylation wysokowydajny alcohol products can be obtained with very high selectivity to p the alcohol and speed of the transformation.

Therefore, the present invention proposes a method of obtaining the composition of the alcohol(s)containing one or more monospitovo at least 60 wt.% which are linear primary monoparty containing at least 7 carbon atoms, where the method involves the following stages:

(a) interaction of carbon monoxide with hydrogen under the reaction conditions of the Fischer-Tropsch process in the presence of a catalyst Fischer-Tropsch containing cobalt;

(b) separating from the product of stage (a)at least one fraction of hydrocarbons containing from 10 to 50 wt.% olefins containing 6 or more carbon atoms;

(C) the interaction of one or more hydrocarbon fractions obtained in stage (b)with carbon monoxide and hydrogen under conditions of hydroformylation in the presence of a catalyst of hydroformylation based on the source of cobalt and one or more alkylphosphines; and

(d) the selection of the composition of the alcohol(s).

The resulting composition of the alcohol(s) comprises at least 60 wt.%, more preferably at least 65 wt.% linear primary monospitovo C7+. Preferred compositions contain at least 65 wt.% primary monospitovo C10+. Normally, the maximum chain length primary monosperma present in the composition of the alcohol(s)is about 20 carbon atoms, more preferred is sustained fashion, 18 carbon atoms, and even more preferably 16 carbon atoms. The method in accordance with this invention is particularly preferred for obtaining compositions containing one or more linear primary monospitovo C11, C12, C13 and C14 as a main component, a particularly preferred composition of the alcohol(s), containing as main components a combination of primary monospitovo C12 and C13 or a combination of primary monospitovo C14 and C15. However, there can be obtained a composition of lower alcohols, namely compositions containing combinations of primary monospitovo C7, C8 and/or C9 and compositions containing combinations of primary monospitovo C9, C10 and/or C11.

At stage (a) of this method hydrocarbons produced by interaction of carbon monoxide and hydrogen in suitable conditions. In General, the preparation of hydrocarbons from a mixture of carbon monoxide and hydrogen at elevated temperature and pressure in the presence of a suitable catalyst known as the synthesis of hydrocarbons by the Fischer-Tropsch. The catalysts used in the synthesis of hydrocarbons, usually referred to as catalysts for Fischer-Tropsch, and they usually include one or more metals of groups 8, 9 and 10 of the Periodic Table of the Elements, optionally together with one or more promoters, and the media. In particular, iron, Nickel, cobalt and Rute is s are well known catalytically active metals for such a catalyst. The catalyst for the Fischer-Tropsch process used in stage (a) of this method, however, must contain cobalt as the catalytically active metal. The catalyst also contains porous media, in particular media based on refractory oxide. Examples of suitable carrier materials based on refractory oxides include aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide or mixtures thereof such as silica - alumina, or physical mixtures, such as silicon dioxide and titanium dioxide. The most suitable carriers are those that contain titanium dioxide, zirconium dioxide or mixtures thereof. Preferred media based on titanium dioxide, in particular, titanium dioxide, which is obtained in the absence of sulfur-containing compounds. These carriers can also contain up to 50 wt.% another refractory oxide, typically silicon dioxide or aluminum oxide. More preferably, the additional refractory oxide, if present, comprises up to 20 wt.%, more preferably up to 10 wt.% from the mass media.

Typically, the catalyst contains 1-100 mass parts of cobalt (calculated as the element), preferably 3-60 mass parts and more preferably 5-40 mass parts, per 100 mass parts of the carrier. These quantities of cobalt relate to the total number of cobalt in ale nteu form and can be determined by known methods of elemental analysis.

In addition to the cobalt catalyst may contain one or more promoters that are known to specialists in this field of technology. Suitable promoters include manganese, zirconium, titanium, ruthenium, platinum, vanadium, palladium and/or rhenium. The amount of promoter, if present, is usually from 0.1 to 150 mass parts (per element), for example, from 0.25 to 50, more preferably from 0.5 to 20, more preferably from 0.5 to 10 mass parts per 100 mass parts of the media.

Usually the catalyst for Fischer-Tropsch does not contain alkali or alkaline earth metals, in addition to possible impurities trapped with the source material in the preparation of catalysts in accordance with this invention. Typically, the atomic ratio of alkali or alkaline earth metal to cobalt is less than 0.01, preferably less than 0,005.

The conditions of the Fischer-Tropsch process used in stage (a) of the method in accordance with this invention include a temperature in the range from 125 to 350°C, preferably from 160 to 275°S, more preferably from 175 to 250°S, even more preferably from 190 to 240°With, especially from 190 to 235°and a pressure in the range from 5 to 150 bar (abs.). Stage (a) of the method in accordance with this invention may be conducted in a commonly used pressure, for example up to 0 bar (abs.), preferably up to 65 bar (abs.), but can also be applied more pressure.

In a preferred embodiment of the present invention stage (a) includes the interaction of carbon monoxide with hydrogen at a temperature in the range from 125 to 350°and at a pressure of from 5 to 150 bar, in the presence of a catalyst containing cobalt on the media containing titanium oxide. It is convenient to choose the catalyst and the process conditions at the stage of (a) so that the product obtained at stage (a)contain from 2 to 20 wt.% hydrocarbon fractions C11-C14, where hydrocarbon fractions contain from 10 to 50 wt.%, from the total mass of this fraction of monoolefins C11-C14. This can be achieved, for example, the use of the catalyst for the Fischer-Tropsch cobalt-based and titanium dioxide at temperatures from 175 to 275°and an operating pressure of 30 to 65 bar (abs.).

In another preferred embodiment of this invention, the pressure applied at the stage (a)is at least 40 bar, preferably at least 50 bar. Most preferably the pressure is from 50 to 150 bar, more preferably from 55 to 140 bar. Working temperature at this pressure can be those which are usually used, but the preferred operating temperature at the specified pressure ranges from 150 to 250°S, more preferably from 160 to 30° C.

Hydrogen and carbon monoxide (synthesis gas) is usually served in a reactor in a molar ratio of from 0.5 to 4, preferably from 0.5 to 3, more preferably from 0.5 to 2.5, especially from 1.0 to 1.5. These molar ratio is preferable to use a reactor with a fixed bed.

The reaction of the Fischer-Tropsch stage (a) can be carried out in reactors of different types and under different conditions of reaction, for example, in the fixed layer, in suspension or in the fluidized bed. It is clear that the particle size of the catalyst may largely depend on the selected mode of response. Specialist in the art can select the most suitable particle size of the catalyst for this mode of reaction.

Further, it should be clear that the specialist in the art can select the most suitable conditions for the reactor specific configuration and mode of action. For example, the preferred hourly space velocity of the gas may depend on the type of mode of response. Thus, if it is desirable to carry out the synthesis of hydrocarbons in the mode of the fixed layer, preferably hourly space velocity of the gas was in the range from 500 to 2500 nl/l/h. If it is desirable to conduct the process of synthesis of hydrocarbons in suspension, preferably hourly space velocity of the gas was the from 1500 to 7500 nl/l/h.

After the interaction of carbon monoxide and hydrogen with obtaining hydrocarbon product at the stage of (a), at the next stage (b) derived hydrocarbon product is separated into one or more hydrocarbon fractions containing from 10 to 50 wt.%, preferably from 15 to 45 wt.% olefins containing 6 or more carbon atoms. Very good results are achieved when the separation of the hydrocarbon at the stage (b) at least one hydrocarbon fraction containing less than 35 wt.% olefins. It was found that this fraction, which has a relatively low content of olefins, is also a very good feedstock for hydroformylation at the stage (C), and also gives products - alcohols with high linearity and excellent selectivity for alcohol. Preferably, the separation stage (b) comprises distillation, namely, fractional distillation. Can be applied by conventional methods of distillation.

The separation stage (b) can be carried out by fractional distillation, but may also include a combination of distillation with other methods of separation, such as condensation and/or extraction.

In a preferred embodiment, the hydrocarbon fraction allocated after fractional distillation in stage (b)represent the fractions C8-C10, C11-C12 and C13-C14, each of which contains at least 5 wt.%, bol is E. preferably, at least 2 wt.% neighboring hydrocarbon fractions. Also the fraction of C6-C8 is the preferred fraction containing at least 5 wt.%, more preferably at least 2 wt.% neighboring hydrocarbon fractions of C5 and C9. Each faction hydrocarbon with the number of carbon atoms n (i.e. n is an integer from 6 to 14) preferably contains from 10 to 50 wt.%, more preferably from 20 to 45 wt.% Cn-olefins. However, as already mentioned, the hydrocarbon fraction containing less than 35 wt.% olefins are also very useful. Such hydrocarbon fractions can be used separately as a source of raw materials for stage hydroformylation (C), but two or more of these fractions can also be combined into a feedstock for hydroformylation at the stage (C). The method in accordance with this invention is particularly suitable for use on stage (C) hydrocarbons C11-C12 and hydrocarbons C13-C14.

At the stage (C) is hydroformylation. For purposes of this invention it was found that very preferably be used as feedstock for the stage (s):

(1) hydrocarbons containing at least 30 wt.% n-alkanes C11 and C12 and from 15 to 50 wt.% linear monoolefins C11 and C12 (i.e. including 1-olefins to 2-olefins and internal olefins), or

(2) a hydrocarbon raw material containing, on ENISA least 30 wt.% n-alkanes C13 and C14 and from 10 to 45 wt.% linear monoolefins C13 and C14.

The above-described raw materials (1) preferably contains from 55 to 75 wt.% n-alkanes and from 20 to 45 wt.% linear monoolefins C11 and C12 at least 75 wt.%, and preferably at least 80 wt.% which are linear mono-a-olefins C11 and C12. In addition to the n-alkanal and monoolefins the feedstock may also contain relatively small amounts of other components (usually up to a total amount of 15 wt.%, preferably, less than 10 wt.%, and more preferably less than 7 wt.%), such as alcohols, n-alkanes C10 and C13, C13 olefins+, branched olefins, and branched alkanes.

The above-described raw materials (2) preferably contains from 60 to 80 wt.% n-alkanes and from 15 to 40 wt.% linear monoolefins C13 and C14, at least 70 wt.%, and preferably at least 80 wt.% which are linear mono-a-olefins, C13 and C14. In addition to the n-alkanal and monoolefins the feedstock may also contain relatively small amounts of other components (usually up to a total amount of 15 wt.%, preferably, less than 10 wt.%, and more preferably less than 8 wt.%), such as alcohols, n-alkanes, C12 and C15, C15 olefins+, branched olefins, and branched alkanes.

The catalyst hydroformylation used in stage (C), based on the source to which Balta and one or more alkylphosphine, more specifically, it is a modified phosphorus-containing ligand of the catalyst based on cobalt. Such catalysts are well known in the art and, for example, described in U.S. patentsâ„–â„– 3239569; 3239571; 3400163; 3420898; 3440291 and 3501515, which are incorporated here by reference. For the purposes of this invention, however, it was found that particularly preferable to apply homogeneous catalysts hydroformylation containing cobalt as the catalytically active metal, in combination with either trialkylphosphine or optionally substituted monophosphorylation as ligands. Particularly preferred substituted or unsubstituted monophosphorylated. Therefore, especially preferred catalysts are the catalysts that are based on the source of cobalt and monophosphorylation the ligand, where the phosphorus atom is substituted by hydrogen or neuchatelois hydrocarbon containing from 1 to 36 carbon atoms (for example, alkyl or aryl), and the phosphorus atom is a member of the bridge connection, not being a atom in the head of the bridge, and the specified monophosphorylated has from 7 to 46 carbon atoms, where 7 or 8 carbon atoms together with the phosphorus atom are members of the bicyclic skeleton structure. Preferred monophosphorylated the new ligands are (i) alkyl substituent, containing from 4 to 30, more preferably from 5 to 25 carbon atoms, or a phenyl substituent or hydrogen, where (ii) 8 carbon atoms together with the phosphorus atom form a bicyclic skeleton structure. Particularly preferred ligands are 9-eicosyl-9-phosphabicyclo[4.2.1]nonan; 9-eicosyl-9-phosphabicyclo[3.3.1]nonan; 9-phenyl-9-phosphabicyclo[4.2.1]nonan and 9-phosphabicyclo[4.2.1]nonan. These ligands, as well as receive them, are described in U.S. patent No. 3400163, and their use in the reaction of hydroformylation described in U.S. patent No. 3420898, each of which is incorporated here by reference.

Alkylphosphine used in an amount such that the molar ratio of alkylphosphine to cobalt ranged from 0.5 to 2, preferably from 0.6 to 1.8. In addition to cobalt and alkylphosphine catalyst hydroformylation may also include additional components to improve system stability Co/phosphine and/or to improve the selectivity of alcohol. Suitable additional components include strong bases such as KOH and NaOH, which is particularly preferred is a CON. An additional component is usually used in an amount such that the molar ratio of this component to the cobalt ranged from 0 to 1.

The reaction hydroformylation at the stage (C) can be carried out in normal conditions of hydroformylation. Accordingly, the right conditions include a reaction temperature in the range from 100 to 300° C, preferably from 125 to 250°C and a pressure of from 1 to 300 bar, preferably from 20 to 150 bar. The amount of catalyst relative to the amount hydroformylation of the olefin is not critical and can vary widely. Typical molar ratios of catalyst and olefin in the reaction mixture at any point during the reaction can be in the range of from 1:1000 to 10:1. Often used in a ratio of from 1:10 to 5:1. Hydroformylation may include a solvent that does not exert a significant effect on the desired reaction. Such solvents include saturated liquid organic solvents, such as alcohols, ethers, acetonitrile, sulfolane, waxes and many others. However, it is preferable not to use an additional solvent, and to use as a liquid reaction medium the flow of the reactants.

The ratio of carbon monoxide and hydrogen, used in stage (C)can vary widely. However, it is preferable that the molar ratio of hydrogen to carbon monoxide at the stage (C) ranged from 1.0 to 5.0, more preferably from 1.5 to 2.5.

Typically used in the synthesis gas, i.e. a mixture of carbon monoxide and hydrogen, but in principle both gas can be supplied into the environment for the reaction of hydroformylation independently from each other. Preferably, however, to apply the synthesis gas. Synthesis is what I usually get partial combustion of oil, and commercial synthesis gas typically contains hydrogen (H2) and carbon monoxide (CO) molar ratio of N2/WITH from 1 to 2.5. Synthesis gas can also have a higher molar ratio of up to 10.0, for example, synthesis gas, obtained by the reaction of the conversion of water gas and such synthetic gas can also be used. Accordingly, a suitable synthesis gas contains hydrogen and carbon monoxide in a molar ratio of N2/WITH from 1.0 to 10.0, preferably from 1.0 to 5.0. Most preferably the molar ratio of from 1.5 to 2.5.

Stage hydroformylation (C) can be conducted in continuous, semi-continuous or periodic mode. Using continuous mode hourly space velocity is typically from 0.1 to 10 h-1. When carrying out stage (C) in the periodic mode, the reaction time can vary from 0.1 to 10 hours or even longer.

When conducting stage hydroformylation (C), as described above, the selectivity for alcohol is at least 90% and even at least 92%, at the same time, the linearity of the resulting alcohol is at least 70 wt.%, preferably 75 wt.%, for monospitovo C7-C13, and at least 60 wt.%, preferably, at least 65 wt.% for alcohols C14-C15. In addition, the degree of conversion of the olefin is up to 95 wt.% or more, or even 99 wt.% or b is more.

Stage (d) of the method in accordance with this invention includes the selection of linear monosperma from the reaction product of hydroformylation. This can be achieved by methods known in the art.

In a preferred embodiment, stage (d) includes the steps of first distillation, saponification, washing, and the second distillation. Accordingly, in this process the reaction product of hydroformylation from stage (C) is first subjected to a first distillation, after which the resulting fraction containing alcohol, amyraut to remove acids and esters, followed by rinsing with water to remove sodium salts. Water-washed product is then subjected to a second distillation to remove the remaining impurities or by-products.

The first distillation is preferably yields an upper fraction containing a major portion (i.e. more than 50 wt.%, preferably, at least 70 wt.%, more preferably at least 80 wt.%) the obtained alcohol, and lower (cubic) fraction containing heavier components, together with the obtained alcohol. The bottom fraction conveniently be recycled, at least partly, and again subjected to distillation. Examples of suitable methods of distillation include a single equilibrium distillation and molecular distillation, where the latter is especially preferred for the data of the invention. However, there may be used other distillation methods.

(Top) fraction containing a major portion of the alcohol, obtained after distillation and then subjected to saponification to remove acids and esters, mainly esters-formate. Saponification is usually carried out by the interaction of the alcohol-containing fraction with an aqueous solution of a strong base is a hydroxide, typically sodium hydroxide (NaOH) or sodium borohydride (NaBH4), at elevated temperature and under stirring. For example, the saponification can be carried out by the interaction of the alcohol fraction with water to 0.5-10%, preferably 1-5%NaOH solution at a ratio of organic/aqueous phase from 10:1 to 1:1, preferably from 8:1 to 2:1, where the exact value depends on the calculated amount present esters and acids. The saponification may be carried out intermittently or continuously, with each faction alcohol usually omelet from one to three times. Normal temperature saponification range from 40 to 99°C, preferably from 60 to 95°C. due to mixing usually get the emulsion, which allows to carry out the saponification reaction. When you stop mixing occurs a separation of the phases, and the organic phase containing 90 wt.% or more alcohol, isolated for further processing.

The organic phase is allocated when the saponification, is subjected to a water rinse DL is remove the present salts of sodium. Usually such washing water comprises from one to five washes. Water washing is usually carried out by mixing the product of the saponification of water and the subsequent provision of opportunities for phase separation. Sodium salt contained in the aqueous phase. The aqueous phase and organic (alcohol-containing) phase is then separated. Details of a suitable washing water is well known to specialists in this field of technology.

To further increase the purity of the obtained alcohol washed with water, the alcohol is subjected to further distillation to remove components that are lighter and/or heavier than the desired alcohol. This separation of "top and tail" fractions can be carried out using conventional methods of distillation. For example, can be applied to fractional distillation, which allows you to collect those fractions that meet specifications, and possibly combine them into one or more fractions of the crude alcohol.

The crude alcohol may contain residual aldehydes and hemiacetals. Such components can be adequately removed during the processing of the alcohol product from the top and tail fractions in the final process of hydrogenation. This hydrogenation reaction is carried out under relatively mild conditions. It can be carried out with conventional methods of hydrogenation, such as the transmission of the crude alcohol along the flow of hydrogen through a layer of a suitable hydrogenation catalyst. Such catalysts are well known in the art and usually contain a metal hydrogenation functionality, such as Nickel, palladium or platinum, on a substrate of refractory oxide such as alumina, silicon dioxide or aluminum oxide-silicon dioxide. The temperature of hydrogenation and pressure hydrogenation may vary within wide limits and generally are, respectively, from 50 to 250°C, preferably from 100 to 200°and from 10 to 150 bar (abs.), preferably from 20 to 100 bar (abs.). Hydrogenated alcohol, obtained the final hydrogenation, is the final alcohol.

In another aspect, the invention also relates to the composition of the alcohol(s)containing:

(a) 70-90 wt.%, preferably 75-85 wt.% linear primary monospitovo C12 and C13;(b) 10-30 wt.%, preferably 15-25 wt.% soperton C12 and C13;

where the weight ratio of linear primary alcohol C12 linear primary alcohol C13 is from 0.5 to 2.0.

The expression "Sospiri" in this description means 2-methyl isomers primary monospitovo specified in (a).

In this latter aspect, the invention also relates to the composition of the alcohol(s)containing:

(a) 55-80 wt.%, preferably 60-75 wt.% linear primary monospitovo C14 and C15,

(b) 20-45 wt.%, preferably 25-40 wt.% soperton C14 and C15,

where ve is the TV against a linear primary alcohol C14 linear primary alcohol C15 is from 1.0 to 3.0.

The above composition of the alcohol(s) produced by the method described in this application.

The invention is further illustrated by the following examples do not limit the present invention data specific options.

Example 1

On stage, including the reaction of the Fischer-Tropsch process, synthesis gas containing hydrogen and carbon monoxide in a molar ratio of about 2:1, is passed over the fixed bed catalyst is activated catalyst Fischer-Tropsch process at a pressure of 60 bar and the weighted average bed temperature (SVTS) 205°C. the Catalyst for the Fischer-Tropsch process is a catalyst CoMn/titanium dioxide. Hourly average volumetric gas flow rate of 800 nl/l/h.

The reaction product is fed into the condenser operating at a pressure of 60 bar and a temperature of 205°obtaining heavy liquid product and a gaseous product containing all of the reaction products having a boiling temperature below 205°C. Specified gaseous stream is condensed by cooling to a temperature of 15°and the liquid stream is subjected to multiple fractional distillations (periodic mode) with the use of Packed distillation columns Fisher, containing 15 plates. First remove the hydrocarbon fraction C6-C10, then the fraction of C11/C12 and C13/C14. The composition of both fractions is given in table 1.

Table 1

The feedstock for hydroformylation
Fraction C11/C12Fraction C13/C14
C9 (wt.%)
alcohol2,0
C10 (wt.%)
n-alkane0,9
alcohol2,0
C11 (wt.%)
1-olefinthe 13.4
2-olefin2,9
internal olefin0,2
n-alkane32,3
alcohol2,3
C12 (wt.%)
1-olefin11,9
2-olefin2,2
internal olefin0,5
n-alkane29,80,9
alcohol1,9
C13 (wt.%)
1-olefin10,4
2-olefin3,1
internal olefin0,6
n-alkane0,736,6
C14 (wt.%)
1-olefin8,1
2-olefin2,1
internal olefin0,7
n-alkane31,9
C15 (wt.%)
1-olefin0,5
n-alkane0,2
The total amount of olefin (wt.%)31,125,7

Example 2

Fraction C11/C12 are hydroformylating as follows.

1.5-liter autoclave load 597,1 g of raw materials for hydroformylation, to 9.9 g of n-alkane C10 (as an internal standard for subsequent GC analysis) and 7.3 g of 5.81 wt.% the solution of KOH in 2-ethylhexanol. In the autoclave create pressure synthesis gas to 30 bar (the ratio of N2/CO=2) and heated to a temperature of 185°C. Then inject a 33.6 g of the solution of catalyst. The solution of catalyst was prepared p is adveritising mixing 214,8 g of 70 wt.% solution octoate cobalt in Shellsol 140T (paraffin solvent; Shellsol is a trademark) with 221,4 g 9-eicosyl-9-phosphabicyclononanes ligand. Accordingly, the amount of cobalt is 0,285 wt.% with respect to the total weight of the contents of the reactor, the molar ratio of ligand/cobalt is 1.2 and the molar ratio C/Co is 0.2. Immediately after introduction of the solution of catalyst, the pressure in the autoclave was raised to 70 bar of synthesis gas (the ratio of N2/CO=2).

After 2 hours, the conversion of olefins ends. During these 2 hours the reaction temperature increased to 196°C. the Composition of the product of the crude alcohol C12/C13 shown in table 2.

Example 3

Repeat the procedure of example 2 except that as a raw material for hydroformylation take a fraction C13/C14. Components use the following number: 546 g fraction C13/C14, and 9.1 g of n-alkane C10, 6.7 g of 5.81 wt.% the solution of KOH in 2-ethylhexanol and 31.0 g of the catalyst solution.

After 2 hours, the conversion of olefins ends. During these 2 hours the reaction temperature was raised to 195°C. the Composition of the product - crude alcohol C14/C15 - also shown in table 2.

Table 2

The crude alcohol
Alcohol C12/C13Alcohol C14/C15
n-alkanes (wt.%)59,168,1
aldehydes (wt.%)0,10,1
alcohol (wt.%)
n-C9-HE2,1
n-C10-HE2,0
n-C11-HE2,1
n-C12-HE/ISO-C12-HE*12,9/3,71,8/0,0
n-C13-HE/ISO-C13-HE10,9/3,3
n-C14-HE/ISO-C14-HE0,5/0,18,4/4,6
n-C15-HE/ISO-C15-HE5,9/3,1
n-C16-HE0,1
Other (wt.%)**5,35,8
Linearity (wt.%)7765
Selectivity for alcohol9494
The degree of conversion (wt.%)99,899,9
* n-CmOH is a linear primary monosperma, having m carbon atoms.

ISO-CmOH is soperton, having m carbon atoms.

** including 2-ethylhexanol, is used as the solvent of the catalyst.

Example 4

The crude alcohols of examples 2 and 3 sequentially subjected to evaporation in the square the night evaporator, the saponification of light fractions, distilled in periodic mode to remove the top and bottom fractions, and final treatment by hydrogenation.

Evaporation in film evaporator is carried out at a temperature of 110°With (for the crude alcohol C12/C13) or 120°With (for alcohol C14/C15) in a vacuum of 1 mbar (abs.), the temperature of the cold pin 5°and the stirring speed 375 rpm, and flow rate 16 ml/min Ratio of about/about received split upper/lower fractions is 91/9 for the crude alcohol C12/C13 and 90/10 for the crude alcohol C14/C15.

The top fraction obtained by evaporation in a film evaporator, amyraut interaction at a temperature of 90°With aqueous 3%solution of NaOH at a ratio of organic:aqueous phase 4:1 for the crude alcohol C12/C13 and aqueous 5%NaOH solution at a ratio of organic:aqueous phase 6:1 for the crude alcohol C14/C15. After phase separation the organic phase is washed three times with water under the same conditions.

From saponified alcohol then distilled light fraction for removal of light by-products and distilled tail fraction for removal of heavy by-products, using distillation in a Packed distillation column Fisher, containing 15 plates. The resulting products - crude alcohols C12/C13 and C14/C15 contain, respectively, 84 wt.% and 89 wt.% the alcohol.

The crude alcohols are then subjected to final treatment by hydrogenation by the interaction of the crude alcohol (0.8 ml/min) with hydrogen (at 5 l/h) in the column for the hydrogenation with a slow transmission fluid through a fixed bed of catalyst containing 14 g of hydrogenation catalyst type Nickel/alumina (HTC 400 ex Crossfield) at a temperature of 120aboutC and a constant hydrogen pressure of 60 bar.

Output (relative to the amount of raw materials C11/C12 or C13/C14 for the reaction of hydroformylation), the composition and the linearity of the obtained alcohol are presented in table 3.

Table 3

Ultimate spirits
Alcohol C12/C13Alcohol C14/C15
n-alkanes (wt.%)0,20,0
alcohol (wt.%)
n-C10-HE0,2
n-C11-HE0,6
n-C12-HE/ISO-C12-HE45,6/5,60,4/0,0
n-C13-HE/ISO-C13-HE35,1/12,10,7/0,0
n-C14-HE/ISO-C14-HE0,1/0,043,6/16,6
n-C15-HE/ISO-C15-HE 22,3/15,3
n-C16-HE0,1
Linearity (wt.%)8166
Yield (wt.%)*5760
* the overall yield of alcohol, including hydroformylation (examples 2 and 3) and treatment (example 4).

1. The method of obtaining the composition of the alcohol(s)containing one or more primary monospitovo at least 60 wt.% which are linear primary monoparty containing at least 7 carbon atoms, where the method includes the stages of (a) interaction of carbon monoxide with hydrogen under the reaction conditions of the Fischer-Tropsch process in the presence of a catalyst Fischer-Tropsch containing cobalt; (b) separating from the product of stage (a)at least one fraction of hydrocarbons containing from 10 to 45 wt.% olefins containing 6 or more carbon atoms; (c) the interaction of one or more hydrocarbon fractions obtained in stage (b)with carbon monoxide and hydrogen under conditions of hydroformylation in the presence of a catalyst of hydroformylation based on the source of cobalt and substituted or unsubstituted monophosphorylation ligand; (d) the selection of the composition of the alcohol(s).

2. The method according to claim 1, in which stage (a) includes the interaction of carbon monoxide is and with hydrogen at a temperature in the range from 125 to 350° C and a pressure in the range from 5 to 150 bar (abs.) in the presence of a catalyst containing cobalt, on a substrate containing titanium dioxide.

3. The method according to claim 1 or 2, wherein the selection stage (b) comprises distillation.

4. The method according to any one of claims 1 to 3, in which the raw material stage (C) is a hydrocarbon stream containing at least 30 wt.% n-alkanes C11 and C12 and from 20 to 45 wt.% linear monoolefins C11 and C12.

5. The method according to any one of claims 1 to 3, in which the raw material stage (C) is a hydrocarbon stream containing at least 30 wt.% n-alkanes C13 and C14 and from 10 to 45 wt.% linear monoolefins C13 and C14.

6. The method according to any one of claims 1 to 5, in which the molar ratio of hydrogen and carbon monoxide at the stage (C) is from 1.0 to 5.0.

7. The method according to any one of claims 1 to 6, in which stage (d) includes the first distillation, saponification, washing with water and a second distillation.

8. The method according to claim 7, in which stage (d) also includes the final stage of hydrogenation.



 

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