Vinylidene olefin isomerization process

FIELD: organic synthesis catalysts.

SUBSTANCE: vinylidene olefin-containing starting material is brought into contact with isomerization catalyst consisting of molecule sieve in H form, which contains pore larger than 0.6 nm.

EFFECT: increased selectivity of catalyst.

12 cl, 1 tbl, 11 ex

 

The scope of the invention

The invention relates to a method of isomerization of the double bond vinylidenes of olefin, comprising contacting the feedstock consisting of vinylidene olefins, isomerization catalyst which comprises a molecular sieve.

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 of 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 vinylidene olefins, comprising the contacting of the feedstock, including vinylidene olefin with an isomerization catalyst, comprising molecular sieve, which is a zeolite in the hydrogen form. Specifically described zeolite is what I H-ZSM-5 with an atomic ratio of silicon/aluminium 25. The pore size of H-ZSM-5 is defined by two types long long, which are interrelated, namely pores with a diameter of 0,h,56 nm and a pore diameter of 0,h,55 nm (cf., 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, p. 100-101). In US-A-5789646 considers the influence of the acidity of the solid acid to be an effective catalyst when vinylidene isomerization and proposed placement of catalysts on a scale of acidity. It is striking that in the examples of processing according to US-A-5789646 the results for catalyst H-ZSM-5 and cross-linked catalyst-based sulfonic acid, essentially identical, on the basis of which it can be assumed that significantly different solid acid catalysts occupy essentially the same position on the scale of acidity.

US-A-4697040 describes a method of isomerization of the double bond vinylidene olefins, comprising the contacting of the feedstock, including vinylidene olefin with an isomerization catalyst, comprising molecular sieve, which is a zeolite in sodium form. The zeolite according to US-A-4697040 is a specific type zeolite Y, denoted by LZ-Y52 (trade mark), having the size of the pores or channels of 0.74 nm (cf., 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 . 62-63).

Brief description of the invention

The present invention provides catalysts based on molecular sieves for the isomerization of the double bond vinylidene olefins having improved performance characteristics as compared with catalysts based on molecular sieves known from the prior art. 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 isomer vinylidenes of the olefin double bond in relation to the formation of other compounds of vinylidene of olefin, such as dimers, trimers, skeletal isomers, etc., or in the formation of one or more isomers of vinylidene of olefin relative to the conversion of other compounds present in the reaction mixture.

Designed according to this invention, the isomerization catalysts include molecular sieve in an acid form, having a large pore size, for example, at least 0,6 nm. This is unexpected, as expected, h is of acidic molecular sieve with a large pore size should promote the conversion of olefins to unwanted isomers and/or dimers and trimers, which tend to very slow diffusion inside the pores of molecular sieves, leading not only to lower the selectivity, but also to more corruption, more carbonation and, consequently, more rapid deterioration of the performance characteristics of the catalyst, i.e. a lower stability of the catalyst.

According to the present invention, a method of isomerization of the double bond vinylidenes of olefin, which comprises contacting the feedstock containing vinylidene olefin with an isomerization catalyst, comprising molecular sieve in an acid form, where the specified molecular sieve contains pores whose size is more than 0.6 nm.

The method according to the present invention with a large benefit can be applied for the implementation of the isomerization vinylidenes of olefin specific type of additive linear α-olefin, which is isomeric to vinylidene the olefin. During isomerization of linear transformations α-olefin does not occur or do 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 oligomerization by Atena, where linear α-Alevi what 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 (cf., 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 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 the isomerization catalyst, comprising molecular sieve in an acid form, where the specified molecular sieve contains pores whose size is more than 0.6 nm, and the separation line α-olefin from isomer vinylidenes of the olefin double bond.

Detailed description of the invention

The method according to the present invention is convenient for on the westline isomerization wide range vinylidene olefins. Vinylidene olefins can be described by 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. Usually R1and R2independently denote an alkyl group having at most 20 carbon atoms, more typically at most 16 carbon atoms.

Usually R1means ethyl group. R2usually means a 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.

Vinylidene olefin may consist of a number 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 iraheta 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 only to a small extent. Examples of the second olefin are eaten, propene, cyclohexene and 2-methylpropan.

A special aspect of the present invention is that vinylidene olefin can be Samaritan in the presence of linear α-olefin as a second olefin, thereby linear α-olefin is not isomerized little or no isomerized, or does not communicate any other way. Preferably linear α-olefin has the same number of carbon atoms that vinylidene olefin, so that linear α-olefin isomer is vinylidenes of olefin. 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 olefins can be samaritani in the presence matched with the appropriate isomeric linear α -olefins.

The isomerization catalyst comprises a molecular sieve in an acid form, where the specified molecular sieve contains pores with a size of more than 0.6 nm.

Preferably the pore size is used as the isomerization catalyst molecular sieve is at least 0,65 nm, more 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. Used as the isomerization catalyst molecular sieve is typically a silica-aluminophosphate molecular sieve or metal-silica-aluminophosphate molecular sieve, in which the metal may be, for example, iron, cobalt or Nickel.

Preferably used as the isomerization catalyst molecular sieve is aljumaili is at, 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. Used herein, 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-NMR.

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. Can be used mordenite zeolites, beta zeolites or omega-zeolites, however, when vinylidene olefin has the above General formula, where R1means ethyl group, and R2means of linear 1-alkyl group, in particular with an even number of carbon atoms preferably, the isomerization catalyst include other molecular sieve than mordantly zeolite in the ammonium form. Used as the isomerization catalyst molecular sieve acid exists in the form of, for example, in ammonium form or in the hydrogen form. This OSN which includes, what cationic centers are used as the isomerization catalyst molecular sieve, at least partially occupied acid particles, such as ammonium ions and/or hydrogen. Preferably 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 ions of alkaline-earth metals, 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 cationic centers are 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 pace atory, at least 300°C, for example to a temperature in the range 400-600°C. a Typical 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 in this case is square, as measured by the method ASTM-D3663-92.

An example of a suitable molecular sieves for use as the isomerization catalyst is a 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 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 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, there 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. Useful 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. Approach asimi are 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 vinylidene olefin and, optionally, a second olefin (for example, linear α-olefin and, optionally, a liquid diluent. In an appropriate case vinylidene olefin is from 0.01% by mass. up to 100% of the mass. of raw materials. It is more convenient to vinylidene olefin ranged from 0.05% of the mass. up to 90% of the mass. from raw materials. The second olefin, if present, is in an appropriate case, 10% of the mass. up to 99.99% of the mass. from raw materials, more convenient from 20% of the mass. to 99.95% of the mass. from raw materials. The mass ratio vinylidenes of the 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 1% of the mass. up to 99.99% of the mass. from a mixture of components, it is more convenient from 10% of the mass. to 99.95% of the mass. from raw materials. Substances present in smaller quantities, usually are not considered for thinners.

This way isomerization can be performed with the isomerization catalyst suspended in the raw material, which is particularly convenient when the and the way isomerization carried out as a periodic process in the liquid phase. The number of suspended 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 the 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 200 kg/l·h, preferably from 0.1 to 100 kg/l·including 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 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 preferably 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.

Preferably one or more vinylidene olefins, the second olefin, if present, and the liquid diluent, if present, is subjected to pre-treatment before bringing into contact with an isomerization catalyst. Appropriate ways of pre-processing are distillation, extraction and, in particular, the contact with the Mat is the Rial for pre-treatment. Can be used in combination of such methods. Suitable materials for pre-treatment are, for example, activated carbon, alumina, silica and zeolites. Pre-processing may be applied to one or more separate, 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.

Without going into theoretical details, it is believed 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 during synthesis, 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 up to 1 mass/million relative to masisira. Usually the content of organic compounds containing heteroatoms of oxygen, is such that the maximum content of heteroatoms of oxygen is 50 mass/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/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/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/million, preferably up to 2 mass/million relative to the weight of raw materials. Such levels of impurities can be achieved by using pre-processing.

The preferred zeolite for use as the material for pre-treatment is a zeolite with a pore size of at least 0.3 nm or at least 0.35 nm, in particular at least 0.5 nm and even better, at least 0,6 nm and is usually specified zeolite has a maximum size is 1.5 nm, more usually 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 contains in its structure 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 of 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 cationization occupied by alkali metal ions and/or ions of alkaline-earth metal, although, in practice, frequently up to 99.9%, often up to 99% of cationic centers occupied by alkali metal ions and/or ions of alkaline-earth metal. Preferably, when at least 10%, more preferably at least 50%, particularly at least 90% of cationic centers are occupied by ions of an alkali metal, although in practice often 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 beads, the cylinder is at 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. The particles may be present 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 CME and 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 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·including 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 MP is.

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, R1means ethyl group, and the alkyl groups of R2mean 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 magnitotelluricheskie 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 Tr is part of 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 acids, for example o-diphenylphosphinomethyl acid and o-dicyclohexylthiourea acid, and 2-dihydrocarbamazepine acid, for example, 2-diphenylphosphinomethyl acid and 2-dicyclohexylphosphino acid and their respective 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 within at up to 200° C, 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, extraction with water 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 in the trail of the relevant examples.

EXAMPLE 1

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 treatment is carried out according to the methods, 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/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-gram 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).

Results in what can be found 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 pre-treatment, 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.)
1Distillation *)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
7 **)Distillation, 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 in air 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 instead 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 essentially the example 9, except that they use a different sample 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 instead 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.

In the examples it is shown that the improved performance of the catalyst is achieved by selection of the isomerization catalyst, which contains molecular sieve acid in the Orme, 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).

The examples also 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 the combined use 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 in the 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).

1. Method of isomerization of the double bond vinylic the new olefin, including the contacting of the feedstock containing vinylidene olefin with an isomerization catalyst, comprising molecular sieve in acid form, with specified molecular sieve contains pores with a size of more than 0.6 nm.

2. The method according to claim 1, where vinylidene olefin has the General formula CH2=C(R1R2where R1means ethyl group, and R2means of linear 1-alkyl group, and where raw materials include linear α-olefin, which is the isomer vinylidene olefins.

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

4. The method according to one of claims 1 to 3, where the pore size molecular sieve catalyst isomerization equal, at least, of 0.65 nm and at most 1 nm.

5. The method according to any one of claims 1 to 3, where the molecular sieve as the isomerization catalyst is a zeolite with an atomic ratio si/al of at least 1.3 and at most 20.

6. The method according to any one of claims 1 to 3, where the molecular sieve of the isomerization catalyst exists in the hydrogen form.

7. The method according to any one of claims 1 to 3, where the molecular sieve has a structure faujasite.

8. The method according to any one of claims 1 to 3, where the isomerization catalyst contains a molecular sieve, other than mordantly zeolite in the ammonium form.

9. The method according to any one of claims 1 to 3, where before bringing raw materials in the context of the act with the isomerization catalyst one or more components of the raw material is subjected to pre-treatment by contact with the material for pre-treatment, comprising a zeolite with a pore size of at least 0.35 nm.

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

11. The method according to claim 9, where the zeolite as a material for pre-treatment is in the sodium form or calcium form and has a pore size of at least 0.5 nm and at most 1.5 nm.

12. 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 of 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 comprising a mixture of olefins feedstock in contact with an isomerization catalyst containing molecular sieve in acid form, with specified molecular sieve contains pores with a size of more than 0.6 nm, and the separation line α-olefin from isomer vinylidenes of the olefin double bond.



 

Same patents:

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

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: chemical and petrochemical industries; isomerization of olefins.

SUBSTANCE: the invention is dealt with of the field of deposition on carbon materials of catalysts of the basic nature being of interest for processes of isomerization of olefins. There is a description of a catalyst of isomerization of olefins containing metal sodium deposited on a composite porous carbon material, which represents a three-dimensional porous carbon die with the following structural characteristics: d002 =0.343-0.350 nm, the average size of the crystallite in a direction of "a"-La=l-14 nm, the average size of the crystallite in a direction of "c"-Lc=2-12 nm, real density of 1.8-2.1 g/cm3, with distribution of pores by sizes having a maximum in the range of 20-200 nm and an additional maximum in the range of 1-20 nm. Also there is a description of a method of preparation of the catalyst providing for deposition of metal sodium on the composite porous carbon material and a method of isomerization of olefins with use of this catalyst. The technical result is a possibility to conduct the process of isomerization at low temperatures, increased catalytic activity and selectivity, decreased output of by-products.

EFFECT: the invention ensures a possibility to conduct the process of isomerization at low temperatures, increased catalytic activity and selectivity, decreased output of by-products.

6 cl, 10 ex, 2 tbl

The invention relates to new furifosmin formula I

< / BR>
where n denotes an integer of 1 or 2; R1denotes a hydrophilic group selected from the following groups: -SO2M, -SO3M, -CO2M, -PO3M, where M represents inorganic or organic cationic residue selected from a proton, cations, alkaline or alkaline earth metals, ammonium cations -- N(R)4where R denotes hydrogen or C1-C14alkyl, and the other cations are based on metals, salts with acids: fullsleeve, fullcarbon, fullsleeve or furylphosphonous soluble in water; m denotes an integer of 1; R2denotes a hydrophilic group,- SO2M, -SO3M, -CO2M, RHO3M, where M denotes hydrogen or an alkaline metal salt with the acid fullsleeve, fullcarbon, fullsleeve or fullfactorial soluble in water, R denotes an integer from 0 to 2

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

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

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

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: 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: 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: 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: 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

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