Method of separating olefins from saturated compounds and the composition of olefins

 

Usage: petrochemistry. Essence: raw materials containing saturated hydrocarbons, internal olefins and alpha-olefins in contact with a linear polyaromatic compound with obtaining a reaction mixture containing the first adducts linear polyaromatic compound-olefin and saturated hydrocarbon. Separating the first olefin adducts from the saturated hydrocarbons in the reaction mixture to obtain a first stream of olefin adduct and the first stream of saturated hydrocarbons. Contacting at least a portion of the first stream of saturated hydrocarbons with a linear polyaromatic compound with obtaining a reaction mixture containing the second adduct linear polyaromatic compound-olefin and saturated hydrocarbon. Separate second olefin adduct from the reaction mixture to obtain a second stream of olefin adduct and the second stream of saturated hydrocarbons, and the concentration of saturated hydrocarbons in the second stream of saturated hydrocarbons higher than the concentration of saturated hydrocarbons in the first stream of saturated hydrocarbons, and the concentration of saturated hydrocarbons in the first stream of saturated hydrocarbons higher than the concentration of us the x linear polyaromatic compounds and the first olefin composition and separating the linear polyaromatic compounds from the first olefin composition. Effect: increase the efficiency of the process. 2 C. and 8 C.p. f-crystals, 7 tab., 1 Il.

The present invention relates to a method for separating olefins from saturated hydrocarbons, followed by the separation of linear alpha-olefins and internal olefins from a stream of saturated hydrocarbon and the olefin stream.

The result of many industrial processes is receiving flows of mixtures of olefin/saturated hydrocarbons, which are a mixture of olefins, saturated hydrocarbons and oxygenates. Olefins are often used in the production of such polymers as polyethylene, as additives for drilling muds or as intermediates in the manufacture of additives to oils, additives and detergents. Some industrial methods allow to obtain flows of olefins by oligomerization of ethylene over a catalyst for alpha-olefin, accompanied by the formation of mixtures of alpha and internal olefins, which have a wide range of content of carbon atoms. However, these streams are formed by using as a raw material of ethylene, which significantly increases the cost of production of olefin. On the other hand, as ishodnogo gas, coal, coke and other carbonaceous compounds, and in the process get oligomers consisting of olefins, aromatic compounds, saturated hydrocarbons and oxygenates. However, the FT process is not very selective in obtaining olefins. Although the reaction conditions and the catalysts can be selected in such a way as to receive a stream enriched in the desired substances inside the product stream of the process FT, a large percentage of the product stream of the process FT (hereinafter - flow FT), contains other types of connections, which must be separated from the olefin and the olefin should be cleaned and then sent for sale to various markets. For example, a typical industrial flow FT will contain a mixture of saturated hydrocarbons having a wide range of molecular masses, olefins, aromatics and oxygenates, such as organic carboxylic acids, alcohols, ethers, esters, ketones and aldehydes. All these connections must be isolated from the crude flow FT before a particular composition can be offered for commercial sale. Further complicating the process of separation that flow FT contains compounds with a wide range of the content of carbon atoms is e C2-C200internal linear olefins, linear alpha olefins, branched internal olefins, branched alpha-olefins and cyclic olefins, many of which have the same molecular weight.

Separation and extraction of these compounds is not an easy task. Traditional distillation methods often do not allow to separate substances having close boiling points.

Proposed various ways of separating different compounds in the stream of FT with sufficient purity so that a particular composition is appropriate to the particular field of use. Such methods of separation of different substances in the flow FT include molecular sieves, the use of which is limited to raw materials, connected with the number of carbon atoms in the average range, which is more limited than the composition containing a wide range of compounds with an average number of carbon atoms within C5-C20the use of ion exchange resins, the use of superactivation columns, often working under high pressure, and the use of catalysts for the oligomerization or methods of esterification, to change the boiling point of the substances in the stream of FT. However, many chemically akhmanova removal of paraffins.

U.S. patent No. 4946560 describes how the Department of internal olefins from alpha-olefins by contacting the feedstock with adductors compound such as anthracene, with the purpose of education olefin adduct, separating the adduct from raw materials, dissociatively olefin adduct under the action of heat to form anthracene and olefin composition is enriched in alpha olefin, and separating anthracene from alpha-olefin. The above link does not imply the need or possibility of application of anthracene for separating olefins from saturated hydrocarbons in the first stage or the subsequent separating linear alpha olefins from saturated hydrocarbons removed in the first stage, along with the separation of linear alpha-olefins from olefins stream output from the first stage.

As soon as the olefins are separated from the saturated hydrocarbons, it would also be desirable to empty the deleted items saturated hydrocarbons and extracted as many as possible of the remaining olefin from a remote saturated hydrocarbon.

Used in the text of the description and the claims, the words “first, second, third, etc. are intended only to distinguish one raw material composition, the compound or the designation of a specific sequence. In order to make it easier to follow a specific thread and for convenience only, olefinic streams marked with the letter "o", threads alpha-olefin is marked with the letters "AO", the threads of the internal olefin is marked with the letters "io" and the threads are saturated compounds marked with the letter 's. Their presence does not contribute to the description and the text of the claims of a particular order, sequence, or values, as well as the lack of letters in the claims or the description of the embodiments does not mean that it is not marked as such technological stage or composition is not required or implied in the description of the embodiments or the claims. When there is no alpha or numeric designation, its use is not mandatory, since other compounds, compositions, stage or reaction zone is not marked similarly, neither in the description of the embodiments or the claims. Their presence or absence does not change or does not specify a specific value, in addition, which is intended to distinguish them from other similarly labeled compounds, compositions, stages of the reaction zones, etc. in the text of the description or the claims.

Now izaberete Ira, containing saturated hydrocarbons, internal olefins and alpha-olefins, including:

(a) contacting the feedstock with a linear polyaromatic compound in a first reaction zone under conditions effective to form a reaction mixture containing the first adducts linear polyaromatic compound-olefin and saturated hydrocarbon;

(b) the Department specified the first olefin adducts from the saturated hydrocarbons in the reaction zone to receive the first stream of olefin adduct and the first stream of saturated hydrocarbons;

s (i) contacting at least part of the first stream of saturated hydrocarbons with a linear polyaromatic compound in a second reaction zone under conditions effective to form a reaction mixture containing the second adducts linear polyaromatic compound-olefin and saturated hydrocarbon;

s (ii) the Department specified second olefin adducts from the reaction mixture in the second reaction zone to obtain a second stream of olefin adduct and the second stream of saturated hydrocarbons, and the concentration of saturated hydrocarbons in the second stream of saturated hydrocarbons is increased compared with the concentration of HB first stream of saturated hydrocarbons is increased compared with the concentration of saturated hydrocarbons in the feedstock;

s (iii) optional dissociation of these second olefin adducts from the first linear aromatic compounds and the first olefin composition;

s (iv) optionally separating the first linear polyaromatic compounds from the said first olefin composition.

Preferably the present invention further includes:

about (i) the dissociation of these first olefin adducts with obtaining a second linear polyaromatic compounds and the second olefin composition containing alpha-olefins and internal olefins;

o (ii) optional separation of the second linear polyaromatic compounds from the said second olefin composition.

AO (i) contacting the second olefin composition with a linear polyaromatic compound in a third reaction zone under conditions effective to form a reaction mixture containing adducts linear polyaromatic compound-alpha-olefin and internal olefin;

ao (ii) the Department specified second adducts of alpha-olefin, and optionally unreacted linear polyaromatic compounds from the reaction mixture in the third reaction zone with the receiving stream adduct of alpha-olefin and the flow of the compounds and alpha-olefin compositions;

ao (iv) optionally separating the linear polyaromatic compounds from the specified alpha-olefin composition; and the concentration of alpha-olefins in the alpha olefin composition is increased compared to the concentration of alpha-olefins in the second olefin composition, and the concentration of alpha-olefins in the second olefin composition is increased compared to the concentration of alpha-olefins in the feedstock.

To be processed, the flow of raw materials includes at least olefins and saturated hydrocarbons. The class of saturated hydrocarbons used in this description, includes at least paraffins. The class of saturated hydrocarbons may also include other molecules such as cycloparaffin.

Olefin means any compound containing at least one double bond in the carbon-carbon bonds. The olefins may be linear, branched, paired, can contain many double bonds in any position along the chain, they may contain substituents that do not contain substituents may contain aryl or alicyclic group, or they may contain heteroatoms. The olefins may contain aryl residues along with aliphatic or cycloaliphatic residues in one connection or m is AMI links in the connection. Preferably, the olefin is aliphatic compound.

The olefin may be branched or linear. Examples of branching include alkyl, aryl or alicyclic chain branching. The number of points of unsaturation along the chain is also not limited. The olefin may be mono-, di-, tri -, etc. unsaturated olefin, optionally paired. The olefin can also contain acetylenic unsaturation.

The alpha-olefin is an olefin, whose double bond is located betweenand-carbon atoms,-carbon atom is any terminal carbon atom no matter what the length of the chain in relation to the lengths of other line segments of the chain in the molecule. The alpha-olefin may be linear or branched. Branching or functional groups can be located on the carbon atoms of the double bond on the carbon atoms adjacent to the carbon atoms of a double bond, or any other location along the main carbon chain. The alpha-olefin can also be Polian, in which two or more points of unsaturation can be located anywhere along the length of the molecule so that at least one double bond was in alpha polnoy circuit, with the exception of any terminal carbon atom. Internal olefin may be linear or branched. The location of branching or a replacement group in the internal olefin is not limited. Branching or functional groups can be located on the carbon atoms of the double bond on the carbon atoms adjacent to the carbon atoms of a double bond, or any other location along the main carbon chain.

Olefins can also be substituted with a chemically reactive functional groups. These types of compounds include compounds identified as oxygenates. Examples of chemically reactive functional groups are carboxyl, aldehyde, keto, thio, ether, hydroxyl and amine groups. The number of functional groups in the molecule is not limited. The functional group can be located anywhere along the main carbon chain.

The raw material is usually formed in such industrial processes as the oligomerization of ethylene, optionally with subsequent isomerization and disproportionation. In another embodiment, the raw material can be obtained by the method of Fischer-Tropsch (Fischer-Tropsch), and it usually contains a high proportion of paraffins. In processes, containing aliphatic molecular chains. Other processes for obtaining raw materials, which may contain a mixture of olefins and paraffins include the dehydrogenation of paraffins, such as those that are formed in the Pacolprocesses of the company “Universal Oil Products (UOP), and the cracking of waxes. Most preferred is a raw material that is formed during the Fischer-Tropsch synthesis (Fischer-Tropsch (FT)).

The FT catalysts and reaction conditions can be selected so as to provide a specific mixture of compounds in the stream of the reaction product. For example, a particular catalyst and reaction conditions may be selected to increase the amount of olefins and to reduce the amount of paraffins and oxygenates in the stream. In another embodiment, the catalyst and reaction conditions may be selected to increase the amount of paraffins and reduce the amount of olefins and oxygenates in the stream.

Typically, the reaction conditions will vary depending on the type of equipment used. The reaction temperature FT change from 100°C to 500°C, the gas pressure at the inlet of the reactor is from atmospheric to 10.3 MPa (1500 psi), and the ratio of hydrogen/carbon monoxide from 0.5:1 to 5:1, preferably from 1.8:1 to 2.2:1, and the volumetric rate of ha is authorizenet layer, a reactor with a fixed bed and the reactor with suspended layer. The temperature of these layers of any specialist in this field can be adjusted to optimize the formation of the products of FT synthesis, including hydrocarbons, especially olefins and types of olefins. To illustrate, without limiting the scope of the claims, in a fluidized bed(s) layer(s) the reaction temperature is usually high, for example in the range from 280 to 350C, preferably from 310 to 340C. If used reactors with a stationary layer, the reaction temperature usually ranges from 200 to 250C, preferably from 210 to 240And when using the reactor(s) with the suspended layer, the temperature usually ranges from 190 to 270C.

The catalyst used in the process FT is any known in the field, but preferably it is chosen from among such metals as molybdenum, tungsten and the elements of group VIII, including iron, cobalt, ruthenium, rhodium, platinum, palladium, iridium, osmium, and combinations of these elements, combinations with other metals, and each is in the form of Svobodova iron and cobalt found wide industrial use, and ruthenium was found to be important as the metal catalysts which promote the formation of waxy compounds with high melting point under conditions of high pressure. Specialists in this field will be able to choose the catalysts, and combinations thereof, which will contribute to the formation of the desired compounds obtained in the synthesis of compositions FT. For example, catalysts in which molten iron containing a promoter such as potassium or oxides deposited on silicon dioxide, aluminum oxide or is a substrate of silicon dioxide-aluminum oxide, known as catalysts for FT synthesis. Another example is the use of metallic cobalt. Cobalt has the advantage that contributes to the formation of smaller amounts of methane in the synthesis process in comparison with the older catalysts based on Nickel and promotes the formation of a wide range of compounds. With proper choice of the substrate, promoters and other combinations of metals cobalt catalyst may be chosen so as to obtain a composition enriched in the desired compounds. Other catalysts, such as catalysts based alloy, iron-cobalt, known for its selective action in otteni, sintered, cemented, impregnated, mixed or deposited on an appropriate substrate.

The catalysts may also contain promoters to increase the catalytic activity, stability or selectivity. Suitable promoters include alkali or alkaline earth metals in free form or in bound form in the form of oxides, hydroxides, salts or combinations thereof.

Flow FT usually contains almost no sulfur or nitrogen, which can be harmful for the other catalysts, which provide the formation of olefins or accelerate the interaction of olefins in other processes of oligomerization or polymerization. However, regardless of the method, the FT process is not very selective to certain compounds and produces a wide range of connections within a single composition.

However, the linear polyaromatic compound used in the method of the present invention is particularly well suited for separating olefins from saturated hydrocarbons in the stream of FT in the presence of oxygenates as oxygenates does not significantly degrade performance properties of the linear polyaromatic compounds.

Although it is still mentioned on the thread FT, SL is igodan as raw material for the method of the present invention. Most crude flows FT contain from 5 to 95 wt.% olefins, and the rest is saturated hydrocarbons, including paraffins and cycloparaffins, and optionally other compounds such as aromatic compounds, optionally containing saturated or unsaturated alkyl branches, and oxygenates, based on the weight of all ingredients in the commodity flow method of the present invention.

The preferred amount of the olefins contained in the stream of FT, lies in the range from 15 to 70 wt.% in the calculation of the mass flow FT. The number of linear alpha olefins in the stream of FT is not limited, but preferably it lies in the range from 15 to 65 wt.% in the calculation of the mass flow FT. A number of other olefins, including branched alpha-olefins and internal olefins, both linear and branched, but are not limited, but preferably lies in the range from 1 to 55 wt.%, more preferably from 5 to 45 wt.% in the calculation of the mass flow FT. The amount of paraffin in most threads FT lies in the range from 5 to 95 wt.% in calculating the weight of all ingredients in the feedstock. In some threads FT FT catalyst is chosen so as to increase the concentration of the olefin and to reduce the concentration of PA is In other threads FT, where the FT catalyst is chosen so as to increase the amount of wax, the amount of paraffin in the stream lies in the range from 65 to 95 wt.%. Other compounds in the stream of FT, such as oxygenates and aromatic compounds constitute the major part of the remaining flow FT and are usually present in amounts ranging from 5 to 40 wt.%. In most threads FT may be present minor amounts of other by-products or impurities in amounts less than 5 wt.%.

The raw material can be recycled stream FT, which is fractionated and/or purified by ordinary distillation, extraction, or other method of separation, to obtain a fraction (wrap) compounds with the desired number of carbon atoms, including composition containing a mixture of compounds with different numbers of carbon atoms, or a composition comprising the fraction of compounds with the same number of carbon atoms, and to remove from the raw stream of high - and low-boiling compounds including olefins, paraffins, aromatics, and oxygenates. When the separation process is carried out by distillation of the reaction mixture containing the adduct, it is preferable that the raw material used in the method of the present sobretudo olefinic compounds in raw materials correspond to the fraction with the number of carbon atoms C5-C20inclusive.

The linear polyaromatic compound effectively separates the saturated hydrocarbons from olefins, when the average number of carbon atoms in the raw material and the prevailing levels of olefinic compounds is in the specified range of values inclusive. When the average number of carbon atoms of the compounds in the raw material exceeds C20, adduct “polyaromatic compound-olefin” boils at a lower temperature than many connections in C20+ raw material composition, resulting in the mentioned high-boiling compounds remain in the residues from the acceleration of the reaction mixture containing the above-mentioned adduct. In accordance with this specific linear polyaromatic compound and a specific commodity composition should be selected so that the composition with the adduct linear polyaromatic compound-olefin in the reaction mixture is boiled at a higher temperature than the unreacted paraffin compounds in the feed feed stream that is subject to division. Therefore, the raw material flow is preferably from the thread that contains compounds with an average number of carbon atoms ranging from 5 to 20, and more preferably in the range from 6 to 18, where the prevailing olefin is processed using one of the methods above, to substantially isolate the fractions containing compounds with the number of carbon atoms above or below the range of C5-C20.

In addition to mixtures of olefins within the specified range can also be used as raw material what is known as a fraction (shoulder straps) olefins with the same number of carbon atoms, when such a single fraction is in the specified range. For example, the raw materials used can be a fraction with the same number of carbon atoms With6With8With9With10With11C12C14or C16. The fraction of compounds with the specified number of carbon atoms is used as comonomers for polyethylene, polyalpha-olefins, sulfonates, alpha-olefin and as drilling fluids.

In the case where it is desirable to use raw materials outside the range of C5-C20can be used by other separation methods to separate the adduct from unreacted reaction mixture, including the choice of more high-boiling aromatic compounds and/or other separation methods such as extraction, liquid/liquid or crystallization. These methods, of course, can also be used raw material in the range Fromis bretania, to get it adduct with olefins in the feed stream. Used in this text, the term "linear polyaromatic compound" refers to a linear polyaromatic compound containing at least three condensed aromatic rings, which may be unsubstituted or may contain substituents, and with the same ability to form adducts that and unsubstituted molecule, and their mixtures. Linearity should cover all three condensed rings, if used as a compound with three condensed rings, and at least four sequentially condensed cyclic ring, if used, the connection of four or more condensed rings. “Linear polyaromatic compound” also refers to mixtures of compounds containing as one of its ingredients linear polyaromatic compound, including, but not limited to, coal tar, anthracene oil and any of the raw mixtures containing fraction separated from naphthalene. “Linear polyaromatic compound” also includes aromatic molecules joined to one another by bridging group, such as a hydrocarbon chain of at least three condensed rings; and those that contain a heteroatom, which does not affect the separation of olefins from saturated hydrocarbons.

The linear polyaromatic compound has the preferred selectivity relative to addactionlistener with a linear alpha-olefin compounds and, secondly, other olefins, and, finally, paraffins, in relation to which the connection is directionspanel in all working conditions outside of the conditions of cracking. Selected linear polyaromatic compound is a compound which has selectivity to linear alpha-olefin compounds in comparison with other olefins greater than 1:1 by moles, preferably 2:1 or more, more preferably 4:1.

Not limiting the scope of the claims examples of the linear polyaromatic compounds include anthracene, 2,3-benzanthracene, pentacene and exact. Suitable examples of substituents in the substituted linear polyaromatic compounds include, but are not limited to the scope of the claims, lower alkyl, for example methyl, ethyl, butyl; halogen atom such as chlorine, bromine, fluorine, nitro-group; a sulfate group; sulfonyloxy; carboxyl; (Carbo-lower-alkane, dimethylamino, methylethylamine; amido; hydroxy; cyano; lower-alkoxygroup, for example methoxy, ethoxy; lower-alkanoyloxy, for example, acetoxy; monocyclic arily, for example phenyl, xylyl, tolyl, benzyl, etc. the Size of a particular Deputy, their number and their location should be selected so that they are relatively inert under the reaction conditions and would not be so large as to prevent the formation of adduct Diels-alder reaction (Diels-Alder). Suitable substituted linear polyaromatic compounds can be determined using routine experimentation. Examples of suitable linear polyaromatic compounds include 9,10-dimethylanthracene, 9,10-dichloroanthracene, 9-methylanthracene, 9-acetylanthracene, 9-(methylaminomethyl)anthracene, 2-chloroanthracene, 2-ethyl-9,10-diethoxyanthracene, antrain and 9-antistreptolysin. Preferred linear polyaromatic compounds are substituted or unsubstituted anthracene and/or benzanthracene, especially unsubstituted anthracene and 2,3-benzanthracene.

In a preferred embodiment of the present invention, in which at each stage the number of linear polyaromatic compounds include anthracene, specified linear polirom the stage a) is contacting the supplied raw material composition, preferably the raw material flow FT containing compounds with an average number of carbon atoms from C6to C18with a linear polyaromatic compound. In the second reaction zone is also the contacting of the flow of the saturated hydrocarbon, remote from the first reaction zone, with a linear polyaromatic compound. In each reaction zone of the reaction of formation of the adduct Diels-alder reaction (Diels-Alder) carried out in the usual way. Examples of suitable equipment to perform the reaction, include the continuous mixing reactor, located in a single installation or a serial or parallel facilities where raw materials or olefinic composition and linear polyaromatic compound is continuously fed into the reactor with stirring to obtain a liquid reaction mixture under the action of heat, and the reaction mixture is continuously away from the reactor with stirring. In another embodiment, the reaction may be carried out in a reactor with a piston flow or series of reactors with piston flow, the column with bubbling or in a batch reactor, the.

The formation of adducts commodity flow and olefin composition is usually carried out in di is the range of preferably from 240 to 265C. the reaction Temperature of addactionmessage exceed 290With, if only in terms of reaction temperature lies below the boiling point of the olefin. Pressures typically range from atmospheric pressure to 100 atmospheres. The reaction can be performed in the gas phase under vacuum or liquid phase or a mixed gas-liquid phase depending on the volatility of raw materials, but they are usually in the liquid phase.

To obtain adducts, can be used in stoichiometric amount or an excess of either the olefin or the linear polyaromatic compounds. The molar ratio of olefins to linear polyaromatic compound is preferably from 0.25:1 to 10:1. It is preferable to use a molar excess of the linear polyaromatic compounds to ensure complete removal of all olefins in the first and subsequent zones addactionmessage. However, with the passage of reaction zones addactionmessage, where the desired high selectivity for the formation of adducts with linear alpha-olefin, the molar ratio of the linear polyaromatic compounds to olefins may be moderate, preferably approaching the molar ratio of olefin to linalool, to form an adduct between the desired number of linear polyaromatic compounds and an olefin. The typical time spent in the reaction zone are in the range from 30 minutes to 4 hours in the case of periodic reactions.

To dissolve the olefins contained in raw materials or linear polyaromatic compound, or both products in the reactor, may be used an inert solvent. Preferred solvents are hydrocarbon solvents, which are liquid at reaction temperatures and in which soluble olefins, linear polyaromatic compound and adducts “olefin-linear polyaromatic compound”. Illustrative examples of suitable solvents include alkanes, such as pentane, ISO-pentane, hexane, heptane, octane and nonan; cycloalkanes such as cyclopentane and cyclohexane; aromatic compounds as benzene, toluene, ethylbenzene and diethylbenzene. The amount of solvent that can be used can vary within a wide range, without exerting a negative influence on the course of the reaction.

Preferably the reaction addactionmessage carried out in the absence of a solvent, thereby increasing the speed the s to separate the solvent. After the formation of the adduct linear polyaromatic compound-olefin” at the stage of (a) the flow of the adduct is fed into the separation device for effective separation of saturated hydrocarbons from the adduct linear polyaromatic compound-olefin and receive the stream of saturated hydrocarbons and the flow associated with the adduct of the olefin at the stage (b). Due to the large molecular mass and structural differences between adducts and other ingredients of the reaction mixtures, such as saturated hydrocarbons and internal olefins, traditional separation methods are well suited for removal of unreacted saturated hydrocarbons at the stage (b). For example, saturated hydrocarbons at the stage (b) can be removed in the form selected from the top of the columns of a shoulder strap or in the form of fractions at a partial vacuum distillation or evaporation by a sudden lowering of the pressure of the reaction mixture with simultaneous drainage of the bottom liquid from the separation equipment containing adducts and unreacted linear polyaromatic compounds. It is desirable to increase the temperature in the lower part of the distillation column to a sufficient extent in order to maintain the distillation of a liquid in a liquid status is te dissociation of adducts. Suitable temperature in the lower part of the separation vessel are in the range from 210 to 280S, more preferably from 230 to 270C. Although the pressure is not specifically limited, and the separation can be carried out under atmospheric pressure, but it is preferable to carry out the separation at a slight vacuum, for example from 26.7 to 93.3 kPa (200 to 700 mm RT.cent.), in order to reduce the operating temperature and the residence time in the reaction zone within the separation apparatus. The residence time in the reaction zone inside the device must be short to avoid excessive dissociation of the adducts, for example from 1 to 30 minutes.

At the stage (b) distillate flow of unreacted saturated hydrocarbons include paraffins and may include, if they are present in the raw material composition, aromatics, and oxygenates, such as alcohols, ketones, acids, along with internal and branched olefins, which could not form an adduct with a linear polyaromatic compound.

In another embodiment, the adducts can be separated by cooling the reaction mixture to crystallization of adducts with subsequent filtration or centrifugation to remove neproreagirovavshimi the connection will be separated from the flows related to the adducts of olefins. Other ingredients such as small amounts of high molecular weight unreacted olefins, internal olefins and branched olefins, can remain in the threads linked in the adduct of the olefin.

The method of the present invention provides flexibility in the regulation of the allocation process flow at each of the stages of addactionmessage and units in order to optimize yield the desired flow and concentration of compounds in a desirable flow. For example, if you want to receive a stream of alpha-olefin with a high concentration of alpha-olefin, the allocation of olefins from raw materials should be moderate to avoid capture of excess amounts of other olefins, some of which otherwise would have been captured at the subsequent stages of separation and reduced the concentration of linear alpha-olefin. However, the high concentration of linear alpha-olefins results in lower stream outputs linear alpha-olefins, than it would be if the allocation rates of olefin from raw materials were set up. On the other hand, if more than the desired output flux linear alpha-olefin than high concentration of linear alpha olefins in the stream linear alpha-olefin, the degree of allocation of olefin, including linear alpha olefins in the olefin composition at the stage of separation, leading to the formation of the exit stream with a higher output stream alpha-olefin, but with lower concentrations of alpha-olefin.

The selection of flow in the branch is determined by the molar ratio of linear polyaromatic compounds to olefins, the residence time in the reaction zone of addactionmessage, the temperature in the separation device and, most importantly, time (speed of separation of the reaction mixture in the separation apparatus. In order to obtain a high degree of extraction of olefinic compositions, install any one of the following variables or their combination: a high molar ratio linear polyaromatic compound to the olefin, for example, >1, a long time spent in the reaction zone to provide a full addactionmessage, and moderate temperature distillation, in order to avoid dissociation of the adducts. To get a smaller selection of olefinic composition and the increased concentration of linear alpha olefins in the composition of linear alpha-olefins, install any one of the following variables or their combination: moderate or close to 1:1 molar Rel is eacli, to provide selective addactionmessage linear alpha olefins in the feedstock. But in any case, the concentration of linear alpha olefin, or any other desirable compounds is higher in the destination stream is compared with the concentration of linear alpha olefin or other desirable compounds in the preceding processed compositions and raw materials.

The speed of separation of olefin from a raw material is not limited and will usually depend on the amount of olefin contained in raw materials. In one of the embodiments of the present invention, the speed of separation of the olefin adducts from the first separation apparatus, in moles per unit of time, is in the range from 0.10 to 0.40, more preferably from 0.15 to 0.35, in each case calculated at the rate of passage of materials 1,00. At these speeds from 40 to 100% of the olefins in the feedstock may be selected as olefin composition. In another embodiment of the present invention, the release rate is in the range from 0.20 to 0.30 in the calculation of the rate of passage of materials to 1.00.

In General, it is desired to obtain a highly concentrated composition of a linear alpha-olefin, from 40 to 70% linear alpha-olefins contained in raw materials, can be highlighted the significant decrease in the concentration of linear alpha olefins in the stream linear alpha-olefin, the selection of the olefin feedstock is in the range from 70 to 100%. As noted above, in any case, the concentration of the desired compounds in the final thread will be higher than the concentration of the desired compounds in previous threads supplied to the reaction zone.

Taking the foregoing into account as an example of optimization of the concentration or amount of linear alpha olefins in the stream of linear alpha-olefins, experts can set the rate of release and the percentage of desirable compounds emitted at each stage of separation, to optimize the concentration or amount of other substances in the feed stream, subject to allocation.

When saturated hydrocarbons are separated from the adduct linear polyaromatic compound-olefin” in the separation apparatus as the first stream of saturated hydrocarbons, the first stream of saturated hydrocarbons is rich in saturated hydrocarbons compared with the saturated hydrocarbons in the feedstock entering the first reaction zone of addactionmessage, and olefin content in the first stream of saturated hydrocarbons is lower than the concentration olefine, proishodit contacting the first stream of saturated hydrocarbons with increased concentration of saturated hydrocarbons and a lower concentration of linear alpha-olefins and internal olefins, linear polyaromatic compounds in the second reaction zone of addactionmessage under conditions effective to form a reaction mixture containing the second adducts linear polyaromatic compound-olefin and a second composition of a saturated hydrocarbon. Suitable reaction conditions and reactors include those used in the reaction zone of addactionmessage for raw materials.

As soon as the second reaction zone at a stage s (i) is formed of the second adduct linear polyaromatic compound-olefin, the flow of the adduct is fed into the separation equipment at the stage s (ii), effective to separate the second adducts linear polyaromatic compound-olefin from saturated hydrocarbons and receiving the second stream of saturated hydrocarbons with increased concentration of saturated hydrocarbons in comparison with the concentration of saturated hydrocarbons in the first stream of saturated hydrocarbons and a second stream adduct linear polyaromatic soedineniya of the methods used to remove bound in olefin adduct from the reaction mixture in the zone of the first compartment. Preferably, the second reaction mixture is distilled, and the second stream of saturated hydrocarbons is withdrawn from the upper part of the distillation column, while the olefin adducts are removed from the column as a stream bottom liquid. The second stream of saturated hydrocarbons includes some internal olefins and alpha-olefins, but in lower concentrations compared to the concentrations of these substances in the first stream of saturated hydrocarbons. However, the concentration of saturated hydrocarbons in the second stream of saturated hydrocarbons higher than their concentration in the first stream of saturated hydrocarbons.

Second adducts linear polyaromatic compound-olefin in the second stream of olefin adduct, selected at stage s (ii) optionally, but preferably, is subjected to dissociation at the stage s (iii) in the area of dissociation to obtain the first linear polyaromatic compounds and the first olefin composition. The first olefin composition preferably includes alpha-olefins and internal olefins and has a high content of these olefins compared with the contents of each of nanno in adduct of olefin in the reactor dissociation, in which the thread linked in the adduct of the olefin is heated and subjected to pyrolysis at a temperature in the range from 200 to 500C, preferably from 300 to 350With in a period of time sufficient for the dissociation of adducts. Next, the temperature of dissociation can be reduced below 200With due distillation gaseous olefin as it is selected using an inert gas. In the pyrolysis of olefins are exempt from the linear polyaromatic compound. For the implementation of dissociation can be used one or more consecutive reactors dissociation, and reactors dissociation can also be operated under pressure from a partial vacuum to pressure above atmospheric.

In an optional but preferred phase s (iv) linear polyaromatic compound can be subsequently separated from the resulting mixture by any known method, which may occur simultaneously with the pyrolysis process in the same pyrolysate, such as distillation by vacuum distillation or evaporation by a sudden pressure reduction of olefins, along with any impurities at temperatures of pyrolysis and linear polearm which melts at a slight vacuum, in order to reduce the boiling point of the dissociated linear alpha-olefin, and at a temperature sufficient for the dissociation of the adduct. Other methods of separation include filtration and centrifugation.

Linear polyaromatic compounds that emit in the areas of dissociation of the present invention, can be re-used in the first reaction zone of addactionmessage where dissociatively linear polyaromatic compounds become a source of linear polyaromatic compounds used for the reaction of addactionmessage in the first zone of addactionmessage, or in the mixing zone, where raw materials, recycled linear polyaromatic compound and some fresh linear polyaromatic compounds are mixed before submit them to the reaction zone addactionmessage.

The first stream of olefin adduct, preferably coming from the separation equipment at the stage (b) in the form of a stream bottom liquid is subjected to dissociation at the stage o (i) in the area of dissociation, to get the second linear polyaromatic compound and the second olefin composition. Equipment and technological conditions for the implementation of the dissociation Pervova dissociation of the second stream of olefin adduct.

In optional stage o (ii) the linear polyaromatic compound is separated from the resulting reaction mixture by any known method, in the same way as described above in optional stage s (iv).

The second olefin composition, separated or in a mixture with disocyanate linear polyaromatic compounds at this stage has a high content of olefins in comparison with olefins in the feedstock. Since the linear polyaromatic compound preferably forms adducts with linear alpha olefins, the concentration of linear alpha olefins in the olefin composition is higher than the concentration of linear alpha-olefins contained in the raw material, based on the weight of all ingredients in the feedstock and the olefinic composition. In the case where the raw material includes branched olefins, the concentration of branched olefins in the second olefin composition may be lower than the concentration of branched olefins in the feedstock. In the case where the olefin composition is not separated from the linear polyaromatic compounds prior to submitting the olefin composition in the reaction zone addactionmessage alpha-olefin, the concentration of ingredients in olefin compositions is in the raw material composition. In addition, the concentration of saturated hydrocarbons and the concentration of paraffins in the olefin composition is lower than the concentration in the raw material.

In the next stage of the way - stage ao (i) to carry out the contact interaction of the second olefin composition with a linear polyaromatic compounds in the third reaction zone under conditions effective to form a reaction mixture containing adducts linear polyaromatic compound-alpha-olefins and internal olefins. Suitable reaction conditions and apparatus include the same that are used in the first reaction zone for raw materials. Because the second olefin composition is used as the power supply unit, almost, if not completely, does not contain saturated hydrocarbons which would otherwise had the effect of dilution of the feedstock, the conversion of olefins in the second olefin composition in adducts linear polyaromatic compound-linear alpha olefin” is higher than the conversion of raw materials into the adducts linear polyaromatic compound-linear alpha olefin”. The preferred selectivity linear polyaromatic compounds in relation to linear alpha-olefins makes possible the separation linebetween internal olefins and branched alpha-olefins.

Once formed adduct linear polyaromatic compound-linear alpha olefin” in the third reaction zone at a stage of ao (i), the flow of the third adduct is sent to the third separating apparatus at the stage of ao (ii), effective for the Department of internal olefins and other unreacted olefin adducts from linear polyaromatic compound-alpha-olefin to receive a stream of internal olefins and a stream of alpha-olefin adduct. Suitable methods and conditions for the Department of adducts from the reaction mixture include any methods used to allocate associated in the olefin adduct from the reaction mixture in the first separation zone. Preferably the reaction mixture is distilled and the flow of internal olefin away from the upper part of the distillation column, whereas the adducts of linear alpha-olefin away from the column as a stream bottom liquid. The distillate separated stream of unreacted internal olefin contains a number of linear internal olefins, branched internal olefins and branched alpha-olefins. The concentration of linear internal olefins, branched internal olefins and branched alpha-olefins in the stream workerist selection of adducts of linear alpha-olefin in the separation apparatus at the stage of ao (ii) may vary and is not limited. In General the percent linear alpha-olefin selected from olefins of the composition, is set so that a total of from 30 to 60% linear alpha-olefins was returned to the stream of alpha-olefin in the calculation of the amount of linear alpha-olefin contained in the raw material. If special attention is paid to the allocation of higher quantities of linear alpha olefins in the stream of alpha-olefin, the percent linear alpha-olefin selected from olefins compositions set such that a total of from more than 60 to 95% linear alpha-olefins in the calculation of the number of alpha-olefins in the feedstock was allocated to the stream of alpha-olefin.

Adducts linear polyaromatic compound-alpha-olefin in the flow of alpha-olefin adduct, taken from the stage ao (ii) is subjected to dissociation at the stage ao (iii) in the area of dissociation with obtaining linear polyaromatic compounds and alpha-olefin compositions. Suitable methods and conditions for dissociation of adducts in the stream alpha-olefin adduct include any methods mentioned as suitable for the dissociation of adducts in the first stream of olefin adduct. The specified stream has a concentration of linear alpha-olefins higher than the concentration of linear alfalfa-olefins and small amounts of other olefins, such as linear internal olefins, branched internal olefin and branched alpha-olefins. The concentration of these other lower olefins in the composition of the linear alpha-olefin than the concentration of these other olefins in the olefin composition. The concentration of linear alpha olefins in the alpha olefin composition is preferably at least 90 wt.%, more preferably at least 95 wt.%, in calculating the weight of all ingredients in the flux of alpha-olefin.

Optionally, but preferably, at the stage of ao (iv) alpha-olefin composition is separated and isolated from the dissociated linear polyaromatic compounds. Alpha-olefin composition at this stage take away from the apparatus for dissociation to obtain alpha-olefin stream. The alpha-olefins can be abstracted from the capacity for dissociation through the top of the cracking apparatus operating under a slight vacuum and at a temperature sufficient to ensure the evaporation of alpha-olefins and dissociation of adducts. More preferably, the removal of alpha-olefins is carried out in the same apparatus that is used for the reaction of dissociation on stage ao (iii).

If desired, the flow of internal olefin may be Oia alpha-olefin is not critical for the concrete industry. In another embodiment, part or all of the combined stream of the internal olefin of the second olefinic stream or a portion of the individual second olefinic stream and/or stream of the internal olefin may be sent for recycling in the raw material stream fed to the first reaction zone of addactionmessage.

In order to measure reductions in the percentage of nutrients in stream concentrations (all concentrations are determined based on the total weight of all ingredients contained in this thread) substances or number of the considered substances contained in the product flow, is subtracted from the concentration of the substance or number of the considered substances contained in this previous thread, and the difference is then divided by the concentration of those substances in the previous thread, multiplied by 100. In order to measure the percent increase of nutrients in the stream concentration of the substance or several substances in the previous or feed stream is subtracted from the concentration of substances or of the number of the considered substances contained in the product flow, the difference is then divided by the concentration of those substances contained in the preceding feed stream, and multiply by 100. For the joint consideration of a number of substances are the total amounts in the product flow then compare with the total value of the sum in the previous thread, to determine whether increased or decreased, the total value for the number of substances in the product flow compared to the total amount in the previous thread. Then carry out the appropriate calculations mentioned above, depending on whether increased or decreased, the total values for a number of substances in the product flow.

The concentration of all olefins in the stream of saturated hydrocarbon is preferably reduced in the method of the present invention only at a single pass, at least 15%, more preferably at least 30%, and most preferably at least 40% compared with the concentration of all olefins in the feedstock.

Since the linear polyaromatic compound is more selective effect when addactionlistener with linear alpha olefins in comparison with other olefins, in another embodiment of the invention, the concentration of linear alpha olefins in the first stream of saturated hydrocarbons is reduced at least 30%, more preferably at least 40%, most preferably at least 50% compared with the concentration of linear alpha-olefins contained in the feed stream.

The concentration of saturated hydrocarbons in the feed stream. The concentration is preferably increased at least 5%, more preferably at least 10%, most preferably at least 20%, and may increase by 100-400%, especially when the concentration of saturated hydrocarbon in the raw material is low. Typically, the degree of increase in the content of saturated hydrocarbons in the stream of saturated hydrocarbons varies inversely proportional to the concentration of saturated hydrocarbons in exactly the raw materials used.

The concentration of saturated hydrocarbons in the second olefin composition is preferably reduced in the method of the present invention only in one passage, at least 80%, more preferably at least 90%, most preferably at least 95%, compared with the concentration of saturated hydrocarbons in the feedstock, and most preferably 100%.

The concentration of linear alpha olefins in the second olefin composition is increased compared with the concentration of linear alpha-olefins contained in the feed stream. The concentration of linear alpha-olefins contained in the second olefin composition, preferably increased at least 30%, more preferably at least on rashisa in the raw material composition. The method of the present invention can achieve the concentration of linear alpha olefins in the olefin composition is higher than 80 wt.%, more preferably at least 90 wt.%.

In addition, the concentration of all olefins in the second olefin composition is increased compared to the concentration of all olefins in the feed stream. The degree of increase of the content of the olefin is inversely proportional to the concentration of olefins contained in raw materials. Preferably the concentration of all olefins in the second olefin composition is increased by at least 40%, preferably at least 60%.

The method of the present invention can provide the separation of olefins from saturated hydrocarbons in a feedstock, consisting mainly of saturated hydrocarbons and olefins, reaching concentrations of olefins in the olefin composition in the range from 90 to 100%.

The method of the present invention increases the concentration of saturated hydrocarbons in the second stream of saturated hydrocarbons as compared with the first stream of saturated hydrocarbons and raw materials. The degree of increase in concentration in the second stream of saturated hydrocarbons compared with the first stream of saturated hydrocarbons of predpochitali will not be too high at this stage, since the first addactionmessage and separation significantly increase the amount of saturated hydrocarbons in the first stream of saturated hydrocarbons.

The concentration of internal olefins in the second stream of saturated hydrocarbons is usually reduced at least by 20% compared with the concentration of internal olefins in the first stream of saturated hydrocarbons.

The first olefin composition and the second olefinic stream have increased the concentration of linear alpha-olefins compared to the concentration of linear alpha olefins in the first stream of saturated hydrocarbons in the feedstock, preferably at least 50%, more preferably at least 100%.

The concentration of internal olefins is also increased in the first olefin composition and the second olefinic stream compared with the concentration of internal olefins in the first stream of saturated hydrocarbons, preferably at least 20%, more preferably at least 50%.

The concentration of linear alpha olefins in the alpha olefin composition is increased compared with the concentration of linear alpha olefins in the second olefin composition and raw materials. The concentration of linear alpha olefins in al is in the second olefin composition, at least 15%, more preferably at least 20%, most preferably at least 30%. The concentration of all other olefins, alpha-olefins stream preferably decreases in total at least 20%, more preferably at least 30%, most preferably at least 40% compared with the concentration of all other olefins total in the second olefin composition. In particular, the concentration of branched olefins, alpha-olefins stream may be reduced to 60%, more preferably by 75%, and even 90% in comparison with the concentration of branched olefins in the feedstock and the second olefin composition.

The concentration of internal olefins in the composition of internal olefins is increased compared with the concentration of internal olefins in the second olefin composition and raw materials. The concentration of internal olefins in the composition of internal olefins is preferably greater than the concentration of internal olefins in the second olefin composition, of at least 10%, more preferably at least 15% and usually by up to 40%. The concentration of branched olefins in the composition of internal olefins preferably increases the PNA 70%. The concentration of linear alpha olefins in the stream of internal olefins is preferably reduced by at least 20%, more preferably at least 30% compared with the concentration of linear alpha-olefin in the second olefin composition.

Hereinafter the present invention will be described using examples with reference to the sole figure of the accompanying diagram, which is a process flowchart of the method of the present invention. Stage addactionmessage, separation and dissociation is carried out in each of the individual blocks 1, 2 and 3, and lines 1-8 mean flows of raw materials and products included in each block and out of each block.

Block 1 indicates the first zone addactionmessage, the separation zone and a zone of dissociation. Unit 2 means the second zone addactionmessage, the separation zone and a zone of dissociation. Unit 3 refers to the third zone addactionmessage, the separation zone and a zone of dissociation.

Line 1 indicates the raw material composition, line 2 refers to the first stream of the composition of saturated hydrocarbons, line 3 indicates the second olefinic stream composition, line 4 means the second stream of saturated hydrocarbons and line 5 is the first olefinic stream composition, line 6 oz is a variant of the method according to the invention, when you combine the second olefinic stream and the flow of internal olefins.

Modeled mass balances presented below in tables illustrate the quality of the forecast one of the variants of the method according to the invention, in which it is desirable to achieve a high concentration of linear alpha olefins in the olefin composition and to remove internal olefins and alpha-olefins from the first stream of saturated hydrocarbons. In table a presents the mass balance calculation on the amount of each substance in raw materials and the product flow, whereas in the table presented In the mass balance calculation for the concentration of each substance in the raw material and product flow. The results tables presented in moles per unit of time and the results table is presented in molar percent composition of each stream. Mass balances calculated in order to illustrate the concept of the present invention, and based on the use of anthracene as a linear polyaromatic compounds and on the assumptions listed below.

Assumptions:

Block allocation 1 is 70% linear alpha-olefins in the stream 1. Block wideleaved 60% linear alpha-olefins, contained in the stream 3. At each stage assumes the establishment of an equilibrium state. It is assumed that the equipment can provide the full retention of saturated hydrocarbons, aromatics and oxygenates. The ratio of the equilibrium constants between the linear alpha-olefins and linear 2-olefins is set equal to 2.1. The ratio of the equilibrium constants between the linear alpha-olefins and 2-methyl-1-olefins is set to 20. In unit 1, the percentage of linear 2-olefin, extracted from the block 1, is 46%, and 2-methyl-1-olefin is 10%. In unit 2 is extracted 88% linear 2-olefins and 49% 2-methyl-1-olefin, each value is calculated in relation to the quantity of materials received in block 2.

Presented in tables C and D mass balances illustrate the quality of the forecast is another variant of implementation of the present invention, in which it is desirable to extract a higher amount of linear alpha olefins in the stream linear alpha-olefin, albeit at the expense of lower concentrations of them in comparison with the embodiment discussed above. Table presents the mass balance calculation on the amount of each compound in the flow of raw materials and the product flow, then to the E. of the product. Mass balances are presented on the settlement basis in order to illustrate the concept of the present invention, and based on the use of anthracene as a linear polyaromatic compounds and on the assumptions listed below.

Assumptions:

Block allocation 1 is set at 85% of linear alpha olefins in the stream 1. Block allocation 2 installed on 95% of linear alpha-olefins and 59% of the olefins contained in the stream 2. Block allocation 3 is set to 75% linear alpha-olefins contained in the stream 3. It is assumed that at each stage is set to the state of equilibrium. It is assumed that the equipment can provide the full retention of saturated hydrocarbons, aromatics and oxygenates. The ratio of the equilibrium constants between the linear alpha-olefins and linear 2-olefins is set equal to 2.7. The ratio of the equilibrium constants between the linear alpha-olefins and 2-methyl-1-olefins is set to 20. In unit 1, the percentage of linear 2-olefins and 2-methyl-1-olefin, extracted from the block 1, is 68 and 22%, respectively. In unit 2 the percentage of extracted linear 2-olefins and 2-methyl is an additional advantage of the stream of the Fischer-Tropsch (Fischer-Tropsch) is it contains a mixture of compounds with an even and odd number of carbon atoms, and the method of the present invention forms a stream containing olefinic compounds with even and odd number of carbon atoms and saturated hydrocarbons in the number of very low to zero with a very high concentration of linear alpha-olefins. The method of the present invention may also provide olefinic composition of Fischer-Tropsch (Fischer-Tropsch), containing a mixture of internal olefins and/or branched olefins and linear alpha-olefins with a very low amount of saturated hydrocarbons.

In one embodiment, the implementation of the method of the present invention provides a composition, preferably of the type Fischer-Tropsch (Fischer-Tropsch) containing olefins with even and odd number of carbon atoms, and the composition has a connection with the average number of carbon atoms ranging from5to C20preferably from C6to C18or more preferably in the range from C6to C12including:

a) at least two linear alpha-olefin compounds having different length of carbon chain;

b) the two most prevalent (in molar terms) of linear alpha-olefin is connected to the lines of carbon atoms from C5to C20or in the case of raw materials on the basis of connections with the number of carbon atoms from C6to C18within the specified range, or in the case of raw materials on the basis of connections with the number of carbon atoms from C6to C12inside the above-mentioned range, inclusive;

c) the two most prevalent linear alpha-olefin compounds are present in amounts of at least 20 wt.%, preferably, at least 30 wt.%, more preferably at least 40 wt.% based on the weight of the olefins in the composition;

d) total total number of linear alpha olefins present in the composition within the specified range, inclusive, is at least 40 wt.%, preferably, at least 60 wt.%, more preferably at least 70 wt.%, and even 90 wt.% or more based on the weight of the olefins in the composition;

e) one or more olefins with an odd number of carbon atoms within the specified range is contained in an amount of at least 10 wt.%, preferably, at least 20 wt.%, more preferably at least 30 wt.% and even 40 wt.% or more total;

f) the total amount of aromatic compounds, the additional 2 wt.% or less, also more preferably 1 wt.% or less, most preferably 0.5 wt.% or less, each based on the weight of the composition; and preferably

g) 6 wt.% or less branched olefins containing branching in position C2 or C3 relative to the nearest double bond, more preferably 4 wt.% or less based on the weight of the composition.

The above composition preferably contains as one of the two most prevalent olefinic compounds linear alpha-olefin with an odd number of carbon atoms.

The present invention also relates to compositions, preferably of the type Fischer-Tropsch (Fischer-Tropsch), containing compounds with an average number of carbon atoms ranging from6to C18comprising at least two linear alpha-olefin compounds having different lengths of carbon chains within a specified range including at least 50 wt.% linear alpha-olefins, and the composition contains the most predominant olefin compounds represented by the compounds with the number of carbon atoms n, with the following most predominant olefin compounds have a number of carbon atoms or n+1 or n-1; and specified to the tion this composition has branched olefins, containing branching in position C2 or C3 with respect to the closest double bond in the amount of 6 wt.%, more preferably 4 wt.% or less based on the weight of the composition.

Further, the present invention relates to a method of contacting a linear polyaromatic compound with a raw material composition comprising linear alpha olefins, internal olefins and saturated hydrocarbons, separating olefins from saturated hydrocarbons in the raw material composition to obtain olefin stream and a stream of saturated hydrocarbons, the subsequent contact of the linear polyaromatic compound with a stream of saturated hydrocarbons comprising linear alpha olefins and internal olefins, and Department of internal olefins and linear alpha-olefins from saturated hydrocarbons in the stream of saturated hydrocarbons to obtain a second stream of saturated hydrocarbon and olefin compositions moreover, the concentration of each internal olefins and linear alpha olefins in the olefin composition is higher than the concentration of each internal olefins and linear alpha olefins in the feedstock and the olefinic stream.

The method of the present invention gives predominantly olefinic composition, the manage, at least 90% and up to 100% pure olefin in the olefin composition. The method of the present invention also provides a selection of olefinic composition of the first stream of saturated hydrocarbon, and olefin composition is enriched in linear alpha olefins and internal olefins.

Olefinic composition of the present invention can be used as a component of drilling fluids to interact with elementary sulfur with the aim of obtaining sulfur-containing products, as agents for extreme pressure in Metalworking fluids, as co monomer for the polymerization of polyethylene, as an intermediate product upon receipt polyalpha-olefins (PAO), used as a lubricant, as a raw material for the chlorination upon receipt of polychlorinated hydrocarbons in applications PVC, for interaction with hydrogen sulfide while receiving primary and secondary mercaptans as pharmaceutical intermediates and as additives to modify the properties of rubbers as solvents and as precursors for the production of alcohol plasticizers, alcohols for the production of detergents and surface-active is different liquids and powders, powders and liquids for washing machines, bulk Soaps, shampoos, liquid Soaps for hands and cleaners for hard surfaces.

Further, the present invention is illustrated with reference to the following examples.

EXAMPLE

In used as raw material flow Fischer-Tropsch (Fischer-Tropsch), consisting of a composition described in table 1. Song FT get by passing synthesis gas over the catalyst FT, followed by distillation of the products in the range of boiling points hexyl and undecylenic hydrocarbons. The above composition is used as raw material. Hydrocarbons with the number of carbon atoms in the range From7-C10contained in the greatest quantity.

0.14 mol of anthracene with a purity of 95% and 62.5 g of material is loaded into the autoclave. The total amount of olefin in the loaded raw materials is approximately 0.15 mol (19,8 g) molar ratio of olefin/anthracene to 1.1:1. The autoclave is pressurized and blown off with nitrogen. The autoclave is heated at 255With over 5,6 hours to get adduct Diels-alder reaction (Diels-Alder) between the olefin and anthracene. In the process of heating the contents of the autoclave are stirred.

Upon completion of the reaction, the autoclave is cooled to 20C. the resulting mixture was transferred into stekljannoi in the form of a stream of saturated hydrocarbons (TM) 1. The composition of NP 1 determined by gas chromatography. The substance remaining in the flask consists of some captured saturated hydrocarbons, unreacted anthracene and adduct the anthracene-olefin”. Then the flask and its contents are heated to a temperature of 310-350With to ensure dissociation of the adduct to anthracene and olefinic product 1, described in table 1. Olefinic product 1 is separated from anthracene by distillation. Remove 9.3 g of olefin product 1, of which 8.7 g is olefin. The composition of the olefinic product 1 is determined by analysis by gas chromatography.

The results show that NP 1 enriched in saturated hydrocarbons (alkanes) compared to the concentration of saturated hydrocarbons in the flow of raw materials by 24%. The concentration of alpha-olefin in the TM 1 55% lower than the concentration of alpha-olefin in the feedstock.

Olefinic product 1 has a significantly higher alpha olefin and content of all olefins in comparison with the concentration of alpha-olefin and content of all olefins in the feed stream. Olefinic product 1 has alpha olefin by 202% more, and the content of all olefins in 197% more([(88,21+5,77)-(27,18+4,43)]/(27,18+4,43)100).

The presence of saturated hydrocarbons in the olefin product 1 due to its incomplete removal through distillation of unreacted material from the adduct at the stage of dissociation.

The concentration of saturated hydrocarbons in the TM 1 increases and the concentration of internal olefins in the TM 1 is reduced by the separation of part of the internal olefins in the stream NP 1 from saturated hydrocarbons.

44,3 g NP 1, containing 7.5 g (0,059 mol of olefin, process 0,034 mole of anthracene for 6 hours at 255With the above equipment. The molar ratio of olefin to anthracene is 1.7:1. 30,24 g of unreacted material is removed by distillation in a stream NP 2. Distillation residues of the distillation column is subjected to thermal dissociation at 310-350Since, as described above. 1,67 g of the resulting stream of internal olefin Olefin 2 is removed by distillation from dissociated anthracene. Each thread NP 2 and olefin 2 analyze by gas chromatography. The results are presented in table 2.

NP 2 compared with the feed stream NP 1 enriched alkanes by 7.3%. The concentration of internal olefins in the TM 2 compared with the feed stream NP 1 is the s concentration of each of the olefin in the feed stream NP 1. The contents of internal olefin increases by about 98%, and the content of alpha-olefin increases by about 570%.

Olefinic product 1 is also treated as follows in order to increase the concentration of alpha-olefin. by 0.055 mole of anthracene having a purity of 95%, and 9.3 g of olefin product 1 is loaded into the autoclave. The total amount of olefin in the loaded raw materials is approximately 0,068 mol (8.7 g) in a molar ratio of olefin/anthracene, 1,2:1. The autoclave is pressurized and then rinsed with nitrogen. The autoclave is heated at 255C for 6 hours to form the adduct of the Diels-alder reaction (Diels-Alder) between the olefin and anthracene. In the process of heating the contents of the autoclave are stirred.

Upon completion of the reaction, the autoclave is cooled to 20C. the Mixture of products is transferred into a glass flask and unreacted olefin, saturated hydrocarbons and unreacted oxygenates are removed by distillation in the form of internal olefin product. The structure of the internal olefin product is determined by analysis by gas chromatography, the results of which predstavleny below in table 3.

The substance remaining in the flask consists of nekotorogo at a temperature of 250-280With to ensure dissociation of the adduct of anthracene and alpha-olefin product, described in table 3. In the process stage of dissociation above adduct “anthracene-olefin” miss gaseous nitrogen, to expedite removal and selection of olefin. Alpha-olefin product is separated and recovered from anthracene by distillation. Allocate 2.6 g alpha-olefin product. The composition of the alpha-olefin product is determined by analysis by gas chromatography.

Alpha-olefin product compared with the feed stream of olefin 1 is the concentration of alpha-olefin is 10% higher.

The concentration of internal olefins in the alpha olefin product compared with the feed stream of olefin 1 is less than 50%.

Internal olefin product enriched internal olefins compared to the concentration of internal olefins in the feed stream of olefin 1 to 112%.

Claims

1. The method of processing raw materials containing saturated hydrocarbons, internal olefins and alpha-olefins comprising (a) contacting the feedstock with a linear polyaromatic compound in a first reaction zone under conditions effective to form a reaction mixture containing p what's the first olefin adducts from the saturated hydrocarbons in the reaction mixture to obtain the first stream of olefin adduct and the first stream of saturated hydrocarbons; s(i) contacting at least part of the first stream of saturated hydrocarbons with a linear polyaromatic compound in a second reaction zone under conditions effective to form a reaction mixture containing the second adduct linear polyaromatic compound-olefin and saturated hydrocarbons; s(ii) the Department specified second olefin adducts from the reaction mixture in the second reaction zone to obtain a second stream of olefin adduct and the second stream of saturated hydrocarbons, and the concentration of saturated hydrocarbons in the second stream of saturated hydrocarbons higher than the concentration of saturated hydrocarbons in the first stream of saturated hydrocarbons, and the concentration of saturated hydrocarbons in the first stream of saturated hydrocarbons higher than the concentration of saturated hydrocarbons in the feedstock; s(iii) optional dissociation of these second olefin adducts from the first linear polyaromatic compounds and the first olefin composition; and s(iv) optional separation of the first linear polyaromatic compounds from the said first olefin composition.

2. The method according to p. 1, comprising about(i) the dissociation of these first olefin adducts from Levine and internal olefins; (ii) optionally separating the second linear polyaromatic compounds from the said second olefin composition; AO(i) contacting the second olefin composition with a linear polyaromatic compound in a third reaction zone under conditions effective to form a reaction mixture containing adducts linear polyaromatic compound-alpha-olefin and internal olefin; AO(ii) the separation of these alpha-olefin adducts, and, optionally, unreacted linear polyaromatic compounds from the reaction mixture in the third reaction zone to obtain a stream of alpha olefin adduct and flow of internal olefin; SC(iii) dissociation of alpha-olefin adducts with obtaining linear polyaromatic compounds and an alpha olefin composition; AO(iv) optionally separating the linear polyaromatic compounds from the specified alpha-olefin composition, and the concentration of alpha-olefins in the alpha olefin composition is higher than the concentration of alpha-olefins in the second olefin composition, and the concentration of alpha-olefins in the second olefin composition is higher than the concentration of alpha-olefins in the feedstock.

3. The method according to p. 1 or 2, in which contact>4. The method according to any of paragraphs.1-3, in which the raw material includes a thread formed in the Fischer-Tropsch process (Fischer-Tropsch).

5. The method according to any of paragraphs.1-4, in which the feedstock comprises from 15 to 70 wt.% the olefin based on the weight of all ingredients in the feedstock.

6. The method according to any of paragraphs.1-5, in which the number of the paraffin is in the range from 5 to 95 wt.% in calculating the weight of all ingredients in the feedstock.

7. The method according to any of paragraphs.1-6, in which the raw material contains compounds with an average number of carbon atoms in the range From5-C20and in which the prevailing olefinic compounds in the raw materials have a number of carbon atoms within5-C20inclusive.

8. The method according to any of paragraphs.1-7, in which the total concentration of olefins, and the concentration of linear alpha-olefins higher in the second olefin composition than the concentration of olefins and linear alpha olefins in the feedstock, and the concentration of saturated hydrocarbons is less than the second olefin composition than the concentration of saturated hydrocarbons in the feedstock.

9. The method according to any of paragraphs.1-8, in which the linear polyaromatic compound at each stage includes a substituted or unsubstituted anthracene and/or benzanthracene.

10. The composition including olefins with even and odd cisi with an average number of carbon atoms ranging from5to C20and includes (a) at least two linear alpha-olefin compounds having different lengths of carbon chains; (b) the two most prevalent (in molar terms) of linear alpha-olefin compound of the above, at least two linear alpha-olefin compounds are each in the range of the numbers of carbon atoms from C5to C20inclusive; (C) the two most prevalent linear alpha-olefin compounds are present in amounts of at least 20 wt.%, based on the weight of the olefins in the composition; (d) cumulatively, the total number of linear alpha-olefins contained in the composition within the specified range of values inclusive, is at least 40 wt.%, based on the weight of the olefins in the composition; (e) one or more olefins with an odd number of carbon atoms within a specified range of values contained in an amount of at least 10 wt.% total; (f) the total amount of aromatic compounds, saturated hydrocarbons and oxygenates 10 wt.% or less based on the weight of the composition; and optionally (g) 6 wt.% or less branched olefins having branching in the provisions of the C2 or C3 relative to the nearest double

 

Same patents:

The invention relates to a method of separation of olefins from saturated hydrocarbons, and more specifically to a method of separation of olefins from saturated hydrocarbons in the stream of the Fischer-Tropsch (FT)

The invention relates to a method of separation of linear olefins with internal double bonds from branched olefins with internal double bonds

The invention relates to the field of production of olefinic hydrocarbons obtained from paraffin hydrocarbons by dehydrogenation in a fluidized bed of catalyst and used for the synthesis of isoprene, ethers or other organic products and can be used in the petrochemical industry

The invention relates to the field of organic chemistry, namely, the method of production of Ala-4Z-ENES

The invention relates to the field of petrochemicals, in particular the production of trimers and tetramers of propylene, which are widely used as raw material in the manufacture of additives to oils, plasticizers, flotation agents and other surfactants and synthetic oils

FIELD: regeneration of heat and extraction of impurities.

SUBSTANCE: the invention is pertaining to the method of regeneration of heat and extraction of impurities from the area of the heat-producing reaction in the fluidized flow, conducted for conversion into light olefins of oxygenates present in the flow of the oxygenate (oxygen-containing) raw. raw. The offered method includes the new system of a two-stage quick chilling intended for extraction at the first stage of water from the outgoing from the reactor flow and regeneration of heat of this flow for the purpose, at least, of the partial evaporation of the raw flow due to indirect heat-exchange between the oxygenated raw and the flow of the upper product of the first stage or the flow of recirculation of the first stage. The flow of purification being withdrawn from the first stage, contains the large share of impurities and the high-boiling oxygenates. In the second stage besides conduct extraction of water from the products flow containing light olefins, and produce the flow of the purified water, which requires only the minimum evaporation of the water for production of the water flow of the high degree purification. The method allows to concentrate the impurities in a rather small flow and ensures the significant saving of power and money resources at production of a flow of the vaporous raw guided into the area of realization of the heat-exchange reaction in the fluidized flow.

EFFECT: the invention ensures concentration of the impurities in a rather small flow and the significant saving of power and money at production of the flow of the vaporous raw directed into the area of realization of the heat-exchange reaction in the fluidized flow.

19 cl, 3 tbl, 4 dwg, 5 ex

FIELD: petrochemical processes.

SUBSTANCE: narrow-range hydrocarbon stock is fed into reaction-distillation tower at a level located between lower and upper tower parts to perform isomerization and disproportionation of hydrocarbons. Reaction mixture is maintained in vapor-liquid equilibrium state to concentrate lighter reaction products in vapor phase and higher ones in liquid phase by means of controlling temperature profile and in-tower pressure. Higher olefins are withdrawn as bottom product and lighter olefins from the top of tower.

EFFECT: increased yield of desired product.

41 cl, 4 dwg, 5 ex

FIELD: petroleum chemistry.

SUBSTANCE: claimed method includes oligomerization of one or more alpha-olefins with ethylene in presence of metal-containing catalytic system, using one or more bisaryl pyrimidine-MXa complex and/or one or more [bisaryl pyrimidine-MYpLb+]q- complex. Process is carried out at ethylene pressure less than 2.5 MPa.

EFFECT: method for production of target product of increased yield.

10 cl, 1 tbl, 3 dwg, 17 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: catalyst contains following active components: Pd (0.001-1%), Bi (0.001-5%), at least of Ag, Cu, Zn, K, Na, Mg, Ca, Be, Sn, Pb, Cd, Sr, Ba, Ra, Mn, Zr, Mo, and Ge (0.001-10%), and at least one of rare-earth metals deposited on porous inorganic carrier (the balance.). Catalyst is capable of selectively and rapidly hydrogenating strongly unsaturated hydrocarbons such as alkynes. Catalyst is suitable for industrial cracking process and is characterized by favorable long regeneration period, long service time, and low cost.

EFFECT: improved performance characteristics of catalyst at low cost.

23 cl, 5 tbl, 22 ex

FIELD: petroleum chemistry.

SUBSTANCE: 1,3-butadiene is exposed to telomerization with telogene of general formula H-X-Y-H, wherein X represents oxygen, sulfur, nitrogen or phosphorus; Y represents carbon, nitrogen or silicium; and X and Y optionally may have substituents according to valence thereof to form telomer of general formula H2C=CH-CH2-CH2-CH2-CH=CH-CH2-X-Y-H. Said telomer is hydrolyzed to 1-substituted 2-octene of formula H3C-CH-CH2-CH2-CH2-CH=CH-CH2-X-Y-H. Substituted 2-octene is splitted to produce 1-octene.

EFFECT: improved method for production of 1-octene.

28 cl, 4 ex

FIELD: organic chemistry.

SUBSTANCE: claimed method includes a) reaction of carbon monoxide and hydrogen in presence of effective amount of Fischer-Tropsch catalyst; b) separation of at least one hydrocarbon cut containing 95 % of C15+-hydrocarbons from obtained hydrocarbon mixture; c) contacting separated cut with hydrogen in presence of effective amount of hydration catalyst under hydration conditions; d) treatment of hydrated hydrocarbon cut by medium thermal cracking; and e) separation of mixture, including linear C5+-olefins from obtained cracking-product. Method for production of linear alcohols by oxidative synthesis of abovementioned olefins also is disclosed.

EFFECT: improved method for production of linear olefins.

12 cl, 3 tbl, 1 dwg, 2 ex

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