Process of producing branched olefins, branched aromatic hydrocarbon, branched alkylarenesulfonates, compositions of branched olefins, branched aromatic hydrocarbon, and branched alkylarenesulfonates

FIELD: petrochemical processes.

SUBSTANCE: branched olefins are obtained via dehydrogenation of isoparaffin composition containing 0.5% or less quaternary aliphatic carbon atoms in presence of suitable catalyst. Isoparaffin composition is prepared via hydrocracking and hydroisomerization of paraffin wax and contains paraffins with 7 to 18 carbon atoms, these paraffins or at least a part of them are branched with average number of branches between 0.5 and 2.5 per paraffin molecule, the branches including methyl and optionally ethyl ones. Original paraffin wax is prepared using Fischer-Tropsch reaction. Resulting branched olefins are characterized by content of quaternary aliphatic structures 0.5% or less. Branched aromatic hydrocarbon and compositions of branched olefins, branched aromatic hydrocarbon, and branched alkylarenesulfonates are also disclosed.

EFFECT: improved quality characteristics of target products.

10 cl, 19 ex

 

This invention relates to a method for producing a branched alkylarylsulfonates and the compositions of branched alkylarylsulfonates. This invention relates to a method for producing an intermediate of aromatic hydrocarbons containing branched alkyl, and the aromatic hydrocarbons containing branched alkyl.

WO-A-99/05244, WO-A-99/05082 and US-A-6111158 refers to surface-active alkylarylsulfonates, in which the alkyl groups are branched. Sources alkyl groups are, for example, paraffins with limited branching obtained by the violation of the linearity of linear paraffins.

US-A-5849960 refers to surface-active sulfates based on branched alcohols. Consider branched alcohols have an average number of branches at the molecular chain of at least 0.5 in. Branches contain only methyl branches, but also ethyl branches, that may have longer branches. Branched alcohols derived from branched olefins obtained skeletal isomerization of linear olefins.

The market always requires performance improvements of existing detergents with improved, among other things, surface-active substances present in detergents. For example, in Laundry business requires washing cf is DSTV with enhanced biodegradation of surfactants, their solubility in cold water and detergent action in cold water. At least, looking for a better balance of properties. The expression "balance improved property" means improving at least one property, despite the fact that at least one of the remaining properties is not affected.

The present invention is to provide improve the performance of known surface-active alkylarylsulfonates or, at least, the improvement of the balance of their performance. The invention operating 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. The other related to the performance of the invention is the compatibility of the surface-active alkylarylsulfonates with other components present in the detergents, which are described later, in particular compatibility with enzymes, such as the inability denaturation of surface-active alkylarylsulfonate enzymes during storage in the aquatic environment. Other inventive performance, particularly in the case of personal use, is the smooth action on the skin and eyes and pic the institutional capacity of high foaming, preferably providing the foam with a thin structure of the foam. In addition, another object of the invention is the provision improve performance chemicals for the best oil extraction and removal of spilled oil, namely 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, the present invention is the provision of a method of obtaining a surface-active alkylarylsulfonates, which is more versatile and more attractive economically than known methods.

According to this invention the surface-active alkylarylsulfonate is produced by dehydrogenation of selected branched paraffins with obtaining branched olefins. Data branched olefins can be converted into branched alkylaromatic compounds and then surface-active alkylarylsulfonate. The advantage of this invention is that it is possible to obtain surface-active substances and intermediate products with a very low content of molecules with a linear carbon chain. Another advantage of this invention is the fact that you can get the products, the molecules of which have a low content the 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. The inventors believe that the presence of Quaternary aliphatic carbon atoms in the molecules of surface-active branched alkylarylsulfonates 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 surfactants.

Thus, the present invention provides a method of obtaining a branched olefins, and specified the method comprises the dehydrogenation of isoparaffin composition containing 0.5% or less Quaternary aliphatic carbon atoms, at a suitable catalyst, and the specified isoparaffin composition obtained by hydrocracking and hydroisomerization of wax, and contains paraffins with the number of carbons in the range from 7 to 18, and these paraffins, at least part of their molecules are branched, the average number of branches per paraffin molecule sostav the et from 0.7 to 2.5, and branches contain methyl and optionally ethyl branches, and these branched olefins contain 0.5% or less Quaternary aliphatic carbon.

The present invention also provides a method of obtaining a branched alkylaromatic hydrocarbons which comprises the interaction of branched olefins with aromatic hydrocarbons in the alkylation conditions, and branched olefins obtained by the process which comprises the dehydrogenation of isoparaffin composition on a suitable catalyst 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 molecules are branched, the average number of branches per paraffin molecule is at least 0.5 and branches include methyl, and optionally ethyl branches. In particular, the present invention provides a method of obtaining a branched alkylaromatic hydrocarbons which comprises the interaction of branched olefins with aromatic hydrocarbons in the alkylation conditions, and branched olefins obtained by the process which comprises the dehydrogenation of isoparaffin composition containing 0.5% or less Quaternary carbon atoms on a suitable catalyst, specified from the paraffin composition obtained by hydrocracking and hydroisomerization of wax and contains paraffins with the number of carbons in the range from 7 to 35, moreover, these paraffins, at least part of their molecules are branched, the average number of branches per paraffin molecule is from 0.5 to 2.5, and branches contain methyl and optionally ethyl branches, these branched olefins contain 0.5% or less Quaternary aliphatic carbon.

This invention also provides a method of obtaining a branched alkylarylsulfonates, including sulfonation branched alkylaromatic hydrocarbons, where the branched alkylaromatic hydrocarbons obtained by the method of obtaining branched alkylaromatic hydrocarbons according to the present invention.

In addition, this invention provides a composition of branched olefins, which can be obtained according to the present invention.

In addition, this invention provides a composition of branched alkylaromatic hydrocarbons which can be obtained according to the present invention.

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

The inventors believe that some improvement in the operational characteristics of the branched alkylarylsulfonates received under this izaberete the Oia, in comparison with the known branched alkylarylsulfonate it is possible to achieve due to differences in the distribution of branches along the corresponding paraffin chains. Such differences in the distribution of branches is really unexpected from the standpoint of prior art and, therefore, are inventive.

As described here, isoparaffin composition and composition of branched olefins, branched alkylaromatic compounds and their derivatives of branched alkylarylsulfonates 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 the number of carbons in the range from 7 to 35, where the paraffins, at least part of their molecules are branched. Preferred isoparaffin composition comprises paraffins with the number of carbons in the range from 7 to 18, more preferably from 10 to 18. Preferably, at least 75 wt.%, more preferably at least 90 wt.% isoparaffin composition comprises paraffins with the number is the your carbon in the range from 10 to 18. In practice, often no 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. Most preferably, when the isoparaffin composition contains the number of carbons in the range of 11 to 14, 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 of 11 to 14. In practice, often no more than 99.99 wt.%, often not more than 99.9 wt.% isoparaffin composition comprises paraffins with the number of carbons in the range of 11 to 14. 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 surfactants with lower solubility in water.

The average number of branches per mole of paraffin to isoparaffin composition is at least 0.5 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 0.7 and more appropriate - at least to 0.8, for example, of 1.0. A suitable average number of branches is not more than the 2,0, preferably not more than 1.8, in particular not more than 1.4.

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 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 present in the isoparaffin composition, is preferably low. For applications where biodegradation is not critical, suitable if estvo Quaternary aliphatic carbon atoms is less than 2% of present carbon atoms, a more convenient 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 attendees aliphatic carbon atoms, often more than 0.02%.

The content of branched paraffins isoparaffin composition is typically at least 50 wt.%, often, smaller least 70 wt.%, most typically at least 90 wt.%, preferably, at least 95 wt.%, more preferably at least 99 wt.%, in particular, at least about 99.9 wt.% relative to the 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.% relative to the weight of isoparaffin composition. The content of linear paraffins isoparaffin composition typically does not exceed 50 wt.%, often does not exceed 30 wt.%, most typically 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. On the right is tick the content of linear paraffins often is, at least 0.01 wt.%, more is at least 0.02 wt.% relative to the 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 partial or, more preferably, to the complete removal of components containing sulfur and/or nitrogen.

Alternatively, the 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 (after hydrogenation). Linear 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.

Preferably isoparaffin composition get what hydrocracking and hydroisomerization of wax, in particular, crude paraffin, paraffin, obtained in the 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 in the 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, for example, 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. Usually the method of hydrocracking/hydroisomerization 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 which may be present, 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, 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, palladium, 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, for example, 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 the data group. 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.% relative to the 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 appropriately from the group IIIa, group IVa and group Va of the Periodic table of 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 IIIa, tin from group IVa and bismuth from group Va. 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 group IVa, preferably in combination with tin. The preferred halogen is chlorine is.

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.% relative to the weight of the catalyst.

Suitable catalysts for dehydrogenation 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 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 01 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 30 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. Neprevyshenie 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. This separation 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 this step is not preferred.

Specialist known methods for the preparation of catalysts, stage dehydr the simulation and the associated stages of separation, used 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 per molecule is at least 0.5 and branches include methyl, and optionally ethyl branches. Preferably, the composition of the branched olefins include olefins with the number of carbons in the range from 7 to 18, more preferably 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 not more than 99.9 wt.% composition of branched olefins consists of olefins with the number of carbons in the range of the zone from 10 to 18. Most preferably, the composition of the branched olefins contained olefins with the number of carbons in the range of 11 to 14, 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 of 11 to 14. 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 of 11 to 14.

A suitable average number of branches per mole of olefin in the composition of branched olefins is at least 0.7 and more appropriate, at least to 0.8, for example, of 1.0. A suitable average number of branches is not more than 2.0, preferably not more than 1.8, and particularly 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. Suitably the number of ethyl branches is not more than 20%, in particular 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 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 branched olefins, often is more than 0.01% of attendees aliphatic carbon atoms, often more than 0.02%.

The content of branched olefins in the composition of branched olefins, usually with the hat, at least 50 wt.%, often, smaller least 70 wt.%, most typically at least 90 wt.%, preferably, at least 95 wt.%, more preferably at least 99 wt.%, in particular, at least about 99.9 wt.% relative to the 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.% relative to the weight of the composition of branched olefins. The content of linear olefins in the composition of branched olefins usually does not exceed 50 wt.%, more typically does not exceed 30 wt.%, most typically 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 the 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.% relative to the weight of the composition of branched olefins.

Composition of branched olefins may contain paraffins, which are not converted in the dehydrogenation. Such non-convertible waxes can be removed in a suitable way at the next stage, in particular, when processing the alkylation reaction mixture, as described below, and return to the stage dehydrogenation. If the composition of the branched olefins VK is uchet paraffins, the descriptions given in the three paragraphs preceding this paragraph, refer to the olefinic part of the composition of branched olefins. Generally, the amount of olefinic part in the composition of branched olefins is from 1 to 50 mol.% relative to the total number of moles present of olefins and paraffins, more typically from 5 to 30 mol.%, in particular from 10 to 20 mol.% with respect to the same. Typically, the amount of paraffin part, which is present in the composition of branched olefins ranges from 50 to 99 mol.% relative to the total number of moles present of olefins and paraffins, more typically from 80 to 90 mol.% with respect to the same.

Obtaining branched alkylaromatic hydrocarbons by the interaction of branched olefins, aromatic hydrocarbons can be carried out in a variety of conditions alkylation. Preferably specified alkylation leads to monoalkylammonium, and only to a lesser extent to dialkylamino or higher alkylation, if it occurs.

Aromatic hydrocarbon applicable in this alkylation may be one or more of the following hydrocarbons: benzene; toluene; xylene, for example ortho-xylene or a mixture of xylenes; and naphthalene. The preferred aromatic hydrocarbon is benzene.

The molar ratio of branched Olaf is new to aromatic hydrocarbons can be selected in a wide range. To facilitate monoalkylammonium is suitable molar ratio of at least 0.5, and preferably at least 1, in particular at least a 1.5. In practice, this molar ratio is often less than 1000, more often less than 100.

Specified alkylation can be performed or not performed in presence of a liquid diluent. Suitable diluents are, for example, paraffin mixture with a suitable range of boiling points, such as paraffins, which are not converted in the dehydrogenation and which are not removed from the dehydrogenation product. As diluent can act aromatic hydrocarbon.

Used alkylation catalysts can be, for example, from a large range of zeolite alkylation catalysts. To facilitate monoalkylammonium preferably, the zeolite alkylation catalysts have pore sizes in the range from 4 to 9 Åmore preferably from 5 to 8 Å and most preferably from 5.5 to 7 Å in the notion that the pores have an elliptical shape and is considered a larger pore size. The pore size of the zeolites were determined in W.M. Meier and D.H. Olson "Atlas of Zeolite Structure Types, 2nd revised edition (1987)published by the Structure Commission of the International Zeolite Association. Suitable zeolite alkylation catalysts are zeolites in KIS is now of the form selected from zeolite Y and zeolite ZSM-5 and ZSM-11. The preferred zeolite alkylation catalysts are zeolites in acid form, selected from mordenite, ZSM-4, ZSM-12, ZSM-20, offretite, hellenica and cancrinite. A particularly preferred zeolite alkylation catalysts are zeolites, which have a NEZ-zeolite of structural type, including structures with isotopically lattices, such as NU-87 and Gottardi, as disclosed in US-A-6111158. Zeolites, which have a NEZ-zeolite of structural type, predominantly give high selectivity relative to the 2-arylalkenes. Other examples of suitable zeolite alkylation catalysts are given in WO-A-99/05082.

Appropriate is a variant in which the zeolite alkylation catalyst has a molar ratio of Si to Al of at least 5:1 and 500:1, in particular not more than 100:1. In particular, if the zeolite alkylation catalyst is NES-zeolite of structural type, the molar ratio of Si to Al is preferably from 5:1 to 25:1, more preferably from 10:1 to 20:1. The molar ratio of Si to Al zeolite alkylation catalyst believe the molar ratio of tetrahedra SiO4the tetrahedra AlO4, i.e. the molar ratio Si/Al in the lattice.

The zeolite alkylation catalyst preferably has at least a portion of the cationic places, employment is s ions, different from the ions of alkali or alkaline-earth metals. This replacement ion may be one or more ions selected from the group including, for example, ammonium, hydrogen and rare earth elements. In a preferred embodiment, the zeolite alkylation catalyst, at least, is partly in the hydrogen form, that is the acid form, in particular, in the hydrogen form. Appropriate is when at least 10%, preferably at least 50%, more preferably at least 90% of cationic places are occupied by hydrogen ions. In practice, often not more than 99%, usually not more than 95% of cationic places are occupied by hydrogen ions. This is usually achieved by exchange of alkali metal ions or other ions ions precursor of hydrogen, for example, ammonium ions, which, after calcination yield the hydrogen form.

It is preferable to use the zeolite alkylation catalyst in the form of granules, containing, for example, at least 1 wt.%, typically, at least 50 wt.%, preferably, at least 90 wt.% zeolite alkylation catalyst. Granules may be present conventional binder. Useful well-known binder may be an inorganic substance, such as clay, silica and/or metal oxides. The zeolite alkylation catalyst which can be put together with other materials, such as a porous matrix materials, for example, aluminum oxide, silicon dioxide/aluminum oxide, silicon dioxide/magnesium oxide, silicon dioxide/zirconium dioxide and silicon dioxide/titanium oxide, silicon dioxide/aluminum oxide/oxide of thorium and silicon dioxide/aluminum oxide/zirconium dioxide.

The processing method of the zeolite alkylation catalyst or its predecessors in order to obtain the active form of the zeolite alkylation catalyst described in WO-A-99/05082. Examples of such treatments are ion exchange reactions, dealumination, treatment with live steam, annealed in air, hydrogen or inert gas and activation.

Suitable is the use of zeolite alkylation catalyst in an amount of from 0.5 to 100 wt.%, preferably from 1 to 50 wt.% relative to the weight used branched olefins.

Obtaining branched alkylaromatic hydrocarbons by the interaction of branched olefins, aromatic hydrocarbons can be carried out at alkylation conditions including the reaction temperature selected from a wide range. Appropriate is the reaction temperature selected from a range from 30 to 300°With more suitable temperature in the range from 100 to 250°C.

Processing of the reaction mixture alkylation can be completed well known in this field with whom persons. For example, the solid catalyst can be removed from the reaction mixture by filtration or by centrifugation. Unreacted hydrocarbons, for example branched olefins, excess introduced aromatic hydrocarbons or paraffin can be removed by distillation.

A General class of branched alkylaromatic compounds, which can be obtained according to this invention can be characterized by the chemical formula R-A, where R represents a radical derived from branched olefins of the present invention addition of hydrogen atoms, and branched olefins have the number of carbons in the range from 7 to 35, in particular from 7 to 18, more preferably from 10 to 18, most preferably from 11 to 14; and a represents an aromatic hydrocarbon radical, in particular phenyl radical.

Branched alkylaromatic compounds of this invention can be alfirevich any way sulphonation known in this field. Examples of such methods include sulfonation using sulfuric acid, chlorosulfonic acid, oleum or sulfur trioxide. The details of the preferred method of sulfonation, which includes the application of a mixture of air/sulfur trioxide, is known from US-A-3427342.

After sulfonation can be applied to any well-known method of treatment. Re clonney the sulphonation mixture can be neutralized with a base to obtain branched alkylarylsulfonate in the form of a salt. Suitable bases are hydroxides of alkali metals and alkaline-earth metals and ammonium hydroxide, which provide the cation M salts, as described below. A General class of branched alkylarylsulfonates, which can be obtained according to this invention can be characterized by the chemical formula (R-A'-SO3)nM, where R represents a radical derived from branched olefins of the present invention addition of hydrogen atoms, and branched olefins have the number of carbons in the range from 7 to 35, in particular from 7 to 18, more preferably from 10 to 18, most preferably from 11 to 14; A' represents a bivalent aromatic hydrocarbon radical, in particular phenylenebis radical, M represents a cation selected from the ions of alkali metals, ions of alkaline-earth metals, 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 CA is s or magnesium, as potassium ions can contribute to the water solubility of the branched alkylarylsulfonates and magnesium ions can contribute to their performance in soft water.

Surface-active branched alkylarylsulfonate, which can be obtained according to this invention, can be used as surfactants in a variety of 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 branched alkylarylsulfonate find particular application in detergents, in particular in detergents for washing clothes. These drugs usually contain a number of components, except the surfactant branched alkylarylsulfonates: 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.

These liquid detergents for washing clothes can enable the same to the components, that and the granulated detergent, but they usually contain less inorganic binder 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, up to 90 wt.%, preferably, between 5 and 35 wt.% relative to the weight 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 the granular detergent 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, ion exchange. In particular, for solving this problem are very useful comprehensive materialobject known the AK zeolites of type A.

These drugs may also include peresoedineniya with bleaching effect, such as perborate, percarbonate, 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 task are substituted amides of carboxylic acids, for example, 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 ethers alcohols.

Examples of agents that regulate foaming, are fatty acid Soaps of high molecular weight, paraffinic hydrocarbons and silicon panonychus agents. In particular, hydrophobia particles of silicon dioxide are effective agents, regulatory foaming, such 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 detergents for washing clothes 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.

Surface-active branched alkylarylsulfonate, which can be obtained according to this invention, 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 the liquid detergent is x drugs is usually an inert solvent or diluent, 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 techniques.

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 illustriou the t nature of this 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 interaction of 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 20° "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, and thus, isoparaffin composition, which consists of branched and linear paraffins with the number of carbons in the range from 10 to 15. 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 of branched paraffins composition is yet 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 interaction 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 interacts with the benzene alkylation conditions at a molar ratio of benzene/olefin equal to 20, at a temperature of 190°and in the presence of a catalyst of acidic mordenite in the amount of 15 wt.% by weight of olefinic fraction.

The alkylation product is isolated and purified by filtration and removal of volatile components by distillation.

Isolated and purified product of alkylation sulfurous known method.

Example 2 (predictive)

Repeat the procedure of example 1, except that lower the time the bookmark on molecular sieves, and the number of branched paraffins present in the received isoparaffin composition is 70 wt.%, and the number of linear paraffins present in the received isoparaffin composition is 30 wt.% relative to the weight of isoparaffin composition, and the average number of branches in the received isoparaffin composition is equal to 1.3 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.% relative to the weight of isoparaffin composition, and the average number of branches in the received isoparaffin composition is 1.7 per mole of paraffin. In other aspects of isoparaffin the new composition is the same as indicated 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 10 to 14, instead of the range from 10 to 15. In other aspects received isoparaffin composition are the same as specified in the corresponding example from examples 1-4.

Examples 9-16 (predictive)

Repeat the procedure of examples 1-8, except that in each case, cancel the removal of paraffins from the product of the dehydrogenation and instead removed by distillation paraffins from the products of alkylation. In each case receive does not contain paraffin product of alkylation and then it sulfurous.

Example 17

Carry out the hydrocracking9-22waxes obtained by polymerization using as starting substances methane and synthesis gas (H2and WITH) to obtain the branched paraffins, separate them by distillation and collect fractions. Individual fractions will be analyzed by the distribution of the number of carbons. Based on the analysis of selected fractions are mixed together in the following way, to the mixture corresponded to the specified distribution of the number of carbons: <10% C10; <2% C14; balance11-13(here d is more "C 11-13paraffins").

The following analytical data contain structural information obtained branched paraffin. Note: samples a and B in the table below represent the same sample was investigated at different times. The sample should be more accurate, as it later and reflects some minor improvements of the analytical method with time.

Sample11-13paraffin digitalout using mainly known methods for the dehydrogenation. For NMR analysis and confirm that the dehydrogenation process did not cause any significant changes in the structure of the obtained olefin, the resulting product again hydronaut using a commercial platinum catalyst at an angle, the resulting product (sample C in table) analyzed using the same method that was used for samples a and B. the Results are presented in the column of the first table and the first set of NMR data.

SAMPLEAndInControl 1Control 2
The ratio of branched paraffins to linear paraffins1,91,81,82,62,6
The ratio of mmp paraffins to linear paraffins 0,90,90,92,42,5
The ratio of highly branched paraffins to linear paraffins1,00,90,90,10,1

Data of NMR and chromatographic data provide information on the distribution of the length of the carbon chains and the structure:

21,6
NMR analysis of the ramifications of dehydrogenated paraffin
The number of carbons in the chain alkane12 (GC-data)
The branching index1,1
% branches all types
C1 (methyl)79,3
C2 (ethyl)19,4
C3+ (cut+)1,3
NMR analysis of the ramifications of the re-hydrogenated waxes
The number of carbons in the chain alkane12 (GC-data)
The branching index1,1
% branches all types
C1 (methyl)73,7
C2 (ethyl)
C3+ (cut+)4,6

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), NMR 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), NMR 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 longer 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 which, containing Quaternary carbon, hard biologically restrukturizuota. Therefore, the content of Quaternary carbons below 0.5% makes these materials very useful and quickly biodegradable restruktureerimine.

Example 18

Using the techniques described in example 17 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 does not require rapid biological degradation".

Example 19 (predictive)

Paraffins11-13example 17 is exposed to the conditions described in example 1, obtaining the olefin fraction containing paraffins.

This olefinic fraction interacts with the benzene alkylation conditions at a molar ratio of benzene/olefin 20, at a temperature of 190°and in the presence of a catalyst of acidic mordenite in the amount of 15 wt.% by weight of olefinic fraction.

Read the t alkylation is isolated and purified by filtration and removal of volatile components by distillation. Isolated and purified product of alkylation sulfurous known method.

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 having a content of Quaternary aliphatic carbon of 0.5% or less, including the dehydrogenation of isoparaffin composition containing 0.5% or less Quaternary aliphatic carbon atoms, at a suitable catalyst, in which the isoparaffin composition obtained by hydrocracking and hydroisomerization of wax and includes paraffins with the number of carbons from 7 to 18, and these paraffins, at least part of their molecules are branched, the average number of branches per paraffin molecule is from 0.5 to 2.5, branches include metal and optional ethyl branches and the wax obtained by the reaction of the Fischer-Tropsch process.

2. The method according to claim 1, wherein a content of branched paraffins isoparaffin composition is at least 50% by weight of isoparaffin composition.

3. The method according to 1 or 2, where the amount of metal branches present in the isoparaffin composition is at least 20% of the total number of branches.

4. A method of obtaining a branched alkylaromatic hydrocarbon, including the interaction of branched olefins having a content of Quaternary aliphatic carbon of 0.5% or less, with an aromatic hydrocarbon in the alkylation conditions, in which the branched olefins is produced by dehydrogenation of isoparaffin composition containing 0.5% or less Quaternary aliphatic carbon atoms, at a suitable catalyst, specified isoparaffin composition obtained by hydrocracking and hydroisomerization of wax includes paraffin with the number of carbons from 7 to 35, and these paraffins, at least part of their molecules are branched, the average number of branches per paraffin molecule is from 0.5 to 2.5, branches include metal and optional ethyl branches, these branched olefins and the wax obtained by the reaction of the Fischer-Tropsch process.

5. The method according to claim 4, where the aromatic hydrocarbon is benzene.

6. A method of obtaining a branched alkylarylsulfonates, including sulfonation branched alkylaromatic hydrocarbons, in which the branched alkylaromatic hydrocarbons floor is obtained by the method according to claim 4 or 5.

7. The method according to claim 4, 5 or 6, where at least 75 wt.% isoparaffin composition comprises paraffins with the number of carbons from 11 to 14.

8. Composition of branched olefins, suitable for surface-active alkylarylsulfonates obtained by the method according to claim 1, 2 or 3.

9. The composition of the branched alkylaromatic hydrocarbons, suitable for surface-active alkylarylsulfonates obtained by the method according to claim 4 or 5.

10. The composition of the branched alkylarylsulfonate as surface-active component obtained by the method according to claim 6 or 7.



 

Same patents:

The invention relates to household chemicals, in particular the production of synthetic detergents for washing articles made of linen, cotton and mixed fibres

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

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
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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

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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

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

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