Branched olefin production process, surfactant production process, alcohol sulfate production process, branched olefin composition, isoparaffin composition, and surfactant

FIELD: petrochemical processes.

SUBSTANCE: branched olefins are obtained via catalytic dehydration of isoparaffin composition including 0.5% or less of quaternary aliphatic carbon atoms. This isoparaffin composition comprises paraffins with number of carbons within a range of 7 to 35, said paraffins or at least a part thereof being branched with average number of branches from 0.7 to 2.5 and said branches including methyl and optionally ethyl branches. Indicated isoparaffin composition with is obtained via hydrocracking and hydroisomerization of wax. Thus obtained branched olefins contain 0.5% or less of quaternary aliphatic carbon atoms.

EFFECT: upgraded quality characteristics of desired products.

8 cl, 4 tbl, 11 ex

 

This invention relates to a method for producing branched olefins, the use of branched olefins for the production of surfactant and the surfactant.

US-A-5849960 concerns sulfate surfactants based on branched alcohols. Consider branched alcohols have an average number of branches in the molecular chain, at least to 0.7. Ramifications include not only methyl branches, but also ethyl, this does not exclude the presence of long branches. Branched alcohols derived from branched olefins obtained skeletal isomerization of linear olefins. Surface-active sulfates application US-A-5849960 simultaneously satisfy the requirements of biodegradation, solubility in cold water and washing steps in cold water.

On the market there is always a demand for detergents with improved performance when improving, among other things, surface-active substances present in detergents. For example, the Laundry business requires improving the biodegradation of surfactants, their solubility in cold water and washing steps in cold water. At least, looking for a better balance of properties. The expression "balance improved property" means improved, at least on the but property, despite the fact that at least one of the remaining properties is not affected.

The present invention is the provision of improved performance of surface-active sulfates application US-A-5849960 or, at least, improve the balance of their performance. Relevant performance characteristics are biodegradation, solubility in cold water and detergent action in cold water, such as detergency in cold water with low hardness in water with high hardness. Other relevant operational characteristic is the compatibility of the surface-active sulfates with other components present in the detergents, which are described hereafter, in particular compatibility with enzymes, such as the inability denaturation of surface-active sulfates enzymes during storage in the aquatic environment. Other relevant performance characteristics, particularly for use in personal care, is a gentle action on the skin and eyes and the ability of high foaming, preferably providing foam with a thin structure of the foam. In addition, the present invention is directed to improving the performance of chemical reagents for the best oil extraction and removal of spilled oil and it is the best ability to emulsify system oil/water and oil/salt solution and to stabilize emulsions of oil and water or oil and salt solution, in particular, at high temperature. Regardless of this, another objective of this invention is the provision of a method of manufacturing a surface-active sulfates, which is more versatile and more attractive economically than the method known from US-A-5849960. Similarly, the invention seeks to provide such improvements in the anionic surface-active materials, non-ionic surface-active materials or cationic surface-active materials other than the above-mentioned surface-active sulfates, and methods for their production.

According to this invention the surface-active sulfates obtained by dehydrogenation of selected branched paraffins with obtaining branched olefins. Data branched olefins can be converted into branched alcohols and then surface-active sulfates. Alternatively, the branched olefins can be converted into a surface-active substances of other types, in particular anionic surfactants, non-surface-active sulfates, such as surface-active sulfonates; and nonionic surface-active materials and cationic surface-active materials. The advantage of this invention is that it is possible to obtain surface-active in the society and intermediate products with a very low content of molecules with a linear carbon chain. Another advantage of this invention is that it is possible to obtain products whose molecules have a low content of branches with three or more carbon atoms. The advantage of this invention is that it is possible to obtain products whose molecules have a low content of Quaternary aliphatic carbon atoms. Not wanting to contact theory, I believe that the presence of Quaternary aliphatic carbon atoms in the molecules of surface-active substances to some extent prevents them from biodegradable and, therefore, it is preferable to avoid the presence of Quaternary aliphatic carbon atoms in isoparaffin compositions. In fact determined that the presence of 0.5% or less Quaternary aliphatic carbon atoms in the molecules of surface-active substances greatly facilitates the biodegradation of surface-active materials.

Thus, the present invention provides a method of obtaining a branched olefins, which comprises the dehydrogenation of isoparaffin composition containing 0.5% or less Quaternary aliphatic carbon atoms, at a suitable catalyst, where the specified isoparaffin composition comprises paraffins with the number of carbons in the range from 7 to 35, and these paraffins, at least part of their m is of the molecules, are branched, the average number of branches per paraffin molecule ranges from 0.7 to 2.5 and branches include methyl, and, optionally, ethyl branches, specified isoparaffin composition obtained by hydrocracking and hydroisomerization paraffin, and these branched olefins content of the Quaternary carbon of 0.5% or less.

The present invention also provides the use of olefins for the production of anionic surfactants, nonionic surfactants or cationic surfactants, in particular surface-active sulfate or sulfonate, including the conversion of branched olefins in surfactant, branched olefins, which are obtained according to the present invention. In particular, the present invention provides a method of producing alcoholrelated, including the conversion of branched olefins to branched alcoholically, and branched olefins obtained by the process which comprises the dehydrogenation of isoparaffin composition containing 0.5% or less Quaternary aliphatic carbon atoms, at a suitable catalyst, specified isoparaffin composition comprises paraffins with the number of carbons in the range from 7 to 35, and these waxes, by at least a portion of their molecules, are branched, the average number of branches per paraffin molecule ranges from 0.7 to 2.5 and branches include methyl, and, optionally, ethyl branches, these alcoholically contain 0.5% or less Quaternary aliphatic carbon atoms.

In addition, this invention provides a method of producing alcoholrelated, including the conversion of branched olefins to branched alcoholically, where the branched olefins obtained according to this invention.

Another aspect of the present invention is the provision of a composition of branched olefins comprising olefins with different number of consecutive carbon in the range from 7 to 35, in which the olefins, at least part of their molecules are branched, the average number of branches per molecule is at least 0.7 and branches include methyl, and, optionally, ethyl branches. In particular, the present invention provides a composition of branched chain olefins having a content of the Quaternary carbon atoms of 0.5% or less and comprising olefins with different number of consecutive carbon in the range from 7 to 35, in which the olefins, at least part of their molecules are branched, the average number of branches per molecule is from 0.7 to 2.5 and otvet the program include methyl, and optional, ethyl branches, the specified composition of branched olefins can be obtained by a method which comprises the dehydrogenation of isoparaffin composition, which is obtained by hydrocracking and hydroisomerization of wax, and specified isoparaffin composition contains less than 0.5 percent aliphatic Quaternary carbon atoms.

Another aspect of the present invention is the provision of a composition of branched alcohols which can be obtained by the method of the present invention, for example, which includes the interaction of branched olefins of the present invention with carbon monoxide and hydrogen, preferably in the presence of a suitable catalyst.

Another aspect of the present invention is the provision of anionic surfactants, nonionic surfactants and cationic surfactants, in particular surface-active sulfate or sulfonate, which can be obtained by applying the method of the present invention.

Another aspect of the present invention provides an isoparaffin composition comprising less than 0.5 percent aliphatic Quaternary carbon atoms and containing paraffins with different number of consecutive carbon in the range from 7 to 35, where the paraffins, at least part of their molecules, are OSVETLENIE, the average number of branches per paraffin molecule ranges from 0.7 to 2.5 and branches include methyl, and, optionally, ethyl branches.

Another aspect of the present invention is the provision of a composition of branched olefins, which can be obtained according to the present invention.

Not wanting to contact theory, believe that some improvement in the operational characteristics of the surface-active sulfates obtained according to this invention, in comparison with surface-active sulfates, well-known, in particular, from US-A-5849960 inherent difference in the distribution of branches along the corresponding paraffin chains. Such differences in the distribution of branches is really unexpected from the point of view of prototypes and, therefore, are inventive.

As described here, isoparaffin composition and composition of branched olefins and their derivatives alcohols usually represent a mixture comprising molecules with different number of consecutive carbon atoms. Usually, at least 75 wt.%, more typically, at least 90 wt.% these songs represent the range of molecules, where the heaviest molecules containing up to 6 carbon atoms more than the lightest molecules.

Isoparaffin composition comprises paraffins having a number what about the carbon in the range from 7 to 35, where paraffins, at least part of their molecules are branched. Preferred isoparaffin composition comprises paraffins with the number of carbons in the range from 10 to 18. Preferably, when at least 75 wt.%, more preferably at least 90 wt.% isoparaffin composition comprises paraffins with the number of carbons in the range from 10 to 18. In practice, often not more than 99.99 wt.%, often not more than 99.9 wt.% isoparaffin composition comprises paraffins with the number of carbons in the range from 10 to 18. If isoparaffin composition intend to obtain a surface-active sulfates, preferably of isoparaffin composition contained paraffins with the number of carbons in the range from 14 to 17, in this case preferably at least 75 wt.%, more preferably at least 90 wt.% isoparaffin composition contained paraffins with the number of carbons in the range from 14 to 17. In practice, often not more than 99.99 wt.%, often not more than 99.9 wt.% isoparaffin composition comprises paraffins with the number of carbons in the range from 14 to 17. This choice is based on the effects, when paraffins with less carbon, ultimately, provide a more volatile surfactants and waxes with a large number of hydrocarbons, ultimately, give the surface the IDT-active substances with lower solubility in water.

The average number of branches per mole of paraffin to isoparaffin composition is at least 0.7 in the calculation of the total number of branched paraffins and linear paraffins, if they are present. A suitable average number of branches is at least 0.8 and preferably at least 0,9, for example, of 1.0. A suitable average number of branches is not more than 2.0, preferably not more than 1.5, in particular not more than 1.4. On the other hand, in some cases, it is desirable that the average number of branches was at least 1.5 and, accordingly, not more than 2.5.

An appropriate number of methyl branches present in the isoparaffin composition is at least 20%, more appropriate, at least 40%, preferably at least 50% of the total number of branches. In practice, the number of methyl branches often amounts to no more than 99%, usually not more than 98% of the total number of branches. A suitable number of ethyl branches, if present, is at least 0.1%, in particular at least 1%, more preferably at least 2% of the total number of branches. A suitable number of ethyl branches is not more than 20%, particularly not more than 15%, more preferably not more than 10% of the number of branches. The number of all branches other than methyl and ethyl branches, if present, may be less than 10%, in particular less than 5% of the total number of branches. The number of all branches other than methyl and ethyl branches, if present, may be more than 0.1%, usually more than 1% of the total number of branches.

The number of Quaternary aliphatic carbon atoms present in the isoparaffin composition, is preferably low. For applications where biodegradation is not critical, a suitable amount of Quaternary aliphatic carbon atoms is less than 2% from the present carbon atoms, more relevant quantity is less than 1%. For all applications and, in particular, for applications where it is important biodegradation, the number of Quaternary aliphatic carbon atoms is preferably 0.5% or less, most preferably less than 0.5% and in particular less than 0.3%. In practice, the number of Quaternary aliphatic carbon atoms present in the isoparaffin composition is often more than 0.01% of the present aliphatic carbon atoms, more often than 0.05%.

The content of branched paraffins isoparaffin composition is typically at least 70 wt.%, often, smaller least 90 wt.%, predpochtitel is about, at least 95 wt.%, more preferably at least 99 wt.%, in particular, at least about 99.9 wt.% by weight of isoparaffin composition. In practice, the content of branched paraffins is often not less than 99.99 wt.%, more is not greater than 99.95 wt.% by weight of isoparaffin composition. The content of linear paraffins isoparaffin composition typically does not exceed 30 wt.%, often does not exceed 10 wt.%, preferably does not exceed 5 wt.%, more preferably does not exceed 1 wt.%, in particular not more than 0.1 wt.% relative to the weight of isoparaffin composition. In practice, the content of linear paraffins often is, at least 0.01 wt.%, often is, at least, of 0.05 wt.% by weight of isoparaffin composition.

Isoparaffin composition can come from various sources. For example, suitable isoparaffin composition can be isolated from fractions of the distillation of crude oil. Such fraction distillation of crude oil can be processed to partially or, preferably, to the complete removal of components containing sulfur and/or nitrogen.

Otherwise isoparaffin composition can be obtained by the hydroisomerization paraffin composition, namely composition, which consists mainly of linear paraffins, such as obtained by the method of Fischer-Tropsch or oligomerization of ethylene. If anye paraffins, obtained in the Fischer-Tropsch synthesis, are particularly preferred, because the products of the Fischer-Tropsch usually contain very little sulfur and nitrogen and cost-effective. The products of the Fischer-Tropsch process can include or not to include oxygen-containing substances. The products obtained by the hydroisomerization, you can fractionate, for example, by distillation or another way to highlight isoparaffin product of the desired composition. This method of hydroisomerization and subsequent fractionation is known for example from US-A-5866748.

Isoparaffin composition is preferably obtained by hydrocracking and hydroisomerization paraffin, in particular crude paraffin, paraffin obtained by a Fischer-Tropsch synthesis, or polyethylene wax. Usually paraffin contains linear paraffins having at least 5 carbon atoms, preferably at least 15 carbon atoms, more preferably at least 25 carbon atoms. In practice, paraffin often contains linear paraffins, the number of carbon atoms which may be high, for example up to 100 or up to 200 and even more. Paraffin obtained by a Fischer-Tropsch synthesis, is particularly preferred because it usually contains very little sulfur and nitrogen and cost-effective. The product obtained by the method of hydrocracking/hydroisomerization, you can fractionate, e.g. the, by distillation or another way to highlight isoparaffin product of the desired composition. This method of hydrocracking/hydroisomerization and subsequent fractionation is known for example from US-A-5833839. Method of hydrocracking/hydroisomerization usually includes hydrocracking with simultaneous hydroisomerization.

Isoparaffin composition can be processed, reducing the content of linear paraffins, in order to favorably adjust the average number of branches in the isoparaffin composition. This allocation can be performed using molecular sieve as the adsorbent. Molecular sieves can imagine, for example, zeolite 4A, zeolite 5A, zeolite X or zeolite Y. it is Possible to make reference to the "Kirk-Othmer Encyclopedia of Chemical Technology, 4thedition, Volume 1, pp.589-590 and Volume 16, pp.911-916; and "Handbook of Petroleum Refining Processes" (R. A. Meyers, Ed.), 2thedition, pp.10.45-10.51, 10.75-10.77.

Catalysts suitable for the dehydrogenation of isoparaffin composition can be selected from a wide range. For example, they can be based on metal or compound of the metal is deposited on a porous substrate, and a metal or compound of the metal is one or more compounds selected from, for example, chromium oxide, iron oxide and preferably noble metals. Under the noble metals understand the metals of the group formed by platinum, pall who diem, iridium, ruthenium, osmium and rhodium. Preferred noble metals are palladium and particularly platinum.

Suitable porous substrates can represent the carbon substrate of nature, such as activated carbon, coke or charcoal; silicon dioxide, silica gel, or other natural or synthetic clays or silicates, such as hydrotalcite; ceramics; refractory inorganic oxides such as aluminum oxide, titanium oxide or magnesium oxide; natural or synthetic crystalline aluminosilicates such as mordenite or tasit; and combinations of two or more elements selected from these groups. The preferred porous substrate is alumina, particularly gamma alumina or ETA-alumina.

The amount of metal or compound of metal deposited on a porous substrate, is not the subject of the present invention. A suitable amount can be selected in the range from 0.01 to 5 wt.%, preferably from 0.02 to 2 wt.%by weight of the catalyst.

In the catalyst used for the dehydrogenation of isoparaffin composition, in particular catalysts, which include precious metal, there may be additional metals. Such additional metals you can choose a suitable way of group 3A, group 4A and group 5A intermittent the second table of the elements (see R. C. Weast (Ed) "Handbook of Chemistry and Physics", 5thedition, CRC Press, inside cover). In particular, we can choose the Indies from the group 3A, tin from groups 4A and bismuth from group 5A. Particularly suitable additional metals are the alkali and alkaline earth metals. Preferred alkali metals are potassium and especially lithium.

Additional elements that may be present in the catalyst used for the dehydrogenation of isoparaffin composition, are halogen, in particular in combination with metals of the groups 4A, more preferably in combination with tin. The preferred halogen is chlorine.

The number of such additional metals or Halogens may independently be a value in the range from 0.01 to 5 wt.%, preferably from 0.02 to 2 wt.% by weight of the catalyst.

Suitable dehydrogenation catalysts are, for example, chromium oxide on gamma alumina, platinum on gamma-alumina, palladium on gamma alumina, platinum/Li on gamma alumina, platinum/potassium on gamma alumina, platinum/tin on gamma alumina, platinum/tin on hydrotalcite, platinum/indium on gamma-alumina and platinum/bismuth on gamma-alumina.

The dehydrogenation can be performed in a wide range of conditions. A suitable temperature is in di the range from 300 to 700° With more appropriate in the range from 400 to 600°With, in particular in the range from 450 to 550°C. the Total pressure may be elevated, such as a pressure in the range from 110 to 1500 kPa abs.(from 1.1 to 15 bar abs.) (that is, kPa or bar, absolute), preferably in the range of from 130 to 1000 kPa abs.(from 1.3 to 10 bar abs.), in particular in the range from 150 to 500 kPa abs.(from 1.5 to 5 bar abs.). To prevent coking together with isoparaffin mixture can be served hydrogen. In a suitable embodiment, the hydrogen and paraffins present in the isoparaffin composition, served in a molar ratio in the range from 0.1 to 20, more suitable molar ratio is the ratio in the range from 0.5 to 15, in particular the molar ratio in the range from 1 to 10.

Usually opt for this length of dehydrogenation to support the conversion of isoparaffin composition below 50 mol %, preferably in the range of from 5 to 50 mol %, in particular in the range from 10 to 20 mol %. By maintaining a low degree of conversion, it is possible to some extent to prevent side reactions such as the formation of dienes and cyclization reaction. Not converted paraffins and daydreamy compounds can be separated from the products of dehydrogenation and, if required, neprevyshenie paraffins can be returned back into the cycle at the stage of dehydrogenation. That is the second branch can be accomplished by extraction, extractive distillation or, preferably, using a molecular sieve as the adsorbent. Molecular sieves can imagine, for example, zeolite 4A, zeolite 5A, zeolite X or zeolite Y. If you want, you can separate linear olefins from branched olefins, at least to some extent, to increase the content of branched olefins in the product obtained by dehydrogenation, but usually such a right is not preferred.

Specialist known methods for the preparation of catalysts, stage dehydrogenation and the associated stages of separation for use in this invention. For example, suitable methods for the preparation of catalysts and carrying out dehydrogenation known from US-A-5012021, US-A-3274287, US-A-3315007, US-A-3315008, US-A-3745112, US-A-4430517. For methods that are suitable for the separation of branched olefins from linear olefins, it is possible to make reference to the "Kirk-Othmer Encyclopedia of Chemical Technology, 4thedition, Volume 1, pp.589-591 and Volume 16, pp.911-916; and "Handbook of Petroleum Refining Processes" (R. A. Meyers, Ed.), 2thedition, pp.10.45-10.51, 10.79-10.81.

In the dehydrogenation according to the invention is generally formed composition of branched olefins comprising olefins with the number of carbons in the range from 7 to 35, with olefins, at least part of their molecules are branched, the average number of branches n the molecule is at least 0.7 and branching include methyl, and, optionally, ethyl branches. Composition of branched olefins preferably includes olefins with the number of carbons in the range from 10 to 18. Preferably, when at least 75 wt.%, more preferably at least 90 wt.% composition of branched olefins consists of olefins with the number of carbons in the range from 10 to 18. In practice, often not more than 99.99 wt.%, often no more than about 99.9 wt.% composition of branched olefins consists of olefins with the number of carbons in the range from 10 to 18. If the composition of the branched olefins intend to obtain a surface-active sulfates, preferably, the composition of the branched olefins contained olefins with the number of carbons in the range from 14 to 17, in this case preferably at least 75 wt.%, more preferably at least 90 wt.% composition of branched olefins contained olefins with the number of carbons in the range from 14 to 17. In practice, often not more than 99.99 wt.%, often not more than 99.9 wt.% composition of branched olefins consists of olefins with the number of carbons in the range from 14 to 17.

A suitable average number of branches per mole of olefin in the composition of branched olefins is at least 0.8 and preferred by ENISA least of 0.9, for example, of 1.0. A suitable average number of branches is not more than 2.0, preferably not more than 1.5, in particular not more than 1.4. An appropriate number of methyl branches is at least 20%, more appropriate, at least 40%, preferably at least 50% of the total number of branches. In practice, the number of methyl branches often amounts to no more than 99%, usually not more than 98% of the total number of branches. A suitable number of ethyl branches, if present, is at least 0.1%, in particular at least 1%, more preferably at least 2% of the total number of branches. A suitable number of ethyl branches is not more than 20%, particularly not more than 15%, more preferably not more than 10% of the total number of branches. The number of all branches other than methyl and ethyl, if present, may be less than 10%, in particular less than 5% of the total number of branches. The number of all branches other than methyl and ethyl branches, if present, may be more than 0.1%, usually more than 1% of the total number of branches.

The number of Quaternary aliphatic carbon atoms present in branched olefins, preferably is low. For applications where biodestruction which is not critical, an appropriate amount of Quaternary aliphatic carbon atoms is less than 2% from the present carbon atoms, more relevant quantity is less than 1%. For all applications and, in particular, for applications where it is important biodegradation, the number of Quaternary aliphatic carbon atoms is preferably 0.5% or less, most preferably less than 0.5% and in particular less than 0.3%. In practice, the number of Quaternary aliphatic carbon atoms present in branched olefins, often is more than 0.01% of the present aliphatic carbon atoms, more often than 0.05%.

The content of branched olefins in the composition of branched olefins is usually at least 70 wt.%, often, smaller least 90 wt.%, preferably, at least 95 wt.%, more preferably at least 99 wt.%, in particular, at least about 99.9 wt.% by weight of the composition of branched olefins. In practice, the content of branched olefins is often not less than 99.99 wt.%, more is not greater than 99.95 wt.% by weight of the composition of branched olefins. The content of linear olefins in the composition of branched olefins usually does not exceed 30 wt.%, often does not exceed 10 wt.%, preferably does not exceed 5 wt.%, more preferably does not exceed 1 wt.%, in particular not more than 0.1 wt.% otnositelno mass composition of branched olefins. In practice, the content of linear olefins is often, at least 0.01 wt.%, often is, at least, of 0.05 wt.% by weight of the composition of branched olefins.

The composition of the branched olefins suitable for the production of anionic, nonionic and cationic surfactants, preferably the first two, more preferably anionic drugs.

It is more preferable to apply the composition of branched olefins for the production of surface-active sulfates, including alcoholically and oxyalkylene alcoholically, or non-ionic oxyalkylated alcohols. To this end branched olefins can be converted into branched alcohols. Preferred branched alcohols are branched primary alcohols. Alternatively, the branched alcohols may represent a branched secondary alcohols.

Conversion of branched olefins to branched alcohols usually performed, for example, by hydroformylation, oxidation and hydrolysis, sulfation and hydration, amoxicilline and hydration or similar.

When hydroformylating branched olefins in turn branched primary alcohols by reacting carbon monoxide and hydrogen in the presence of a suitable catalyst. How is hydroformylation, suitable for use in this invention are known, for example from US-A-3231621, US-A-3239566, US-A-3239569, US-A-3239570, US-A-3239571, US-A-3420898, US-A-3440291, US-A-3448158, US-A-3448157, US-A-3496203, US-A-3496204, US-A-3501515, US-A-3527818 and US-A-6037506. Additional methods are described in Kirk-Othmer "Encyclopedia of Chemical Technology, 3rdedition, Vol.16, pp.637-653; "Monohydric Alcohols: Manufacture, Applications and Chemistry", E.J. Wickson (Ed.), Am. Chem. Soc., 1981.

The term "hydroformylation" use this field to indicate the interaction of the olefin with carbon monoxide and hydrogen with obtaining aldehyde or alcohol, which has one carbon atom more than the reacting olefin. Often in this field use the term "hydroformylation" to refer generally obtain aldehyde, and recovering the alcohol, that is, the term "hydroformylation" refers to the production of alcohols from olefins via carbonylation and recovery of the aldehyde. Used herein, the term "hydroformylation" refers to the final production of alcohols.

Suitable catalysts based on metals of group 8 of the periodic table. Preferred metals of group 8 can be selected from palladium, platinum, rhodium, Nickel and cobalt, particularly cobalt, rhodium and palladium. The metal of group 8, you can apply (or not) in the form of complex compounds, where the metal of group 8 is combined with the ligand, for example, phosphine, positivum, and synonym, stavinovym or pyridine ligand. Illustrative catalysts hydroformylation include hydrocarbonyl cobalt, cobalt-phosphine ligand and rhodium-phosphine ligand.

A source metal of group 8 may be Sol. Preferred salts of acids which have a pKa value less than 6, in particular less than 4, more preferably less than 2 when measured in water at 20aboutC. Examples of suitable acids are nitric acid, sulfuric acid, carboxylic acid and sulfonic acid. Preferred carboxylic acids are halogenecarbonate acid, such as dichloracetic acid, triperoxonane acid and performatively acid. Preferred sulfonic acids are pair-toluensulfonate acid, benzolsulfonat acid and methanesulfonamide acid.

As the source of the metal of group 8, you can also use the metal elements or complexes of metals with zero valency, for example, the complex with carbon monoxide. However, this requires the additional presence of a proton acid.

As for the ligands, mention can be made of monophosphines, which include three gidrolabilna and/or hydrocarbonsoluble attached to phosphorus, and the corresponding arsine and STIBINE. Examples of monophosphines are triarylphosphine, trihexalon, di is utilitiesin, deamination, tricyclohexylphosphine, tricyclohexylphosphine, diphenylmethylphosphine, diphenylmethylphosphine, diphenyl(2-pyridyl)phosphine, phenyl[bis(2-pyridyl)]phosphine, triethoxypropane, butyldiethanolamine, triphenylphosphine, dimethylphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine and tricholoroethane.

Alternatively, you can apply bidentate ligands, such as tetrahydrocannabivarin, or the corresponding arsine or STIBINE. Examples of tetrahydrocannabivarin are 1,2-bis(dimethylphosphino)ethane, 1,2 - and 1,3-bis(dimethylphosphino)propane, 1,2-bis(diethylphosphino)ethane, 1,2-bis[di(1-butyl)phosphino]ethane, 1-dimethylphosphino-2-diethylphosphonate, 1,2-bis(diphenylphosphino)ethane, 1,2-bis(departmentsin)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1-dimethylphosphino-2-diphenylphosphinoethyl, 1-diethylphosphino-3-diphenylphosphinoethyl and 1,2-bis[di(ortho-tolyl)phosphino]ethane.

Other suitable ligands are phosphabicyclononanes, such as 9-hydrocarbon-9-phosphabicyclononanes and P,P'-bis(9-phosphabicyclononanes)hydrocarbons, in which the smallest P-containing ring has at least 5 carbon atoms. Such ligands include 9-aryl-9-phosphabicyclo[4.2.1]nonanes, 9-(dialkylated)-9-phosphabicyclo[4.2.1]nonanes, 9-alkyl-9-phosphabicyclo[4.2.1]nonanes, 9-cycloalkyl-9-phosphabicyclo[4.2.1]nonanes, 9-cycloalkenyl-9-phosphabicyclo[4.2.]nonanes, P,P'-bis(9-phosphabicyclononanes)alkanes and their [3.3.1]-isomers. Specific examples of such ligands are 9-phenyl-9-phosphabicyclo[4.2.1]nonan, 9-(2,4-dimetilfenil)-9-phosphabicyclo[4.2.1]nonan, 9-ethyl-9-phosphabicyclo[4.2.1]nonan, 9-cyclohexyl-9-phosphabicyclo[4.2.1]nonan, 9-cyclopentyl-9-phosphabicyclo[4.2.1]nonan, 1,2-P,P'-bis(9-phosphabicyclo[4.2.1]nonyl)ethane, 1,3-P,P'-bis(9-phosphabicyclo[4.2.1]nonyl)propane, 1,4-P,P'-bis(9-phosphabicyclo[4.2.1]nonyl)butane and [3.3.1]-isomers.

The reaction conditions hydroformylation you can choose in a wide range. For example, the temperature may range from 20 to 300aboutC. Usually recommend a temperature in the range from 150 to 250aboutWith, in particular from 125 to 200aboutC. Typically, the pressure has a value in the range from 1000 to 20000 kPa abs.(from 10 to 200 bar abs.), but you can choose less or more high pressure. Preferred is a pressure of from 2000 to 10000 kPa abs.(from 20 to 100 bar abs.). A suitable ratio of the catalyst and olefin ratio is from 1:1000 to 1:1. The ratio of hydrogen and carbon monoxide can be selected in a wide range, but usually it ranges from 1 to the value, contributing to the formation of an alcohol product. Preferably this molar ratio is in the range from 2 to 10.

The process of hydroformylation can be (or not) in the presence of an inert solvent. You can apply once obraznye solvents, for example ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and cyclohexanone; aromatic compounds such as benzene, toluene and xylene; halogenated aromatic hydrocarbons such as chlorobenzene and orthodichlorobenzene; halogenated paraffin hydrocarbons, such as methylene chloride and carbon tetrachloride; saturated hydrocarbons such as hexane, heptane, methylcyclohexane and isooctane; and NITRILES, such as benzonitrile and acetonitrile.

For processing and achieving stabilization and purification of the product can be used conventional methods. With this purpose you can use techniques such as distillation, extraction, hydrolysis and recovery. Recovery can be carried out by treatment with hydrogen using a Nickel catalyst on a carrier of alumina or repair, for example, sodium borohydride. To stabilize the product can be remove by hydrolysis of acetals and aldehydes by recovery.

As a result of hydroformylation according to this invention is usually formed composition of primary alcohols, including alcohols with the number of carbons in the range from 8 to 36, in which the alcohols, at least part of the molecules is branched, the average number of branches per molecule is at least 0.7 and branching in luchot methyl and optional, ethyl branches. The preferred composition of branched primary alcohols include alcohols with the number of carbons in the range of 11 to 19. Preferably, when at least 75 wt.%, more preferably at least 90 wt.% composition of branched primary alcohols consists of alcohols with the number of carbons in the range of 11 to 19. In practice, often not more than 99.99 wt.%, often no more than about 99.9 wt.% composition of branched primary alcohols consists of alcohols with the number of carbons in the range of 11 to 19. If the composition of branched primary alcohols intend to obtain a surface-active sulfates, preferably, the composition of branched primary alcohols contained branched primary alcohols with the number of carbons in the range from 15 to 18, in this case preferably at least 75 wt.%, more preferably at least 90 wt.% composition of branched primary alcohols contained olefins with the number of carbons in the range from 15 to 18. In practice, often not more than 99.99 wt.%, often not more than 99.9 wt.% composition of branched primary alcohols consists of olefins with the number of carbons in the range from 15 to 18.

A suitable average number of branches per mole of alcohol in the composition of branched primary alcohols is, on ENISA least 0.8 and preferred, at least, of 0.9, for example, of 1.0. A suitable average number of branches is not more than 2.0, preferably not more than 1.5, in particular not more than 1.4. An appropriate number of methyl branches is at least 20%, more appropriate, at least 40%, preferably at least 50% of the total number of branches. In practice, the number of methyl branches often amounts to no more than 99%, usually not more than 98% of the total number of branches. A suitable number of ethyl branches, if present, is at least 0.1%, in particular at least 1%, more preferably at least 2% of the total number of branches. A suitable number of ethyl branches is not more than 20%, particularly not more than 15%, more preferably not more than 10% of the total number of branches. The number of all branches other than methyl and ethyl branches, if present, may be less than 10%, in particular less than 5% of the total number of branches. The number of all branches other than methyl and ethyl branches, if present, may be more than 0.1%, usually more than 1% of the total number of branches.

The number of Quaternary aliphatic carbon atoms is preferably low. For applications where bigastro the tion is not critical, an appropriate amount of Quaternary aliphatic carbon atoms is less than 2% from the present carbon atoms, more relevant quantity is less than 1%. For all applications and, in particular, for applications where it is important biodegradation, the number of Quaternary aliphatic carbon atoms is preferably 0.5% or less, most preferably less than 0.5% and in particular less than 0.3%. In practice, the number of Quaternary aliphatic carbon atoms is often more than 0.01% of the present aliphatic carbon atoms, more often than 0.05%.

The content of branched primary alcohols in the composition of branched primary alcohols is usually at least 70 wt.%, often, smaller least 90 wt.%, preferably, at least 95 wt.%, more preferably at least 99 wt.%, in particular, at least about 99.9 wt.% by weight of the composition of branched primary alcohols. In practice, the content of branched primary alcohols is often not less than 99.99 wt.%, more is not greater than 99.95 wt.% by weight of the composition of branched primary alcohols. The content of linear primary alcohols in the composition of branched primary alcohols usually does not exceed 30 wt.%, often does not exceed 10 wt.%, preferably does not exceed 5 wt.%, more preferably does not exceed 1 wt.%, in sh does not exceed 0.1 wt.% relative to the weight of the composition of branched primary alcohols. In practice, the content of linear primary alcohols often is, at least 0.01 wt.%, often is, at least, of 0.05 wt.% by weight of the composition of branched primary alcohols.

Branched alcohols can be directly sulfotyrosine or first oxyalkylated and subsequent sulfation. In this invention it is possible to use any of the methods known for the sulfation of alcohols. For example, the method of sulfation, suitable for use in the present invention, is known from US-A-3462525, US-A-3428654, US-A-3420875, US-A-3506580, US-A-3579537 and US-A-3524864. Suitable procedures include sulfation sulphation by interacting with oleum, sulfur trioxide (SO3), chlorosulfonic acid (ClSO3H) or sulfamic acid (NH2SO3H).

If you use the oleum, the concentration of sulfur trioxide in sulfuric acid is usually from 1 to 30 wt.%, preferably from 2 to 20 wt.% by weight of oleum. Suitable amounts of sulfur trioxide are usually from 0.3 to 1.3 moles per mole of branched alcohol, preferably from 0.4 to 1.0 moles per mole of branched alcohol. The sulfation can be achieved through the interaction of branched alcohols and oleum at a temperature of from 20 to 70aboutC.

The standard method of sulfation with sulfur trioxide involves the interaction of liquid alcohol is whether its ethoxylates and gaseous sulfur trioxide in the reaction zone of the water cooled setup for sulfation from the drop-down film at a temperature in the range from 20 to 70° With obtaining ether sulfuric acid and alcohol or its ethoxylate. The interaction is conducted in an appropriate manner at atmospheric pressure, for example at a pressure in the range from 80 to 120 kPa abs.(from 0.8 to 1.2 bar abs.). Then the ether sulfuric acid and alcohol or its ethoxylate is removed from the column drop-down film and neutralized with base such as sodium hydroxide or potassium, with the formation of the corresponding salts alcoholzoloft or the corresponding salts alcoholautomount.

Suitable oxyalkylene alcohols can be obtained by adding to the branched alcohols certain amount, for example from 0.1 to 0.6 wt.%, preferably from 0.1 to 0.4 wt.% by weight of branched alcohols, strong bases, usually a hydroxide of an alkali metal or alkaline earth metal, such as sodium hydroxide or potassium hydroxide, which serves as a catalyst for oxyalkylene. The resulting mixture is dried by removing from the evaporating phase all water present, and then enter a number of accelerated, designed in such a way as to ensure 1-12 moles of accelerated per mole of alcohol. The resulting mixture was allowed to interact until complete consumption of accelerated. Over the course of the reaction is observed by monitoring the reduction of the reaction pressure.

Suitable acceleratedly are, for example, ethylene oxide, 1,2-ol is pileated, 1,2-butylenes and 2,3-butylenes. The preferred acceleratedly are the ethylene oxide and 1,2-propylene oxide. The alcohol of the reaction mixture, you can add two or more alkalisation in the form of a mixture or sequentially to obtain a block structure. Oxyalkylene usually carried out at elevated temperatures and pressures. Suitable reaction temperatures range from range from 120 to 220°With a preferred range of from 140 to 160°C. a Suitable reaction pressure reached by introducing into the reaction vessel of the required number of accelerated, which has a high vapor pressure at the desired reaction temperature. For security reasons, process the partial pressure alkalinizing reagent is preferably limited, for example, a value below 500 kPa abs.(5 bar abs.) and/or preferably diluted with reagent with an inert gas, such as nitrogen, for example, to the concentration in the vapor phase is 50% or less. However, you can safely spend interaction at higher concentrations accelerated, higher total pressure and a higher partial pressure of accelerated, if you take well-known in this field necessary precautions to manage the risk of explosion. As accelerated, preferred is the total pressure of 400 to 1000 kPa abs.(4 to 10 bar AB is.) and the partial pressure of from 200 to 600 kPa (2 to 6 bar abs.) and more preferable is the total pressure of from 500 to 800 kPa abs.(5 to 8 bar abs.) and the partial pressure of from 250 to 500 kPa abs.(from 2.5 to 5 bar abs.). When pressure is used as a measure of the degree of interaction, this pressure should appreciate relative to the initial pressure. In such cases, the interaction is considered substantially completed when the pressure no longer decreases with time.

It should be understood that the procedure oxyalkylene serves to introduce the required average number of units accelerated per mole of branched alcoholassociated. For example, the processing is branched alcohols with 3 moles of ethylene oxide per mole of branched alcohol gives amoxilonline each molecule of alcohol on average 3 ethylenoxide fragments per mole of alcohol fragment, although a significant portion of alcohol fragments may be combined with more than 3 ethylenoxide fragments and about the same part will be combined with less than 3. In a typical mixture of products amoxilonline can also be a minor part of the unreacted alcohol.

A General class of surface-active sulfates, which can match this invention can be characterized by the chemical formula (R-O-Ax-SO3)nM, where R represents the fragment of a branched primary alcohols corresponding to this invention, which have the number of carbons in the range from 8 to 36, in particular from 11 to 19, more preferably from 15 to 18; And present the returned fragment accelerated; x represents the average number of fragments And fragment R and has a value in the range 0 to 15; M is a cation selected from the ions of alkali metals, alkaline earth metal ions, ammonium ion and mixtures thereof; and n equals the number depending on the valence of the cation (cation) M, so that the total electric charge was zero. Ion ammonium may represent a derived organic amine with 1, 2 or 3 organic groups attached to the nitrogen atom. Suitable ammonium ions are derivatives of monoethanolamine, diethanolamine and triethanolamine. Preferably, ammonium ion had the formula NH4+. In preferred embodiments, M is potassium or magnesium, as potassium ions can contribute to the water solubility (branched alkyl)arylsulfonate and magnesium ions can contribute to their performance in soft water.

Preferred classes of surface-active sulfates include sulfates of alkali metals branched primary alcohols of this invention, which have the number of carbons in the range of 11 to 19, in particular from 15 to 18, and alkali-metal sulfates of the condensation products of branched primary alcohols having the number of carbons in the range of 11 to 19, in particular from 15 to 18, with ethylene oxide and 1,2-propylene oxide, in the decree is " a product of condensation of a number of taksigrup is from 3 to 12, and the ratio of taksigrup to 1,2-propoxyphen is from 4 to 12.

Surfactants that can be obtained in accordance with this invention, in particular surface-active sulfates, can be used as surfactants in a wide range of diverse applications, including detergents, such as granular detergents for washing clothes, liquid detergents for washing clothes, liquid, means for washing; and in a variety of preparations, such as cleaning agents General application, liquid soap, shampoo and liquid cleaning agents.

Surface-active sulfates find particular application in detergents, in particular in detergents for washing clothes. These drugs usually contain a number of components, except the surface-active sulfates, other surfactants, ionic, nonionic, amphoteric or cationic type, linking together existing binder, bleaches and activators, agents, regulatory foaming, enzymes, agents against gray RAID, optical agents for brightness and stabilizers.

The liquid detergents of the present invention for washing clothes can include the same components as granular detergent, but they usually contain less inorganic light of the ith component. In liquid detergents can be present hydrotropic. Cleaning agents of General application may include other surfactants, binders, agents, regulatory foaming, hydrotropes and alcohols to increase the solubility.

These preparations may contain a large number of binders and shared binders to 90 wt.%, preferably from 5 to 35 wt.% from the mass of the drug to intensify the cleaning action. Examples of well-known inorganic binders are phosphates, polyphosphates, carbonates of alkali metals, silicates and sulfates. Examples of organic binders are polycarboxylate, aminocarboxylate, such as ethylenediaminetetraacetate, nitrilotriacetate, hydroxycarboxylic, citrates, succinate and substituted and unsubstituted, alkindi - and polycarboxylic acids. Another type of binder, useful in granular media for washing and binding liquid agents for Laundry, includes a variety of essentially water-insoluble materials which are able to reduce the hardness of water, for example, by ion exchange. In particular, for this purpose a very useful comprehensive materialobject known as zeolites of type A.

These drugs may also include peresoedineniya with bleaching effect, such as perborate, perkar the courses, persulfates and organic nagkalat. Drugs, including peresoedineniya may also contain stabilizing agents, such as magnesium silicate, sodium ethylenediaminetetraacetate or sodium salt of phosphonic acids. In addition, you can apply the bleaching activators to improve the efficiency of inorganic persona at low wash temperatures. Particularly useful for this purpose are substituted amides of carboxylic acids, such as tetraacetylethylenediamine, substituted carboxylic acids, for example isanonymousallowed and nutritioned.

Examples of suitable hydrotropic substances are the alkali metal salts of benzene-, toluene - and Killswitch acids, alkali metal salts of formic acid, citric acid and succinic acid, chlorides of alkali metals, urea, mono-, di - and triethanolamine. Examples of alcohols that enhance solubility, are ethanol, isopropanol, mono - or polyethylene glycols, monopropellant and partial ethers of polyols.

Examples of agents that regulate foaming, are fatty acid Soaps of high molecular weight, paraffinic hydrocarbons and silicon panonychus agents. In particular, hydrophobic particles of silicon dioxide are effective agents that regulate foaming in t the fir detergents for washing clothes.

Examples of known enzymes that are effective in detergents for washing clothes, are protease, amylase and lipase. Preferred enzymes that have optimal performance under certain conditions, the detergent and cleaning agent.

The literature describes a large number of fluorescent brighteners. For washing detergents are particularly suitable derivatives diaminodiphenylsulfone and substituted distribiter.

As an agent against gray plaque is preferable to use water-soluble colloids of organic nature. Examples are water-soluble polyanionic polymers, such as polymers and copolymers of acrylic and maleic acid, derivatives of cellulose, such as carboxymethyl cellulose, methyl and hydroxyethyl cellulose.

Surfactants, which can be obtained according to this invention, in particular surface-active sulfates, can also be successfully used in personal care products, in applications with increased removal of oils and removal of oil stains off shore and on inland waterways, canals and lakes.

The preparations of the present invention typically include one or more inert components. For example, the balance of liquid detergents is usually an inert solvent or RA shall movitel, most typically water. Powder or granular detergent preparations usually contain large amounts of inert fillers or carriers.

In US-A-5849960 characterized used here is the average number of branches per molecule, for more details on the type and position of the branches and content of Quaternary aliphatic carbon atoms, define them in ways that are described in US-A-5849960. In US-A-5849960 also described additional analytical methods and research.

Unless otherwise indicated, referred to here organic compounds with low molecular weight are usually not more than 40 carbon atoms, more typically not more than 20 carbon atoms, particularly not more than 10 carbon atoms, more preferably not more than 6 carbon atoms. Organic compounds considered compounds, which include the composition of the molecules, the atoms of carbon and hydrogen. A group of organic compounds with low molecular weight does not include polymers and enzymes.

Defined here ranges for the number of carbon atoms (i.e. the number of carbons) include the number specified for the limits of the ranges. Defined here, the number of atoms of carbon include carbon atoms of the main chain, and, if present, the carbon atoms of the branches. The following example illustrates the nature the DN of the present invention, without defining its scope.

Example 1 (predictive)

The mixture of hydrocarbons using the Fischer-Tropsch from linear paraffins having at least 5 carbon atoms, including, in addition, a small amount of oxygenates, is exposed to conditions of hydrocracking and hydroisomerization by reacting a mixture of hydrocarbons in the presence of hydrogen with a palladium catalyst in a mixture of silica-alumina (0.5 wt.% Pd, 55 wt.% Al2O3, 45 wt.% SiO2) at a temperature of 350°and pressure of 6000 kPa abs.(60 bar abs.), using a constant volumetric rate of fluid 0,5 l/l/h and the ratio of hydrogen/wax when applying 400 Nl/l (the volume of liquids at room temperature, "Nl" means the volume of gas at 0°C, 100 kPa (1 bar)).

Product flow hydrocracking/hydroisomerization fractionary by distillation and dividing by the molecular sieve zeolite 5A, thus obtaining the isoparaffin composition, which consists of branched and linear paraffins with the number of carbons in the range from 14 to 17. The average number of branches is 1.9 per mole of paraffin. The number of methyl branches is 60% of the total number of branches. The number of ethyl branches is 15% of the total number of branches. The amount present in isoparaffin composition razvetvlennye the paraffin is more than 96 wt.%, and the number present in the isoparaffin composition of linear paraffins is less than 4 wt.% of the total weight of isoparaffin composition.

This isoparaffin composition is exposed to conditions of dehydrogenation by the interaction of isoparaffin composition in the presence of hydrogen with a catalyst of platinum on gamma-alumina (0.5 wt.% platinum) at a temperature of 490°and a pressure of 250 kPa abs.(2.5 bar abs.), using the feed molar ratio of hydrogen/paraffins equal to 4. The duration of stay of isoparaffin composition adjusted so that the conversion was 15%.

The product of the dehydrogenation fractionary by dividing by the molecular sieve zeolite 5A, removing waxes. Get olefinic fraction containing paraffins.

This olefinic fraction hydroformylation by reaction of olefinic fraction with hydrogen and carbon monoxide at a molar ratio of hydrogen/carbon monoxide of 1.7:1 in the presence of the modified phosphine cobalt catalyst at a temperature of 185°and a pressure of 8000 kPa abs.(80 bar abs.) to complete the reaction.

The reaction product of hydroformylation subjected to the usual treatments for deactivation of the catalyst hydroformylation and stabilization, cleaning, and drying the resulting alcoholic product.

Next alcohols is th product sulfation known method.

Example 2 (predictive)

Repeat the procedure of example 1 except that the lower division at the molecular sieves and the amount of branched paraffins present in the received isoparaffin composition, 80 wt.%, and the number of linear paraffins present in the received isoparaffin composition is 20 wt.% by weight of isoparaffin composition and average number of branches in the received isoparaffin composition is 1.5 per mole of paraffin. In other aspects of isoparaffin composition is the same as that specified in example 1.

Example 3 (predictive)

Repeat the procedure of example 1 except that a mixture of hydrocarbons using the Fischer-Tropsch consists mainly of linear paraffins having at least 30 carbon atoms. Received isoparaffin composition similar to the composition defined in example 1.

Example 4 (predictive)

Repeat the procedure of example 3 except that the lower division at the molecular sieves, and the number of branched paraffins present in the received isoparaffin composition is 90 wt.%, and the number of linear paraffins present in the received isoparaffin composition is 10 wt.% by weight of isoparaffin composition and average number of response the areas obtained in isoparaffin composition is 1.7 per mole of paraffin. In other aspects of isoparaffin composition is the same as that specified in example 1.

Examples 5-8 (predictive)

Repeat the procedure of examples 1-4 except that in each case, the isoparaffin composition consists of branched and linear paraffins having the number of carbons in the range from 13 to 17 instead of the range of 14-17. In other aspects received isoparaffin composition are as specified in the corresponding example from examples 1-4.

Example 9

With9-24waxes obtained by polymerization using as starting substances methane and synthesis gas (H2and WITH), separated by distillation. Sample15-16paraffin digitalout, using essentially known methods of dehydrogenation/extraction of olefins, receiving branched C15-16olefins (olefin-candidates").

Control olefinic feedstock, which typically has a content of the Quaternary carbons of 0.20 or less, is With15-16branched olefins obtained by the isomerization of linear internal olefins ("ISO-olefins"). Isomerization of control carried out essentially as described in example 2 application US-A-5849960. Olefins candidates and ISO-olefins have the following characteristics:

Table 1. olefinic cheese is e
The type of olefinISO-olefinsOlefins-candidates
Olefin,

Paraffin,

Aromatics,
98,3

1,7

0
62

25

13

With16-17the branched alcohols are synthesized from samples of olefins by hydroformylation essentially as described in US-A-5849960. To obtain comparative data for sample candidate (E in table 4 below) using parallel procedures (the same conditions and methods), making ISO-olefins in the C16-17branched alcohols (ISO-alcohols, D in table 4 below).

Over the course of the reaction being followed by a flow of synthesis gas. Stage separation and purification include vacuum flash separation to remove heavy ends and catalytic residues of the crude alcohol, treatment with sodium borohydride (NaBH4to restore the formate esters and aldehydes to alcohols, the stage of washing with water (3 times) to remove unreacted borohydride and decomposed borate compounds and vacuum distilled to separate the alcohol from the unreacted olefins, paraffin by-products, residual catalyst and heavy ends. Recovery of aldehydes and formate esters during treatment with sodium borohydride control via IR with Fourier transform (FTIR).

Alcohols candidates demon is tryout the branching index of 1.5 and an average number of carbon 16,1. For alcohols candidates see the following results:

Table 2. Analysis of the branches relative to the alcohol end (C1 denotes the alcohol carbon)
% no branches or branches on the position of the C4+72,0
% branches at position C311,7
% methyl branching in position C26,7
% ethyl branches at position C21,4
% sawn or longer branches at the position C28,3
% branches all types
C1 (methyl)60,7
C2 (ethyl)7,6
C3+(cut+)31,6

The control shows the following results:

/tr>
Table 3. Analysis of the branches relative to the alcohol end (C1 denotes the alcohol carbon)
% no branches or branches on the position of the C4+63,6
% branches at position C321,8
% methyl branching in position C24,8
% ethyl branches at position C21,3
% sawn or longer branches at the position C28,6
% branches all types
C1 (methyl)79,9
C2 (ethyl)10,0
C3+(cut+)the 10.1

The distribution of the number of carbon determined using the method Townsend gas chromatography/mass spectrometry with chemical ionization and nitrogen oxide as a gas-reagent described in I. Dzidic, etc., Analytical Chemistry, Vol.64, pp.2227-2232 (1992). The results are presented in the following table:

Table 4. The distribution of the number of carbon
D (ISO-alcohols)E(alcohols candidate)
% razwell. alcohols% LINEST. alcoholsCND % razwell. alcohols% LINEST. alcoholsCND
C140,10,00,10,00,00,0
C150,70,41,10,73,03,7
C1626,51,027,533,914,748,6
C1766,70,967,5a 38.50,839,3
C183,40,03,47,80,07,8
C190,40,00,40,50,00,5
totalof 97.82,2100,081,518,5100,0

Note: the number is inany alcohols calculated on the basis of calibration for pure standard compounds. However, due to the lack of suitable standards for the branched components distribution of branched alcohols expect, assuming equal response for all components. The resulting distribution may be close, but not quite accurate.

Section "analysis of the branches relative to the alcohol end (C1 denotes the alcohol carbon)describes the branching in the molecule, as it corresponds to the location of these branches relative to the alcohol end of the molecule. If a branch is present in the following carbon after alcohol carbon (carbon C2), the NMR method is able to accurately distinguish methyl, ethyl and propyl or longer types of branches. If the branch is on the second carbon from the alcohol carbon (C3), the NMR method can only determine that there is a branch, but cannot tell whether it stands, ethyl, propylene or longer branch. At a distance of three from the alcohol carbon NMR cannot say whether there is any type of branch. Thus, the expression "% absence of branches or branches on the position of the C4+" denotes linear molecules, and molecules that have branches 3+ at a distance of more than three links from the alcohol carbon.

Section "% branches all types" gives the number C1 (methyl), C2 (ethyl), C3+(propyl or b is more long branches in the molecule regardless of their location from alcohol end.

NMR analysis of a sample of candidate shows the content of the Quaternary carbons below 0.5%. It is known that molecules containing Quaternary carbon, hard biologically restrukturizuota. Therefore, the content of Quaternary carbons below 0.5% makes these materials very useful and quickly biodegradable restruktureerimine.

The speed With-hydroformylation rely on the consumption of synthesis gas, using data for the first hour. During distillation collect multiple fractions and analyzed by the methods of GC-FID and FT-IR. The last two fractions of alcohol candidate (E), collected by distillation, harden at room temperature, the reference sample (D) remains in the liquid state.

Example 10

Using the techniques described in example 9, to measure the content of the Quaternary carbons in the molecules of alcohol in a competing product. A competing product is alcohol with a high content of methyl branches obtained by oligomerization of propylene with subsequent hydroformylation that turns olefin in alcohol with a high content of methyl branches. The content of the Quaternary carbon is approximately 0.6. US-A-5112519 describes this product as "tridecylamine alcohol with a high content of methyl branches, known for its use in lubricants and cleaning preparations, which do not require rapid Biol the environmental destruction".

Example 11

Sulfates D and E of example 9 is obtained by chlorsulfuron and analyze. Here are the results:

Source%SUOMH20SulfateOnly
D (Example 9)28,81,465,60,8296,6
E (Example 9)30,91,362,80,7395,7

AM=active material

UOM=unreacted organic material

It is clear that some of the distinctive features of the present invention, which, for clarity, described in the context of individual cases, it is also possible to provide in combination in a single embodiment. Conversely, the distinctive features of the present invention, which are described in the context of a single variant, it is possible to provide separately or in any suitable podnominatsii.

1. A method of obtaining a branched olefins, which comprises the dehydrogenation of isoparaffin composition containing 0.5% or less Quaternary aliphatic carbon atoms, at a suitable catalyst, specified isoparaffin composition comprises paraffins with a number of carbon is s from 7 to 35, moreover, these paraffins, at least part of their molecules are branched, the average number of branches per paraffin molecule ranges from 0.7 to 2.5 and branches include metal and, optionally, ethyl branches, specified isoparaffin composition obtained by hydrocracking and hydroisomerization paraffin, and these branched olefins content of the Quaternary carbon of 0.5% or less.

2. The method according to claim 1, where the content of branched paraffins isoparaffin composition is at least 70% by weight of isoparaffin composition.

3. A method of obtaining a surfactant selected from anionic surfactants or nonionic surfactants, in particular surface-active sulfate or sulfonate, including the conversion of branched olefins, obtained by the method according to claim 1 or 2, surfactant, where the branched olefins in turn branched alcohols by reacting branched olefins with carbon monoxide and hydrogen in the presence of a suitable catalyst.

4. The method of producing alcoholrelated, including the conversion of branched olefins to branched alcoholically, and these branched olefins obtained by a method that includes degidrirovanie the isoparaffin composition, contains 0.5% or less Quaternary aliphatic carbon atoms, at a suitable catalyst, specified isoparaffin composition comprises paraffins with a number of carbons ranging from 7 to 35, and these paraffins, at least part of their molecules are branched, the average number of branches per paraffin molecule ranges from 0.7 to 2.5 and branches include methyl, and, optionally, ethyl branches, these alcoholically contain 0.5% or less Quaternary aliphatic carbon atoms, where the branched olefins in turn branched alcohols by reacting branched olefins with carbon monoxide and hydrogen in the presence of a suitable catalyst, followed by sulfation of branched alcohols.

5. Composition of branched olefins, suitable for surface-active substances having 0.5% or less Quaternary carbon atoms and comprising olefins with different number of carbons from 7 to 35, in which the olefins, at least part of their molecules are branched, the average number of branches per molecule is from 0.7 to 2.5 and branches include methyl, and, optionally, ethyl branches, and the specified composition of branched olefins get method, which involves the dehydrogenation of isoparaffin composition, which is obtained by hydrocracking and hydroisomerization of wax, moreover, the specified isoparaffin composition contains less than 0.5 percent aliphatic Quaternary carbon atoms.

6. Composition of branched alcohols, suitable for receiving surfactant having from 8 to 36 carbon atoms, in which the alcohols, at least part of the molecules is branched, the average number of branches per molecule is at least 0.7 and branching includes metal and, optionally, ethyl branches, and the specified composition of branched alcohols produced by the interaction of branched olefins with carbon monoxide and hydrogen in the presence of a suitable catalyst and it contains less than 0.5 percent aliphatic Quaternary carbon atoms.

7. Surfactant selected from anionic surfactants, nonionic surfactants obtained by the method according to any of p-4.

8. Isoparaffin composition suitable for the production of surface-active substances containing less than 0.5 percent aliphatic Quaternary carbon atoms and containing paraffins with different number of carbons from 10 to 35, where the paraffins, at least part of their molecules are branched, the average number of branches per paraffin molecule ranges from 0.7 to 2.5 and branches include metal and, optionally, the tilen branches.



 

Same patents:

FIELD: cleaning agents.

SUBSTANCE: cleansing paste suitable to clean and sanify enamel and metallic kitchen dishes, sanitary ware such as washing stands, bathes, lavatory pans, gas burners and the like, marble and ceramic surfaces contains, wt %: sulfonol 3-5, soda ash 10-20, odorant 0.4-1.2, mineral sludge coming as waste from production of protein-vitamin concentrate 52-58, brine of naturally occurring bischofite mineral MgCl2·6h2O (density 1.2-1.3 t/m3) 4-6, and water the balance. Cleansing paste production line comprises sulfonol, soda ash, and odorant supply tanks, transportation means, mixer, vibrator for delivering finished produce, off-line and in-line tanks for finished produce, screw dispensing mechanism, finished produce packaging means, and conveyor for delivering packaged cleansing paste. The line is provided with receiving bin for above mineral sludge, drier, intermediate bin for dried sludge, crusher, sieve classifier, tanks for standard and non-standard sludge, cyclone, fan, hose filter to collect dust fraction of sludge, and sliding shutter. Upstream of mixer, bischofite brine and water tanks are disposed.

EFFECT: improved quality of cleansing household equipment surfaces and ensured high degree of killing pathogenic microorganisms.

2 cl, 1 dwg, 11 tbl

FIELD: medicine, in particular disinfections and cleaning of medicine articles, surgery tools, hospital clothes, etc, in bacterial, viral and fungus infections.

SUBSTANCE: claimed composition contains (mass %): glutaric aldehyde 3.8-4.2; ortho-phenylphenol 2.8-3.2; ortho-benzyl-para-chlorophenol 2.8-3.2; propylene glycol 60-70; ethanol 5-10; benzoic acid 2.8-3.2; sodium benzoate 2.8-3.2; lauryl sulfate 10-15; water 5-10.

EFFECT: safe composition of increased antibacterial activity.

4 tbl, 1 ex

The invention relates to the technical detergents for handling the technological equipment of the dairy industry from burns and "milk stone", made of glass, plastic, metal or combinations of these materials
The invention relates to cleaning tools designed for effective removal of resistant formations rust, sediment, hardness salts with faience and tile surfaces, and can be used for washing dishes

The invention relates to detergent compositions for soaking

The invention relates to household chemicals, in particular to compositions for cleaning sanitary-technical equipment in the home, and for cleaning surfaces made of glass from rust and grease before painting

The invention relates to a concentrate cleaner for cleaning medical and/or surgical instruments and/or apparatus containing at least one ionic surfactant, at least one solubilizer, at least one proteolytic enzyme and water, characterized in that as the ionic surface-active substances it contains salt (C5-C12) alkylsulfate and further comprises at least one alkanolamine in the following ratio, wt.%: Sol (C5-C12) alkylsulfate 0,5-8,0, solubilizer 4,0-15,0, alkanolamine 4,0-10,0, a proteolytic enzyme in an amount of from 0.005 to 0.1 Anson units/g purifier, water up to 100

The invention relates to fine granular anionic surfactant for detergents and/or cleaning agents, which has a microporous structure without dust-raising share, and its bulk density is at least 150 g/l, and the content of residual water - up to 20 wt

The invention relates to new compositions of detergent compositions with high foaming capacity, containing non-ionic surface-active agent (surfactant) as the main active ingredient, complemented by smaller quantities of a specific group of anionic surfactants and even smaller quantities zwitterionic betainovuyu surfactants in the aquatic environment

FIELD: industrial organic synthesis.

SUBSTANCE: ethylbenzene blend obtained through blending fresh ethylbenzene and recycled ethylbenzene with styrene content not above 0.1 wt % is subjected to catalytic dehydrogenation in presence of water steam at feed-to-steam weight ratio 1:2, temperature 600°C, ethylbenzene blend supply space velocity 0.5-1.0 h-1, and reactor pressure maintained within a range of 45 to 80 kPa absolute. Multistep rectification gives rectified styrene with concentration of desired product at least 99.8% and phenylacetylene impurity level not higher than 0.01 wt %. Recycled ethylbenzene is blended with fresh ethylbenzene and resulting ethylbenzene blend containing no more than 0.1 wt % styrene is supplied to dehydrogenation unit.

EFFECT: increased ethylbenzene-to-styrene conversion, improved process selectivity, and reduced level of phenylacetylene in commercial product.

5 tbl

FIELD: petrochemical industry; methods of production of styrene.

SUBSTANCE: the invention is pertaining to the field of petrochemical industry, in particular, to the method of production of styrene. The invention provides for dehydrogenation of the ethylbenzene charge gained after mixing of the fresh ethylbenzene with the recycled ethylbenzene on the ferrioxide catalytic agent at presence of the steam at the mass ratio of the raw to the steam of no less than 1:2, at the temperature of 580-640°С and the volumetric speed of feeding of the ethylbenzene charge of 0.23-0.45 m3/h. The hydrocarbon condensate (the product of the dehydrogenation) containing styrene, the unreacted ethylbenzene, the by-products including the phenyl acetylene impurity before the stage of the rectification is hydrogenated using the palladium-containing catalytic agents at the temperature of 20-30°С, the volumetric speed of 4.5-5.0 m3/h-1 and at the volumetric ratio of the hydrogen : raw - 35-45. The technical result of the invention is the increased purity of the produced styrene without reduction of productivity of the whole process of the marketable styrene.

EFFECT: the invention ensures the increased purity of the produced styrene without reduction of productivity of the whole process of the marketable styrene.

1 tbl, 8 ex

FIELD: organic chemistry, chemical technology, catalysts.

SUBSTANCE: invention describes a catalyst for dehydrogenation of (C2-C5)-hydrocarbons that comprises aluminum, chrome oxides, compound of modifying metal, alkaline and/or alkaline-earth metal. Catalyst comprises additionally silicon and/or boron compounds and as a modifying agent the proposed catalyst comprises at least one compound chosen from the following group: zirconium, titanium, iron, gallium, cobalt, molybdenum, manganese, tin. The catalyst is formed in the process of thermal treatment of aluminum compound of the formula Al2O3. n H2O wherein n = 0.3-1.5 and in common with compounds of abovementioned elements and shows the following composition, wt.-% (as measure for oxide): chrome oxide as measured for Cr2O3, 12-23; compound of a modifying metal from the group: Zr, Ti, Ga, Co, Sn, Mo and Mn, 0.1-1.5; silicon and/or boron compound, 0.1-10.0; alkaline and/or alkaline-earth metal compound, 0.5-3.5, and aluminum oxide, the balance. Catalyst shows the specific surface value 50-150 m2/g, the pore volume value 0.15-0.4 cm3/g and particles size 40-200 mcm. Also, invention describes a method for preparing this catalyst. Invention provides preparing the catalyst showing the enhanced strength and catalytic activity.

EFFECT: improved and valuable properties of catalyst.

12 cl, 2 tbl

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention provides catalytic composition for dehydration of alkylaromatic hydrocarbons optionally combined with ethane comprising: carrier consisting of alumina in δ phase or in θ phase, or in mixed δ+θ or θ+α, or δ+θ+α phase, modified with silicon oxide and having surface area less than 150 m2/g as measured by BET method; 0.1-35% gallium in the form of Ca2O3; 0.01-5% manganese in the form of Mn2O3; 0-100 ppm platinum; and 0.05-4% alkali or alkali-earth metal oxide, all percentages being based on the total weight of composition. Other variants of composition are also covered by invention. Methods of preparing such catalytic composition (options) envisage use of alumina-based carrier in the form of particles corresponding to group A of the Geldart Classification. Process of dehydration of alkylaromatic hydrocarbons optionally combined with ethane comprises: (i) dehydration of hydrocarbon stream optionally mixed with inert gas in fluidized-bed reactor in presence of catalytic composition consisted of alumina-supported and silica-modified gallium and manganese at temperature within a range of 400 to 700°C, total pressure within a range of 0.1 to 3 atmospheres, and gas hourly space velocity from 50 to 10000 h-1; and (ii) regeneration and heating of catalyst caused by catalytic oxidation of fuel in fluidized-bed reactor at temperature above 400°C.

EFFECT: increased activity of catalytic composition and prolonged lifetime thereof.

22 cl, 2 tbl, 16 ex

FIELD: petroleum chemistry, organic chemistry, chemical technology.

SUBSTANCE: method involves contacting the parent raw flow in the flow-type reactor with oxygen-free gas flow at increased temperature with a catalyst comprising a precious metal of VII group of the periodic system of elements. The industrial isomerization platinum-containing catalyst SI-1 or industrial hydrogenation catalyst "palladium on active aluminum oxide in sulfured form" is used as a catalyst. Contact of the parent raw with catalyst is carried out by its feeding in inert gas flow, for example, nitrogen at the volume rate 1-2 h-1 at temperature 320-370°C in the presence of the additive representing a solution of hydroquinone or p-benzoquinone in isopropyl alcohol and taken in the concentration 0.01-0.5 mole/l wherein the additive is fed to the parent raw flow in the amount 5-30 vol.%. Invention provides carrying out the highly selective isomerization and cyclization of light petroleum fractions in on industrial Pt- and/or Pd-containing catalysts with the high yield of the end products no containing aromatic compounds and not requiring the presence of hydrogen or hydrogen-containing gas for its realization and regeneration of the catalyst.

EFFECT: improved method for isomerization.

4 cl, 2 tbl, 2 ex

FIELD: chemistry of aromatic compounds, chemical technology.

SUBSTANCE: process involves the following stages: feeding (C2-C5)-alkane, for example, ethane and (C2-C5)-alkyl-substituted aromatic compound, for example, ethylbenzene into dehydrogenation reactor for the simultaneous dehydrogenation to (C2-C5)-alkene, for example, to ethylene, and (C2-C5)-alkenyl-substituted aromatic compound, for example, styrene; separation of the outlet dehydrogenation flow for extraction of gaseous flow containing alkene, hydrogen and alkane, and for extraction of aromatic compounds with the high effectiveness by cooling and compression; feeding a gaseous flow and (C6-C12)-aromatic compound into the alkylation reactor for preparing the corresponding (C2-C5)-alkyl-substituted aromatic compound that is recirculated into the dehydrogenation reactor; feeding the blowing flow from the alkylation unit containing alkane and hydrogen for the separation stage by using cryogenic separator for extraction of alkane that is recirculated into the dehydrogenation reactor, and hydrogen that is extracted with the purity value 99%. Invention provides the development of economic and highly effective process for preparing alkenyl-substituted aromatic compounds.

EFFECT: improved preparing method.

61 cl, 2 tbl, 2 dwg, 2 ex

FIELD: petroleum chemistry, chemical technology.

SUBSTANCE: invention relates to dehydrogenation of isoamylenes to isoprene on iron oxide self-regenerating catalysts. Method involves addition of piperylenes in the concentration up to 4 wt.-% representing a by-side product in manufacturing process of isoprene by the indicated method to the parent isoamylenes before their dehydrogenation. Method provides enhancing selectivity of method for isoamylenes dehydrogenation to isoprene in the presence of iron oxide self-regenerating catalysts.

EFFECT: improved preparing method.

1 tbl, 6 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention concerns catalysts for dehydrogenation of C2-C5-alkanes into corresponding olefin hydrocarbons. Alumina-supported catalyst of invention contains 10-20% chromium oxide, 1-2% alkali metal compound, 0.5-2% zirconium oxide, and 0.03-2% promoter oxide selected from zinc, copper, and iron. Precursor of alumina support is aluminum oxide hydrate of formula Al2O3·nH2O, where n varies from 0.3 to 1.5.

EFFECT: increased mechanical strength and stability in paraffin dehydrogenation process.

9 cl, 1 dwg, 3 tbl, 7 ex

FIELD: petrochemical processes.

SUBSTANCE: 1,3-butadiene is obtained via catalytic dehydrogenation of n-butylenes at 580-640°C and essentially atmospheric pressure while diluting butylenes with water steam at molar ratio 1:(10-12) and supplying butylenes at space velocity 500-750 h-1. Catalyst is composed of, wt %: K2O 10-20, rare-earth elements (on conversion to CeO2) 2-6, CaO and/or MgO 5-10. MoO3 0.5-5, Co2O3 0.01-0.1, V2O5 0.01-0.1, and F2O3 the balance. Once steady condition is attained, dehydrogenation is carried out continuously during all service period of catalyst.

EFFECT: increased yield of 1,3-butadiene and process efficiency.

2 ex

FIELD: petrochemical processes.

SUBSTANCE: simultaneous dehydrogenation of mixture containing alkyl and alkylaromatic hydrocarbons is followed by separating thus obtained dehydrogenated alkyl hydrocarbon and recycling it to alkylation unit. Dehydrogenation reactor-regenerator employs C2-C5-alkyl hydrocarbon as catalyst-transportation carrying medium.

EFFECT: increased process flexibility and extended choice of catalysts.

36 cl

FIELD: petrochemical processes.

SUBSTANCE: branched olefins from isomerization feedstock in the form of linear olefin/paraffin mixture containing 5 to 50% of linear olefins having 7 to 28 carbon atoms are obtained in the first isomerization stage, wherein carbon backbone of linear olefins in the isomerization feedstock is isomerized when in contact with isomerization catalyst, which is effective to isomerize carbon backbone in linear olefin blend to convert the latter into olefin blend, wherein average number of branches in molecule chain is at least 0.7, followed by second stage, wherein branched and linear molecules are separated, the former being essentially olefinic molecules and the latter olefinic and/or paraffin molecules. Resulting branched olefins are served as starting material for production of alcohols and alkylbenzenes.

EFFECT: enabled olefin branching control.

6 cl, 4 tbl, 3 ex

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