Olefin isomerization process

FIELD: industrial organic synthesis.

SUBSTANCE: before olefin-containing raw material is brought into contact with isomerization catalyst, one or several components of the raw material are subjected to preliminary treatment coming into contact with preliminary treatment material containing zeolite with pore size at least 0.35 nm. Initial olefin is, in particular, vinylidene olefin of general formula CH2=C(R1)R2, wherein R1 and R2 independently represent alkyl groups having at least 2 carbon atoms so that molecular structure includes at least one allyl hydrogen atom.

EFFECT: increased selectivity.

10 cl, 1 tbl, 11 ex

 

The scope of the invention

The invention relates to a method of isomerization of the double bond of the olefin, where the method includes contacting the feedstock comprising olefins, the isomerization catalyst.

As used here, the term "isomerization of double bonds" means the shift of the double bond in the molecular structure of the olefin of thermodynamically less favorable position in thermodynamically more favorable position. An example of isomerization of the double bond is offset double bond line α-olefin from an external, α-provisions in the internal position, for example βor γ-position. Another example is the displacement of one or two double bonds non-paired diolefine with the formation of paired diolefin. Another example is the shift of the double bond vinylidenes of the olefin with the formation of trisemester of Athena, such as the isomerization of 2-ethyl-1-hexene to 3-methyl-2-Heptene or 3-methyl-3-Heptene.

Background of the invention

US-A-5789646 describes a method of isomerization of the double bond of the olefin, where the method includes contacting the feedstock comprising olefins, the isomerization catalyst which is a solid acid catalyst. Solid acid catalysts, which are presented in the examples of processing according to US-A-5789646 are H-ZSM-5 with an atomic ratio to AMNI/aluminium 25 and cross-linked ion exchange resin based on sulfonic acid. In US-A-5789646 indicated that raw materials, including olefin, preferably should be dry.

US-A-4697040 describes a method of isomerization of the double bond of the olefin, where the method includes contacting the feedstock comprising olefins, the isomerization catalyst which comprises zeolite in sodium form. Zeolite catalyst for US-A-4697040 is a specific type zeolite Y, denoted by LZ-Y52 (trade mark). Under US-A-4697040 devoted to the description of the preceding techniques, reference is made to US-A-3686250, which States that a strongly acidic isomerization catalysts have the disadvantage that they are deactivated with undesirable high speed trace amounts of impurities, so that the isomerization catalysts moderate acidity particularly preferred from the viewpoint of cost due to the long period of activity and reasons low cost. In US-A-3686250 the methodology of the protective layer to load the catalyst in the form of the previous party, download in the line of flow layer before the main catalytic Converter.

US-A-4749819 describes a method of isomerization of the double bond of the olefin, comprising contacting the feedstock containing olefins, isomerization catalyst, which is a zeolite with a suitable pore size, preferably ferrierite. In US-A-4749819 indicated that raw materials can be the seat reservation is treated by bringing it in contact with the refractory inorganic oxide, for example, aluminum oxide, silicon dioxide, zirconium dioxide, magnesium oxide, silicon dioxide, aluminum oxide, silicon dioxide, aluminum oxide - chromium, etc. or other molecular sieve unspecified type.

US-A-5237120 describes a method of isomerization of the double bond of the olefin, comprising contacting the feedstock containing olefins, isomerization catalyst consisting of a zeolite, the outer surface which at least partially deactivated for acid catalyzed reactions. In the example of the processing according to US-A-5237120 the raw material is pre-treated by bringing it into contact with the material for pre-treatment,consisting of γ-aluminium oxide recovered copper chromite and molecular sieve zeolite-zeolite-has a pore size of 0.4 nm.

Although much attention was paid to the pre-treatment of raw materials for the method of isomerization of the double bond of the olefin, it is still desirable to improve pre-processing, thereby improving the operational characteristics of the isomerization catalyst.

Brief description of the invention

The present invention relates to an improved material for pre-treatment in relation to method of isomerization of the double bond of the olefin. The use of Matera the Ala for pre-treatment of the present invention results in improved performance of the catalyst. Improved performance of the catalyst can be treated in one or more aspects, such as improved catalytic activity, improved selectivity, improved stability of the catalyst in terms of activity and improved stability of the catalyst in terms of selectivity. In this context, selectivity can be viewed in different ways, for example, in the formation of the isomer of the olefin double bond with respect to the formation of other compounds from the olefin, for example dimers, trimers, skeletal isomers, etc., or in the formation of one or more isomers of olefins, with respect to the conversion of other compounds present in the reaction mixture.

Designed according to this invention, the materials for pre-treatment include zeolite having a large pore size, for example, at least 0.35 nm.

According to the present invention, a method of isomerization of the double bond of the olefin, which comprises contacting the feedstock comprising olefins, the isomerization catalyst, where before bringing into contact of the feedstock with an isomerization catalyst one or more components of the raw material is subjected to pre-treatment, resulting in contact with the material for pre-treatment containing zeolite with pore size of at least 0.35 nm, and according to this method, the olefin means vinylidene olefin of the General formula CH2=C(R1R2where R1and R2independently mean alkyl groups having at least 2 carbon atoms, so that the molecular structure includes at least one allylic hydrogen atom.

The present invention also provides processing equipment, suitable for conducting the method of isomerization of the double bond of the olefin, and the specified processing equipment includes a tank for pre-treatment, containing material for pre-treatment, which contains a zeolite with a pore size of at least 0.35 nm, and the capacity for isomerization containing isomerization catalyst, where the capacity for pre-treatment and capacity for isomerization placed in such a way as to create conditions for bringing into contact of the raw material, comprising the olefin and catalyst for isomerization and prior to contacting of the feedstock with an isomerization catalyst one or more components of the raw materials were pre-processed by bringing into contact with the material prior to processing.

Pre-treatment of the present invention with a large benefit can be applied to the isomerization of a particular type vinylidenes of the olefin to avcoi linear α -olefin, which is isomeric to vinylidene the olefin. During isomerization of linear transformations α-olefin is not or almost does not occur. Consider specific vinylidene olefin has the General formula CH2=C(R1R2where R1means ethyl group, and R2means of linear 1-alkyl group. This combination of olefins may be present in the reaction product of the oligomerization of Atanov, where linear α-olefin is the main product, and vinylidene olefin by-product. Boiling point linear α-olefin and vinylidene olefins are usually so close that their separation by distillation is problematic. Isomerization vinylidenes of olefin leads then to the isomer vinylidene olefins, which may be easier separated from the line α-olefin than vinylidene olefin (see US-A-5789646 and US-A-4697040, the contents of which are incorporated here by reference).

Therefore, the present invention also provides a method of processing a mixture of olefins, including linear α-olefin and vinylidene olefin, which is isomeric to the line α-olefin and has a General formula of CH2=C(R1R2where R1means ethyl group, and R2means of linear 1-alkyl group, where the specified pic is b includes isomerization vinylidenes of the olefin with the formation of isomer vinylidenes of the olefin double bond by bringing into contact comprising a mixture of olefins feedstock with a catalyst for isomerization and separation of linear α-olefin from isomer vinylidenes of the olefin double bond, where before bringing into contact of the feedstock with an isomerization catalyst one or more components of the raw material is subjected to pre-treatment by contact with the material for pre-treatment, including zeolite with pore size of at least 0.35 nm.

Detailed description of the invention

The method according to the present invention is convenient for the implementation of the isomerization vinylidene olefins of General formula CH2=C(R1R2where R1and R2independently mean alkyl groups having at least 2 carbon atoms, so that the molecular structure includes at least one allylic hydrogen atom. Usually, R1and R2independently denote an alkyl group having at most 20 carbon atoms, more typically at most 16 carbon atoms.

Usually R1means ethyl group. Usually R2means of linear 1-alkyl group, which preferably contains an even number of carbon atoms. Preferred vinylidene olefins are, for example, 2-ethyl-1-penten and 2-ethyl-1-hepten, in particular 2-ethyl-1-butene, 2-ethyl-1-hexene, 2-ethyl-1-octene, 2-ethyl-1-mission 2-ethyl-1-dodecen.

Subjected to isomerization of the olefin may consist of a number of olefins, such as number enter the specified vinylidene olefins, in particular from a number vinylidene olefins, each of which carries in its molecular structure an alkyl group, R1meaning ethyl group, and which differ from each other alkyl groups, R2. Preferably, the alkyl groups of R2mean linear 1-alkyl group with the number of carbon atoms, each of which differs from the other two (for example, 5, 7 and 9), and preferably such a number of carbon atoms is expressed even numbers (for example, 4 and 6 or 4, 6, 8 and 10; or 12, 14 and 16).

In isomerizing mixture may contain a second olefin, which is relatively stable and not isomerized or does not interact in any other way under the existing conditions or interacts only to a small extent. Examples of the second olefin are eaten, propene, cyclohexene and 2-methylpropan.

In a specific embodiment, the present invention above vinylidene olefin will isomerized in the presence of linear α-olefin as a second olefin, with linear α-olefin is not isomerized little or no isomerized, or does not react in any other way. Preferably, linear α-olefin has the same number of carbon atoms that vinylidene olefin, so that linear α-olefin isomer is vinylidene about Afina. In particular, vinylidene olefin carries in its molecular structure an alkyl group, R1meaning ethyl group, and alkyl group, R2meaning of linear 1-alkyl group. For example, 2-ethyl-1-butene may be Samaritan in the presence of 1-hexene, 2-ethyl-1-hexene can be Samaritan in the presence of 1-octene and 2-ethyl-1-octene can be Samaritan in the presence of 1-mission. Two or more such vinylidene of olefin can be samaritani in the presence of the corresponding isomeric linear α-olefins.

The isomerization catalyst is preferably a solid catalyst, in particular solid acid. Suitable solid catalyst is a cation exchange resin in the acid form, for example cross-linked catalyst-based sulfonic acid. More typical isomerization catalyst is a molecular sieve. Suitable molecular sieves are molecular sieves based on silicon dioxide-alumophosphate, where the metal may be, for example, iron, cobalt or Nickel.

The pore size is used as the isomerization catalyst molecular sieve can be selected within wide limits. Preferably, the pore size is used as the isomerization catalyst molecular sieve is at least 0,6 nm, more desirably, ENISA least 0,65 nm, most preferably at least 0.7 nm. Typically, the pore size is used as the isomerization catalyst molecular sieve is at most 1 nm, more typical maximum of 0.9 nm, preferably at most 0.8 nm. When the pores or channels of the molecular sieves are not round, the pore size is made the smallest width of the pores or channels. The pore size of many of these molecular sieves specified in the source W.M. Meier and D.H. Olson, Atlas of Zeolite Structure Types", 2ndRevised edition (1987), published by the Structure Commission of the International Zeolite Association. The terms "time" and "channel"as used here in relation to molecular sieves, are interchangeable.

Preferably used as the isomerization catalyst molecular sieve is an aluminosilicate, i.e. zeolite, typically having an atomic ratio of silicon/aluminum (Si/Al), equal to at least 1.3, more preferably at least 1.5, in particular at least 2. Preferably, the atomic ratio Si/Al is at most 20, more preferably up to 8, in particular at most 5. As used here, the term "atomic ratio Si/Al"unless otherwise stated, mean skeletal atomic ratio Si/Al zeolite. For skeletal atomic ratio Si/Al zeolite accepted defined using the29Si-the MP.

Usually used as the isomerization catalyst molecular sieve contains in its molecular structure the sodalite cages. Preferably, the sodalite cages are organized in a structure faujasite. Mordenite zeolites, zeolites ZSM-5, beta-zeolites or omega zeolites can also be used as the isomerization catalyst.

Used as the isomerization catalyst molecular sieve exists preferably in the acid form, such as ammonium form or in the hydrogen form. This means that the cationic centers are used as the isomerization catalyst molecular sieve, at least partially occupied acid particles, such as ammonium ions and/or hydrogen. Preferably, the cationic centers are used as the isomerization catalyst molecular sieve, at least partially occupied by hydrogen ions, i.e. molecular sieve is in the hydrogen form. Other cationic centers can be employed, for example, with alkali metal ions or alkaline earth metal ions such as sodium ions or calcium ions or magnesium. In an appropriate case, at least 10%, more conveniently, at least 50%, particularly at least 75% of cationic centers are occupied by hydrogen ions and/or ammonium, although in practice often to 99.9%, often up to 99% of the cation is of introw occupied by hydrogen ions and/or ammonium. Preferably, when at least 10%, more preferably at least 50%, particularly at least 75% of cationic centers are occupied by hydrogen ions, although in practice often to 99.9%, often up to 99% of cationic centers are occupied by hydrogen ions.

If used as the isomerization catalyst molecular sieve exists in the ammonium form, this form can be transformed before use in the hydrogen form in any convenient way, for example by heating to a temperature of at least 300°C, for example to a temperature in the range 400-600°C.

Usually used as the isomerization catalyst molecular sieve has a surface area in the range from 400 to 1000 m2/g, more usually from 600 to 950 m2/, As used here, the surface area of the adopted area, measured by the method of ASTM-D3662-92.

For example, molecular sieve, which can be used as the isomerization catalyst is a zeolite ZMS-5 in the hydrogen form, with the atomic ratio Si/Al, for example, 25 or 80. An example of a preferred molecular sieves that can be used as the isomerization catalyst is CBV 500 (trade mark), which is a zeolite having the structure faujasite, three-dimensional atomic ratio Si/Al of about 2.6 (it is believed that skeletal atom is th ratio Si/Al is in the range of 2.3-3), the pore size of 0.74 nm and a surface area of about 750 m2/g Zeolite CBV 500 available in the ammonium form, supplied by Zeolyst International. Another example of a preferred molecular sieves for use as the isomerization catalyst is CBV 400 (trade mark), which is a zeolite having the structure faujasite, three-dimensional atomic ratio Si/Al about 2.55 (it is believed that skeletal atomic ratio Si/Al is in the range of 2.3-3), the pore size of 0.74 nm and a surface area of about 730 m2/g Zeolite CBV 400 is available in a hydrogen/sodium form (sodium 2,2% of the mass. in the calculation of Na2O, the form of which is considered is 80-85% cationic centers occupied by hydrogen ions). Zeolite CBV 400 comes Zeolyst International.

Preferably, the molecular sieve that is intended to be used as the isomerization catalyst, existed in the form of particles, such as balls, cylinders or beads, consisting, for example, at least 10 wt. -%, typically, at least 50 wt. -%, preferably, at least 90% of the mass. of the molecular sieve based on the mass of particles. Practically such particles often include up to 99.99 wt. -%, more to 99.9 wt. -%, most often up to 99% of the mass. molecular sieve based on the mass of particles. The particles may be present conventional binder. On the serious conventional binder agents can be inorganic materials, such as clay, silica and/or metal oxides. Used as the isomerization catalyst molecular sieve can be mixed with materials such as porous matrix material, such as 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.

According to the method of isomerization of the present invention the liquid diluent may either be present or absent. Suitable organic liquid diluents, for example hydrocarbons, such as alkanes, cycloalkanes and aromatic hydrocarbons or chlorohydrocarbons.

This way isomerization can be carried out by bringing into contact of the feedstock in the liquid phase with the isomerization catalyst. Raw material includes as components subject to isomerization of the olefin (hereinafter "the first olefin, for example, the above stated vinylidene olefin and, optionally, a second olefin (for example, linear α-olefin, and, optionally, a liquid diluent. In an appropriate case, the first olefin is from 0.01 to 100 wt%. of raw materials. It is more convenient to first olefin ranged from 0.05 to 90% of the mass. from raw materials. The second olefin, if present, extending t is in a suitable case from 10 to 99.99% of the mass. from raw materials, more conveniently, from 20 to 99.95% of the mass. from raw materials. The mass ratio of the first olefin and the second olefin, if present, is preferably in the range from 0.05:100 to 10:100, in particular from 0.1:100 to 5:100. Liquid diluent, if present, is in accordance with the requirements of from 1 to 99.99% of the mass. from a mixture of components, more conveniently from 10 to 99.95% of the mass. from raw materials. Substances present in smaller amounts, usually not considered as diluents.

This way isomerization can be performed with the dissolved catalyst isomerization or by isomerization catalyst in the form of solids suspended in the raw material, which is particularly useful when the method of isomerization was carried out as a periodic process in the liquid phase. The amount of dissolved or suspended the isomerization catalyst may be in the range from 0.1 to 20 g/kg of raw material, preferably from 0.5 to 10 g/kg of raw material.

Alternatively, the method of isomerization can be carried out with a solid isomerization catalyst, present in the form of a fixed layer, which is particularly useful when the method of isomerization was carried out as a continuous process, either in liquid phase or in the gas phase. The preferred continuous process in the liquid phase using a fixed layer. LHSV may be in the range of from 0.01 to 00 kg/(l· h), preferably from 0.1 to 100 kg/(l·h). In this context, the term "LHSV" means the average hourly feed rate of the liquid, which is expressed through the ratio of the mass flow rate to the volume of the catalyst bed. Direction passing through the catalyst bed of the stream is not significant. For example, the flow direction may be upward or downward.

This way isomerization can be carried out in a wide range of values of pressure and temperature, can influence the desired isomerization. In accordance with the requirements of the pressure is in the range from 0.01 to 10 MPa, more conveniently in the range from 0.02 to 2 MPa, in particular from 0.05 to 1 MPa. Suitable temperatures are in the range from 0 to 300°C, more conveniently in the range from 10 to 250°C, most conveniently in the range from 20 to 200°C. When the first olefin is above vinylidene olefin, a suitable temperature is in the range from 0 to 150°C, more conveniently in the range from 10 to 100°C, most conveniently in the range from 20 to 80°C.

Method of isomerization can be carried out in such a way that the conversion vinylidenes of olefin when passing through the isomerization catalyst is at least 5%. Preferably, the conversion vinylidenes of olefin was at least 40%, more predpochtitel is but at least 60%, most preferably at least 80%. Often conversion vinylidenes of olefin is full, but often the conversion vinylidenes of olefin reaches at most 99.9%of the most frequently most 99,8%. When there α-olefin, in particular linear α-olefin, conversion α-olefin when passing through the isomerization catalyst is preferably at most 20%, more preferably up to 10%, most preferably up to 5%. Often α-olefin is not followed exactly, most conversion α-olefin is at least 0,1%, more often at least 0.2 percent.

One or more of the first olefin, a second olefin, if present, and the liquid diluent, if present, is subjected to pre-treatment before bringing into contact with an isomerization catalyst. Without going into theoretical details, believe that pre-treatment leads to the removal of impurities, which may have an adverse impact on the performance of the isomerization catalyst, in particular on the catalyst activity and stability of activity. Presumably, these impurities can be water or organic compounds containing heteroatoms, such as oxygen, nitrogen, sulfur and phosphorus. These impurities can be introduced at the time when NASA, processing, refining or other processing of the individual components.

Usually when casting in contact with the isomerization catalyst raw material includes water, at most 50 mass per million), preferably up to 10 mass/mn, in particular, to 1 mass/million relative to the weight of raw materials. Usually the content of organic compounds containing heteroatoms of oxygen, is such that the maximum content of heteroatoms of oxygen is 50 mass per million), preferably up to 20 mass/million relative to the weight of raw materials. Usually the content of organic compounds containing heteroatoms of nitrogen, is such that the maximum content of the nitrogen heteroatoms is 50 mass per million), preferably up to 20 mass/million relative to the weight of raw materials. Usually the content of organic compounds containing heteroatoms of sulfur, is such that the maximum content of sulfur heteroatoms is 50 mass per million), preferably up to 20 mass/million relative to the weight of raw materials. Typically, the content of organic compounds that include phosphorus heteroatoms, is such that the maximum content of heteroatoms phosphorus is 10 mass per million), preferably up to 2 mass/million relative to the weight of raw materials.

According to the present invention pre-treatment includes contacting the material for the pre-the processing, which contains a zeolite with a pore size of at least 0.35 nm. Can be used in combination with other methods of pre-processing. Other suitable ways of pre-processing are distillation, extraction and contacts with other material for pre-treatment, such as activated carbon, aluminum oxide, silicon dioxide and other zeolites. Pre-processing may be applied to one or more individual components of the raw materials. However, it is preferable to pre-process the ingredients together in the form of a mixture, especially when used as raw material for the method of isomerization, before bringing into contact with an isomerization catalyst.

The preferred zeolite for use as the material for pre-treatment is a zeolite with a pore size of at least 0.5 nm and in particular at least 0,6 nm, and is typically specified zeolite has a maximum pore size of 1.5 nm, more typically, up to a maximum of 1.2 nm, especially up to 1 nm. The pore size of many of these zeolites is given in W.M. Meier and D.H. Olson, Atlas of Zeolite Structure Types", 2ndRevised edition (1987), published by the Structure Commission of the International Zeolite Association.

Preferably, the zeolite for use as a material for pre-treatment will prevail in the structure of the sodalite cages, in particular, the sodalite cages arranged so that they form a structure faujasite. Preferably, the zeolite for use as a material for pre-treatment has an atomic ratio Si/Al higher than 1, in particular at least 1,2. Preferably the maximum atomic ratio Si/Al is 1.5. Preferably, the zeolite for use as a material for pre-treatment is a zeolite-X.

Zeolite for use as a material for pre-treatment usually includes alkali metal ions and/or ions, alkaline earth metal, occupying at least a portion of the cationic centers. Preferred alkali metal ions, particularly sodium ions. Examples of suitable ions of alkaline earth metal ions are calcium and magnesium ions. In an appropriate case, at least 10%, more convenient, and at least 50%, particularly at least 90% of cationic centers are occupied by ions of the alkali metal and/or alkaline earth ions of the metal, although in practice often to 99.9%, often up to 99% of cationic centers are occupied by ions of the alkali metal and/or alkaline earth ions of the metal. Preferably, when at least 10%, more preferably at least 50%, particularly at least 90% of cationic centers are occupied by ions del knogo metal, although, in practice, frequently up to 99.9%, often up to 99% of cationic centers are occupied by ions of the alkali metal.

In a typical case, the zeolite for use as a material for pre-treatment has a surface area in the range from 400 to 1000 m2/g, more usually from 600 to 950 m2/year

Examples of preferred zeolites for use as a material for pre-treatment are zeolite-10X, and in particular zeolite-H. Such zeolites are widely available, for example from UOP. Zeolite-10X is a zeolite of type X in the calcium form, having a pore size of about 0.75 nm, the atomic ratio Si/Al in the range from 1.2 to 1.5 and a surface area of about 700 m2/g Zeolite-H is a zeolite of type X in the sodium form, having a pore size of about 8 nm, the atomic ratio Si/Al in the range from 1.2 to 1.5 and a surface area of about 700 m2/year

Preferably, the zeolite for use as a material for pre-treatment existed in the form of particles, such as balls, cylinders or beads containing, for example, at least 10 wt. -%, typically, at least 50 wt. -%, preferably, at least 90% of the mass. zeolite based on the weight of the particles. Practically such particles often include up to 99.99 wt. -%, more to 99.9 wt. -%, most often up to 99% of the mass. zeolite based on the weight of the particles. In h is stico may be conventional binder. Useful conventional binder agents can be inorganic materials such as clay, silicon oxides and/or metals. Zeolite for use as a material for pre-treatment may be mixed with other materials, such as porous matrix material, such as 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.

Pre-treatment can be carried out by suspension of the material prior to processing in the considered component or mixture of components, which is particularly useful when pre-treatment is carried out as a periodic process in the liquid phase. The amount of suspended material for pre-treatment may be in the range from 0.1 to 50 g/kg component or mixture of components, preferably from 0.2 to 10 g/kg component or mixture of components.

Alternatively, pre-treatment can be carried out with material for pre-processing that is present in the form of a fixed layer, which is particularly useful when the method of pre-processing carried out as a continuous the process, either in liquid phase or in the gas phase. The preferred continuous process in the liquid phase using a fixed layer. LHSV may be in the range of from 0.05 to 50 kg/(l·h), preferably from 0.1 to 20 kg/(l·h). In this context, the term "LHSV" means the average hourly feed rate of the liquid, which is expressed through the ratio of the mass flow rate to the volume of the layer for pre-treatment. Direction passing through the layer of pre-processing flow is not significant. For example, the flow direction may be upward or downward.

Pre-treatment with the use of material for pre-treatment can be carried out in a wide range of temperatures and pressures. In case the temperature ranges from -20 to 100°C, more conveniently in the range from -10 to 80°C. a Suitable pressure is in the range from 0.01 to 10 MPa, more conveniently in the range from 0.02 to 2 MPa, in particular from 0.05 to 1 MPa.

As indicated above, in some embodiments, the run-way isomerization of the present invention is applicable to one or more vinylidene the olefins in the mixture with the corresponding isomeric linear α-olefin (olefin). In the molecular structure of the considered vinylidene olefin alkyl group, R1oz achut ethyl group, and the alkyl groups of R 2mean linear 1-alkyl group with an even number of carbon atoms or consecutive even numbers of carbon atoms. Such mixtures can be obtained by means of oligomerization of Atanov, where one or more linear α-olefins are the main product, and one or more vinylidene olefins are a by-product. Such methods of oligomerization of Atanov known from the prior art, for example from US-A-4749819, US-A-5557027, US-A-4528416, US-A-4472525, US-A-4472522, US-A-4284837, US-A-4260844 and US-A-4020121, the contents of which are incorporated herein by reference.

The method of oligomerization of atenol can be carried out in the presence of a Ziegler catalyst, such as lithium, sodium, potassium, beryllium and magnesium-metal catalysts. Convenient method of oligomerization of Atanov to perform in the presence of Nickel catalyst, where the Nickel complex is associated with bidentate chelate ligand. Preferred bidentate chelate ligands have a tertiary organophosphorus group with a suitable functional group, located as a substituent on the carbon atom attached directly to the phosphorus atom or separated by no more than two carbon atoms from the phosphorus atom of organophosphorus group. Examples of preferred bidentate chelate ligands are o-dihydrocarbamazepine acid is for example o-diphenylphosphinomethyl acid and

o-dicyclohexylthiourea acid, and

2-dihydrocarbamazepine acid, for example

2-diphenylphosphinomethyl acid and

2-dicyclohexylphosphino acid and their corresponding salts with alkaline metals.

The method of oligomerization of atenol can be carried out in the presence or in the absence of liquid diluent. Suitable liquid diluents for use in combination with the Nickel complex catalysts include proton and aprotic polar solvents, such as one - or polyhydric alcohols, in particular aliphatic diols such as ethylene glycol, 1,3-propandiol and 1,4-butanediol; 1,2-alkalescency, such as 1,2-ethylene carbonate resulting, 1,2-propylene carbonate and 2,3-butylaniline; and ethers, in particular cyclic ethers, such as tetrahydrofuran.

The method of oligomerization of atenol can be implemented in a wide range of temperatures and pressures. Preferred temperatures are in the range from 0 to 200, in particular from 30 to 140°C. Preferred pressures are in the range from 0.1 to 35 MPa, in particular from 2.5 to 15 MPa.

The products of the oligomerization can be separated from the mixture after the reaction of oligomerization of one or more of the phase separation, extraction of the proton or aprotic polar solvent, water extraction and distillation.

The product of this method of isomerization can be processed and purified in any suitable way. When vinylidene olefin will isomerized in the presence of linear α-olefin, as described above, the isomer vinylidenes of the olefin double bond may be separated from the linear α-olefin by distillation. The method of processing a mixture of linear α-olefin may be a cleaning process linear α-olefin, as this can provide linear α-olefin in a purer form.

Unless otherwise specifically mentioned herein organic compounds, such as organic solvents and ligands, usually contain a maximum of 40 carbon atoms, usually to a maximum of 20 carbon atoms, in particular at most 10 carbon atoms, better at most 6 carbon atoms. As indicated here, the intervals for the number of atoms of carbon (i.e. carbon number) include the number specified as the limits of the intervals.

The invention is illustrated by the following examples.

EXAMPLE 1 (for comparison)

Zeolite CBV 500 (trade mark) in the form of cylinders with a diameter of 1.6 mm (1/16 inch)supplied by Zeolyst International, is examined for the ability to catalyze the isomerization of 2-ethyl-1-butene as follows.

Sample 1-hexene is obtained by oligomerization of Athena using Nickel catalyst, and the processing executed by Aut methodologies including extraction of water extracting liquids. Distillation gives a sample of 1-hexene in the form of a6the fractions containing as impurities 0.55% mass. 2-ethyl-1-butene and about 20 mass per million of water.

The sample in the form of cylinders of the zeolite is heated to 500°C in air for 15 hours. 0,15-g sample is placed in a flask with 100 ml of sample and 1-hexene. The flask is shaken for 50 minutes at 20°C and a pressure of 0.1 MPa, and then measure the content of 2-ethyl-1-butene 1-hexene. The result is shown in table I.

EXAMPLES 2-4 (for comparison)

Essentially repeating example 1 except that instead of zeolite CBV 500 use samples of the following zeolites:

zeolite LZ-Y52 (trademark), manufactured manufactured zeolite type Y in the sodium form, having a pore size of 0.74 nm and the atomic ratio Si/Al 2.37 (example 2),

zeolite-13X (example 3), and

zeolite-4A (example 4).

All samples of zeolites obtained and investigated in the form of cylinders with a diameter of 1.6 mm (1/16 inch).

The results are shown in table I.

EXAMPLES 5-7 (example 7 for comparison)

Essentially repeat examples 1 and 2 except that the sample of zeolite CBV 500 or sample of zeolite LZ-Y52 in a flask with 100 ml of 1-hexene 1-hexene pretreated zeolite-13X (examples 5 and 7) or zeolite-4A (example 6) as materials for the pre-treatment is, using the method schematically described in example 3 or example 4, and separating the sample 1-hexane from materials pre-treatment. The result is shown in table I.

Table I
ExamplePre-treatment (processing)Isomerization2-ethyl-butan (% wt.)
1 **)Distillation *)Zeolite CBV 5000,49
2 **)DistillationZeolite LZ-Y520,55
3 **)DistillationZeolite-13X0,55
4 **)DistillationZeolite-4A0,55
5Distillation, contact with the zeolite-HZeolite CBV 5000,24
6Distillation, contact with the zeolite-4AZeolite CBV 5000,36
7Distillation, contact with the zeolite-HZeolite LZ-Y520,53
*) get sample 1-hexene;

**) for comparison, not according to the invention.

EXAMPLE 8

A sample of zeolite-13X in the form of cylinders with a diameter of 1.6 mm (1/16 inch) heated air is e at 200° C. the First cylindrical vessel of stainless steel (diameter about 2.5 cm, height of about 25 cm) filled this zeolite to create a layer of particles. A sample of zeolite CBV 500 in the form of cylinders with a diameter of 1.6 mm (1/16 inch) heated in air at 200°C. a Second cylindrical vessel of stainless steel (diameter about 2.5 cm, about 5 cm in height) filled with a second zeolite to create a layer of particles.

Support the current sample 1-hexene, similar to that used in examples 1-7, but containing 0,85% of the mass. 2-ethyl-1-butene and having a water content of about 20 mass/million through the first vessel and from the first vessel through the second vessel. In both vessels the flow is upward at a speed of 250 g/hour. In the first vessel temperature is 2°C and a pressure of 0.5 MPa. In the second vessel temperature is 40°C and a pressure of 0.5 MPa. After passing through the vessels 36 kg sample 1-hexene 2-ethyl-1-butene in the stream of 1-hexene, leaving the second vessel, equal to 0.05% of the mass.

EXAMPLE 9

Repeat essentially the example 8 except that theinstead of zeolite CBV 500 use the sample of zeolite CBV 400 in the form of cylinders with a diameter of 1.6 mm (1/16 inch). After passing through the vessels 36 kg sample 1-hexene 2-ethyl-1-butene in the stream of 1-hexene, leaving the second vessel, equal to 0.11% of the mass.

EXAMPLE 10

Repeat on the merits of the case 9 so the drop is receiving, using another sample of 1-hexene, similar to the model 1-hexene used in examples 1-7, but containing 0,82% of the mass. 2-ethyl-1-butene and having a water content of about 20 mass/million, and that the flow velocity is equal to 240 g/hour. After passing through the vessels of 24 kg sample 1-hexene 2-ethyl-1-butene in the stream of 1-hexene, leaving the second vessel, equal to 0.50% of the mass.

EXAMPLE 11 (for comparison)

Repeat essentially the example 10 except that theinstead of zeolite CBV 400 use the sample of zeolite CBV 8062 in the form of cylinders with a diameter of 1.6 mm (1/16 inch). Zeolite CBV 8062 (trade mark)supplied by Zeolyst International, is a zeolite of type ZSM-5 in the hydrogen form and has an atomic ratio Si/Al equal to 80. After passing through the vessels of 24 kg sample 1-hexene 2-ethyl-1-butene in the stream of 1-hexene, leaving the second vessel is equal to 0.62% of the mass.

The examples show that the isomerization catalysts have superior performance characteristics when used as a material for pre-treatment of zeolite to large pore size, such as zeolite 4A and zeolite-H (cf. examples 5 and 6 with example 1 and example 7 with example 2). In particular, it is shown that the combined use of zeolite for pre-treatment and isomerization catalyst leads to a synergistic action, namely, PR combined the change leads to a decrease in the content vinylidenes of olefin, which is more than the total effect achieved by the use only of zeolites for pre-treatment (examples 3 and 4) and the attainable only isomerization catalysts (examples 1 and 2). This synergetic effect is obvious, and not unexpected, since this combination was not considered prior art, although it is known that zeolites for pre-treatment have the properties of the isomerization catalyst (see US-A-4697040 and US-A-3686250) and isomerization catalysts can be used as a material for pre-treatment (see US-A-3686250).

The examples also show that improved performance characteristics can be achieved by selection of the isomerization catalyst which comprises a molecular sieve in an acid form, having a pore size of at least 0,6 nm (cf. example 1 with example 2, example 5, example 7, example 8-10 example 11).

1. Method of isomerization of the double bond of the olefin, comprising contacting the feedstock containing olefins, isomerization catalyst, where before bringing into contact of the feedstock with an isomerization catalyst one or more components of the raw material is subjected to pre-treatment, resulting in contact with the material for pre-treatment containing zeolite with pore size of at least 0.35 W n is, and where the olefin means vinylidene olefin of the General formula CH2=C (R1R2where R1and R2means alkyl groups having, independently, at least 2 carbon atoms, so that the molecular structure includes at least one allylic hydrogen atom.

2. The method according to claim 1, where R1means ethyl group, and R2means of linear 1-alkyl group, and where raw materials includes, in addition, linear α-olefin, which is the isomer vinylidene olefins.

3. The method according to claim 1 or 2, where R2means of linear 1-alkyl group with an even number of carbon atoms.

4. The method according to claim 1, where the isomerization catalyst contains a molecular sieve with a pore size of at least 0,6 nm and at most 1 nm, which is in the acid form.

5. The method according to claim 4, where the molecular sieve as the isomerization catalyst is a zeolite in the hydrogen form with the atomic ratio si/al of at least 1.3 and at most 20.

6. The method according to claim 5, where the zeolite as the isomerization catalyst has the structure faujasite.

7. The method according to claim 1 where the zeolite as a material for pre-treatment has a pore size of at least 0.5 nm and at most 1.5 nm.

8. The method according to claim 1 where the zeolite as a material for pre-treatment is in the sodium form, or calcium Faure what that is

9. The method according to claim 1, where the components of the pretreated feedstock together in the form of a mixture.

10. The method of processing a mixture of olefins containing linear α-olefin and vinylidene olefin, which is the linear isomer α-olefin and has a General formula CH2=C(R1R2where R1means ethyl group, and R2means of linear 1-alkyl group, where the method includes the isomerization vinylidenes of the olefin with the formation of isomer vinylidenes of the olefin double bond by bringing into contact comprising a mixture of olefins feedstock with a catalyst for isomerization and separation of linear α-olefin from isomer vinylidenes of the olefin double bond, and before the bringing into contact of the feedstock with an isomerization catalyst one or more components of the raw material is subjected to pre-treatment by contact with the material for pre-treatment, including zeolite with pore size of at least 0.35 nm.



 

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