Method for production of 1-octene

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

 

The invention relates to a method for producing 1-octene by telomerization 1,3-butadiene with a telogen in the presence of catalyst telomerization, partial hydrogenation of telomeres and the splitting of the hydrogenated intermediate product.

1-Octene is used in large quantities in the manufacture of various chemical products. For example, 1-octene produced surfactants, wetting, lubricants and polymers. Considerable scope, in addition, is their use as co monomer in polymers, in particular polyethylene.

Almost all used to date industrial methods of producing 1-octene based on the source substance ethene. Aten will oligomerized and get a number of products, comprising as the main products from the α-olefins. With proper choice of catalyst and the process conditions can be optimized, the number of 1-octene in the product and it will be in this case about 25%. Along with the specified way get a basic amount of 1-octene, known allocation of 1-octene from a number of reaction products of the Fischer-Tropsch process.

In the literature, along with processes based on ethene, also known techniques as the initial substance use 1,3-butadiene. However, 1-octene derived from butadiene are not directly through, for example, d is merisalu, as a result, several stages of the process. So, in the international application WO 92/10450 described the method by which 1,3-butadiene is introduced into the reaction preferably with methanol or ethanol with the formation of 2,7-octadienal ether, which after hydrogenation in oktilovom ether is cleaved with the formation of 1-octene. In European patent application EP-A-0440995 described a similar way, but in the first stage with a carboxylic acid. The General way is the first stage of the process, which is called as telomerization. In General, when telomerization telogen (EP-A-0440995 carboxylic acid) interacts with maxogenol (1,3-butadiene, 2 equivalent) with the formation of the telomere.

Examples of reactions telomerization described inter alia in E. J. Smutny, J. Am. Chem. Soc. 1967, 89, 6793; S. Takahashi, T. Shibano, N. Hagihara, Tetrahedron Lett. 1967, 2451; EP-A-0561779, US 3499042, US 3530187, GB 1178812, NL 6816008, GB 1248593, US 3670029, US 3670032, US 3769352, US 3887627, GB 1354507, DE 2040708, US 4142060, US 4146738, US 4196135, GB 1535718, US 4104471, DE 2161750 and EP-A-0218100.

In the case of a method of producing 1-octene based on butadiene, as described in international application WO 92/10450 or in European patent application EP-A 0440995, 1-octene obtained by splitting substituted in the 1-position of n-octane. This selectivity at this stage are often unsatisfactory. So, in the international application WO 92/10450 the cleavage of 1-methoxyacetone when the degree of conversion of 80% of selectionstate of octenol is 66%.

In this regard, tasked to develop a method by which 1-octene can be obtained on the basis of 1,3-butadiene, but which does not contain the above-mentioned stage of cleavage.

It was found that 1-octene with a high degree of purity and in good yield can be obtained in the process, which essentially consists of three stages.

The object of the invention therefore is a method for 1-octene by

1) interaction of 1,3-butadiene in the presence of catalyst telomerization with telogen General formula I,

where X represents an oxygen, nitrogen, sulfur or phosphorus, Y is a carbon, nitrogen or silicon, and X and Y depending on the valency of X and Y may have other substituents with the formation of telomere General formula II with the above values of X and Y

2) partial hydrogenation of the compounds of formula II to the compound of formula III,

and

3) produce 1-octene by splitting the compounds of formula III.

For the process of telomerization stage 1) of the invention can be used as a pure 1,3-butadiene, and mixtures, which contain 1,3-butadiene. As mixtures containing 1,3-butadiene, can be used, preferably a mixture of 1,3-butadiene with other the hydrocarbons with 4 carbon atoms. Such mixtures are obtained, for example, in the process of disintegrating (cracking) in the production of Athena, in which the reaction gases are introduced with oil, light fuel oil, gas oil, associated gas (LPG), PIG (natural liquid gas and other Hydrocarbon fraction having 4 carbon atoms, resulting in these processes as by-products, contain, depending on the method of splitting different amounts of 1,3-butadiene. Typical concentrations of 1,3-butadiene in hydrocarbon fractions to 4 carbon atoms, such as, for example, they are obtained from steam cracking of oil lie in 20-70% of 1,3-butadiene.

Components 4 carbon atoms, such as n-butane, isobutane, 1-butene, CIS-2-butene, TRANS-2-butene and isobutene that are also contained in these fractions, does not inhibit the reaction at the stage of telomerization or slow down slightly. Diene with cumulated double bonds (1,2-butadiene, Allen, etc.) and alkynes, in particular vinylacetylene, are, on the contrary, as moderators in the reaction of telomerization. Therefore, it is appropriate first remove alkynes to 4 carbon atoms and optionally 1,2-butadiene. This can be performed, if possible, physical methods such as distillation or extraction. Chemically alkynes can be recovered by selective hydrogenation of the alkenes or alkanes, and kumul rowanne diene in monoene. Methods such hydrogenation is known from the prior art and described, for example, in international application WO 98/12160, European patent application EP-A-0273900, German patent application DE-A-3744086 or in U.S. patent US 4704492.

As Tulegenov in stage 1 of the proposed method can be used are all compounds which correspond to the General formula I. In formula I, X represents oxygen, nitrogen, sulfur or phosphorus, Y is a carbon, nitrogen or silicon, and X and Y depending on the valency of X and Y can have other substituents. Preferred substituents at X and Y are hydrogen, alkyl residues with 1-50 carbon atoms, aryl residues with 6-50 carbon atoms and/or heteroaryl residues, the substituents can be the same or different and can be substituted by alkyl groups, aryl, fluorine, chlorine, bromine, iodine, CF3, -OR, -COR, -CO2R, -OCOR, -SR, -SO2R, -SOR, -SO3R, -SO2NR2, -NR2, -N=CR2, -NH2where R means hydrogen, substituted or unsubstituted, aliphatic or aromatic hydrocarbon residue with 1-25 carbon atoms. Preferably X represents oxygen or nitrogen and Y is carbon.

Specific examples Tulegenov according to the General formula I are

- monohydroxy alcohols, e.g. the R, such as methanol, ethanol, n-propanol, isopropanol, allyl alcohol, n-butanol, Isobutanol, octanol, 2-ethylhexanol, isononanol, benzyl alcohol, cyclohexanol, Cyclopentanol or 2.7-octadien-1-ol;

- diatomic alcohols, such as ethylene glycol, 1,2-propandiol, 1,3-propandiol, 1,4-butanediol, 1,2-butanediol, 2,3-butanediol and 1,3-butanediol;

- hydroxycodone, such as esters α-hydroxyoctanoic acids;

primary amines such as methylamine, ethylamine, Propylamine, butylamine, octylamine, 2,7-octadienal, dodecylamine, Ethylenediamine or hexamethylenediamine were;

secondary amines such as dimethylamine, diethylamine, N-methylaniline, bis-(2,7-octadiene)-amine, dicyclohexylamine, methylcyclohexylamine, pyrrolidine, piperidine, morpholine, piperazine or hexamethylenimine.

Telogen, which themselves can be obtained by the reaction of telomerization, can be entered directly or can be formed in situ. So, for example, 2,7-octadien-1-ol can be formed in situ from water and butadiene in the presence of catalyst telomerization, 2,7-octadienes from ammonia and 1,3-butadiene, etc.

Particularly preferably used telegrame are methanol, ethanol, n-butanol, ethylene glycol, 1,3-propandiol, dimethylamine and diethylamine. Most preferably methanol is used.

When determining from the relationship telogen to 1,3-butadiene should take into account the number of active hydrogen atoms in the telogen. So, for example, methanol has one active hydrogen atom, ethylene glycol has two atoms, methylamine two atoms etc.

Per mole of active hydrogen atom of the telogen, which can react with 1,3-butadiene in the reaction of telomerization used from 0.001 mole to 10 moles of 1,3-butadiene. When carrying out the reaction with the liquid phase becomes the preferred ratio is from 0.1 mole to 2 moles of 1,3-butadiene per mole of active hydrogen atom.

As catalysts for telomerization can be used homogeneous, heterogeneous or immobilized catalysts or combinations of them. The literature describes many catalysts for this reaction (cf. A. Behr, "Homogeneous Transition Metal Catalysts", Aspects of Homogeneous Catalysis, 1984, 5, 3-73). For example, as catalysts have been used successfully transition metals of the VIII side group of the Periodic system of elements and their complexes.

In the framework of the present invention preferably Nickel, rhodium, palladium and platinum catalysts. Especially preferably using palladium catalysts. At the stage of telomerization can be used as compounds of palladium(0)and palladium(II). Examples of suitable palladium compounds are palladium(II)chloride, palladium(II)bromide, palladium(II)acetate, palladium(II)-formate, palladium(II)-octanoate, palladium(II)-CT is ONAT, palladium(II)sulfate, palladium(II)nitrate, palladium(II)acetylacetonate, palladium(II)-alkyl sulphonates, Na2PdCl4(disodium-tetrachloro-palladium), K2PdCl4(dicale-tetrachloro-palladium), dichloro-bis-(benzonitrile)-palladium, allylpalladium-chloride, allylpalladium-acetate, Tris-(allyl)-palladium, 1,5-cyclooctadiene(II)-chloride, bis-(triphenylphosphine)-palladium(II)chloride, (1,2-bis(diphenylphosphino)ethane)palladium(II)chloride. When using halides of palladium in the reaction must be added to the activator, as free halide ions inhibit the reaction telomerization. Therefore, it is preferable to use salts of palladium (II) with organic residues, for example palladium-acetate or palladium-acetylacetonate. Examples of complexes of palladium(0) include palladium complexes with donor atoms of phosphorus, nitrogen or arsenic complexes with alkynes, alkenes and danami. Examples of the phosphorus ligands are phosphines, phosphites, phosphonites or phosphinite. Examples of nitrogen-containing ligands are amines, NITRILES and pyridine. Specific examples include tetrakis-(triphenylphosphine)-palladium(0),Tris(dibenzylideneacetone)dipalladium(0) and bis(1, 5cyclooctadiene)-palladium.

The amount used of the catalyst telomerization depends on its activity. Fundamentally can be used any number of catalyst, to the which guarantee a sufficient reaction rate. In homogeneous catalyzed reactions, in which initial connection, the products and the catalyst comprising the transition metal are dissolved in one phase, are usually number between 0.1 part per million and 50,000 parts per million of metal (based on the reaction mixture). When using palladium catalysts are used preferably in the amount of between 1 part per million and 1,000 ppm, especially preferably between 3 parts per million and 100 parts per million of a metal catalyst.

If telomerization held in multiphase systems (e.g., heterogeneously catalyzed or two liquid phases, one of which contains the catalyst)indicated concentration area can be moved. If telomerization in several liquid phases is particularly advantageous when the catalyst and the product are in different phases, as the catalyst may be simply separated in a phase separation. Often one of the liquid phases form water. But also used perforated hydrocarbons, ionic liquids and supercritical carbon dioxide (for ionic liquids cf. .Wasserscheid, W.Keim, Angew. Chem., Int. Ed. 2000, 39, 3772-3789. Telomerization butadiene with water in ionic liquids describe J..L. Dullius, P.A.Z. Suarez, S. Einloft, R.F. de Souza, J. Dupont, J. Fischer, A.D. Cian, Organometallics 1999, 17, 997-1000. A review on water as the phase of the carrier for the catalyst is found, n is the sample, in Century Cornils, W.A. Herrmann (Eds.) "Aqueous-Phase Organomefallic Catalysis", Wiley-VCH, Weinheim, New York, Chichester, Brisbane, Singapore, Toronto, 1998. Particularly preferably in the case of a method with multiple liquid phases to use telogen, which together with the catalyst is in the same phase, but the products are mainly in the second phase.

Catalyst telomerization can be introduced into the process in an active way. But it is often easier to use predecessor (the product of the preceding reaction stage), which under the reaction conditions forms a catalytically active form.

By adding to the reaction telomerization ligands can usually be improved significantly during the reaction (to speed up and change the course of the reaction in the desired direction). Therefore, it is preferable stage 1 of the proposed method is carried out in the presence of ligands. Fundamentally fit all ligands that increase the reaction rate, improve the selectivity of the formation of compound II, extend the term of a catalyst, etc. are Examples of suitable ligands are compounds with one or more trivalent atoms of phosphorus, arsenic, antimony or nitrogen.

Examples of the phosphorus ligands are:

phosphines, such as triphenylphosphine, Tris(p-tolyl)-phosphine, Tris(m-tolyl)-phosphine, Tris(o-tolyl)-phosphine, Tris(p-methoxyphenyl)-phosphine, Tris(p-dimethylaminophenyl)-phosphine, critic hexylphenyl, tricyclohexylphosphine, triethylphosphine, Tris-(1-naphthyl)-phosphine, tribenzylphosphine, tri-n-butylphosphine, three-tert-butylphosphine, Tris-(3-sulfonatophenyl)-phosphine (metal salt), bis-(3-sulfonatophenyl)-phenylphosphine (metal salt), (3-sulfonatophenyl)-dif-nilpotent (metal salt),

the phosphites, such as trimethylphosphite, triethylphosphite, tri-n-propylphosphine, three-isopropylphenyl, tri-n-butylphosphate, tri-ISO-butylphosphate, three-tert-butylphosphine, Tris(2-ethylhexyl)-pofit, triphenylphosphite, Tris(2,4-di-tert-butylphenyl)-pofit, Tris-(2-tert-butyl-4-methoxyphenyl)-pofit, Tris-(2-tert-butyl-4-were-pofit, three-(p-cresyl)-pofit,

the phosphonites, for example, such as metaldetection, phenyldimethylsilane, phenylmethanesulfonyl, 2-phenoxy-2H-dibenzo-[C,e][1,2]oxaphosphorin and its derivatives in which the hydrogen atoms are completely or partially substituted by alkyl and/or aryl residues or atoms of halogen,

phosphinite, such as diphenyl-(phenoxy)-phosphine and its derivatives in which the hydrogen atoms are completely or partially substituted by alkyl and/or aryl residues or atoms of halogen, diphenyl-(methoxy)-phosphine, diphenyl-(ethoxy)-phosphine, etc.

In the framework of the present invention postname salt also understood as ligands. Examples of suitable fofanah salts and their use in telomerization we shall be, inter alia, in European patent application EP-A-0296550.

When using as catalysts of transition metal compounds, the ratio of ligand to metal (mol/mol) is usually from 0.1:1 to 500:1, preferably from 0.5:1 to 50:1, particularly preferably from 1:1 to 20:1. The ligand can be introduced into the reaction dissolved in the substance or in the form of metal complexes. Additional ligand can be introduced into the reaction in each moment of time and in any place in the reactor in the substance as a solution or in the form of a metal complex.

Often advantageous to conduct the reaction telomerization in the presence of bases. Examples of suitable bases are metal hydroxides, in particular the hydroxides of alkali metals and hydroxides of alkaline-earth metals, metal carbonates and bicarbonates of metals, in particular carbonates of alkali metals and alkaline-earth metals and hydrogen carbonates of alkali and alkaline-earth metals, hydroxides of Quaternary ammonium or fofanah ions, alcoholate, alkoxides, enolate, reaction, metal salts of carboxylic acids, amides of metals, such as sodium amide or diethylamid lithium, borhydride alkali metals, alumoweld alkali metals and organic nitrogen bases, in particular amines, such as triethylamine, pyridine or trioctylamine.

Especially, it is preferable to use a metal salt is of elovena, corresponding to General formula IV

In this formula, M stands for a monovalent or stoichiometry proportion multivalent metal. Preferably M is an alkali metal, alkaline earth metal, boron or aluminum, especially preferably represents lithium, sodium or potassium. Compounds according to General formula IV can often be obtained simply by the reaction of a telogen of the formula I with a metal. This can also occur in situ.

The amount of base added to the reaction telomerization, strongly depends on the type of Foundation. When using the catalysts, which are compounds of transition metals, typically use 0 to 50 000 moles of base per mole of the transition metal, preferably from 0.5 to 5 000, particularly preferably from 0.5 to 500 mol of base per mole of the transition metal. It is also possible to use several bases at once.

For stage 1 of the proposed process, you can add other auxiliary substances, for example the introduction of inhibitors, which inhibit the polymerization of butadiene. These inhibitors usually are also commercially available (stable) pure butadiene. Standard stabilizer is the example tert-butylpyrocatechol.

Stage 1 of the inventive process can be carried out without solvent or with the addition of solvents. Used solvents should be substantially inert. The addition of solvents, preferably using Tulegenov that the reaction conditions are in the form of solids, or in the case of products, which under the reaction conditions are obtained in the form of solids. Among suitable solvents are aliphatic, cycloaliphatic and aromatic hydrocarbons, such as alkanes with 3-20 carbon atoms, mixtures of lower or higher alkanes (from 3-20 carbon atoms), cyclohexane, cyclooctane, ethylcyclohexane, alkenes and polyene, vinylcyclohexane, 1,3,7-octatriene, hydrocarbons with 4 carbon atoms from the cracking4-fractions, benzene, toluene and xylene; polar solvents such as tertiary and secondary alcohols, amides, such as ndimethylacetamide, dimethylacetamide and dimethylformamide, NITRILES such as acetonitrile and benzonitrile, ketones, such as acetone, methyl-isobutyl-ketone and diethylketone, esters of carboxylic acids, such as ethyl ether, acetic acid, ethers, such as DIPROPYLENE ether, diethyl ether, methyl tert-butyl ether (MTBE), dimethyl the new ether, methylotrophy ether, 3-metaxiotis, dioxane, tetrahydrofuran, anisole, alkalemia and arrowie ethers of ethylene glycol, diethylene glycol and polyethylene glycol, and other polar solvents, such as sulfolane, dimethylsulfoxide, ethylene carbonate resulting and propylene carbonate. Water can also be used as solvent. The solvents can be used alone or as mixtures of different solvents.

Stage 1 of the present invention preferably is carried out without oxygen, as oxygen has a negative effect on the stability of the catalyst system.

The temperature at which the reaction is carried out in telomerization, lies between 10°200°C, preferably between 40°150°S, particularly preferably between 40°and 110°C. the Reaction pressure ranges from 1 bar to 300 bar, preferably from 1 bar to 120 bar, particularly preferably from 1 bar up to 64 bar and entirely preferably from 1 bar to 20 bar.

For the proposed method is not necessary to achieve complete conversion of butadiene in telomerization. The degree of conversion of butadiene is between 5% and 100%, preferably between 50% and 100%, particularly preferably between 80% and 100%.

Stage 1 of the proposed method can be carried out in a continuous mode or intermittent mode and is not limited to using the op is edelenyi reactor types. Examples of reactors that can be carried out response, are the reactor with stirring, the cascade reactor with stirring, flow reactor (in the form of a tube) and a loop reactor. A combination of different reactors is also possible, for example, a reactor with stirring installed behind him running the reactor.

Heat of reaction is given by known methods, for example, using internal or external coolers. Specifically, this may mean using Novotrubny reactors (reactor tube bundle), reactor cooled traps, coils or radiators or cooling of the exhaust stream (reactor circulation, recirculation).

The catalyst telomerization used in stage 1 of the proposed method, may be after reaction telomerization returned (recycled) and fully or partially used for further reactions telomerization (compare EP-A-0218100). Catalyst separation may occur, for example, by distillation, extraction, precipitation or adsorption. If the catalyst is fully or partially located in one of the two phases, the separation can occur simply by phase separation.

It is also possible that the catalyst prior to separation or during the separation was modified. It is similarly estimated full or partial refund was pushing the congestion in the process, which may also include the modification of the catalyst. For example, in U.S. patent US 4146738 describes the way in which before catalyst separation stabilize his use of auxiliary substances. After separation from other products is activating and returning back to the process.

Alternatively, the catalyst after the reaction can also be processed differently (cf. WO 90/13531, US 5254782).

If stage 1 is used telogen responds not completely, excess telogen preferably separated from the discharge from stage 1 of the proposed method and completely or partially returns to stage 1.

In stage 1 of the proposed method along with the product according to the General formula II as by-products receive mainly substituted at the 3-position of 1.7-octadiene, 1,3,7-octatriene and 4 vinylcyclohexane. They also include small amounts of high-boiling components. Another way would be preferable to separate the by-products of all or part of the product according to the General formula II. Basically can find the use of all methods or combination of methods by which a compound according to General formula II can be isolated from a mixture of products. The preferred separation technology is distillation. For distillating the Department the Department may use any available technology, for example, column trays, columns with a nozzle, columns with a dividing partition, extractive distillation, thin-film evaporators and vertical thin-film evaporator. Distillative separation can occur in one or several stages and depends on the boiling points of the components contained in a mixture of products. If the educt used butadienestyrene mixture of hydrocarbons with 4 carbon atoms, the remaining hydrocarbons with 4 carbon atoms have the lowest boiling point and can be separated from the top (of the head of the column).

If the remaining hydrocarbons with 4 carbon atoms contained isobutene and as telogen use alcohols, it becomes possible to separate the excess alcohol together with hydrocarbons with 4 carbon atoms and then enter in the reaction in other processes. If, for example, isobutene contained in the hydrocarbons with 4 carbon atoms and as telogen use methanol, after telomerization remaining hydrocarbons with 4 carbon atoms can be separated together with excess methanol and filed together in the synthesis of methyl tert-butyl ether(MTBE).

In addition, it may be advantageous to allocate other components of the discharge from stage 1 of the proposed method and, if necessary, to return back into the process or used separately. For the technologist is th, used for this purpose is effective the same as in the allocation of the product of General formula II. As subject selection components are suitable, in particular, used telogen, the excess 1,3-butadiene, substituted at the 3-position of 1.7-octadiene, 1,3,7-octatriene, 4-vinylcyclohexane used base or used grounds and, if necessary, the solvent used.

The product of General formula II in stage 2 hereroense with the formation of a product of General formula III. The product of General formula II may be used in pure form or in mixtures with one or more other components of stage 1.

Hydrogenation with the formation of a product of General formula III can be carried out as a liquid and/or gas-phase hydrogenation or using combinations of these technologies and it can be performed in one or several stages, for example, at the stages of pre-and post-hydrogenation.

The hydrogenation can be carried out continuously or periodically. As reactors can be used known standard reactors for hydrogenation, such as reactors with irrigation catalyst layer. The heat of reaction released in the reaction, is given by known methods, for example, using internal or external coolers, Specifically, this may mean using lots of the tubular reactor (reactor tube bundle), reactors cooled traps, coils or radiators or cooling of the exhaust stream (reactor circulation, recirculation).

The hydrogenation is carried out catalytically. This can be used as homogeneous and heterogeneous catalysts. For example, as catalysts for hydrogenation using transition metals, in particular copper, chromium and VIII metals of the side group of the Periodic system.

When using homogeneous catalysts along with catalytic metals used additional ligands. Suitable ligands are, for example, compounds of trivalent phosphorus (for example, phosphines or phosphites), compounds of trivalent arsenic or antimony, nitrogen compounds (e.g. amines, pyridine, NITRILES, halides, carbon monoxide and cyanide.

In the case of heterogeneous catalysts of the above metals can be modified by other metals or moderators (moderators), for example, heterogeneous palladium catalysts often modify in relation to their activity and selectivity by adding sulfur or carbon monoxide. Copper catalysts often add a certain amount of chromium.

The use of catalysts on carriers usually preferred, as they require small amounts of metals and through t the VA device can further affect the properties of the catalyst. As carriers choose, for example, activated carbon, aluminum oxide, silicon dioxide, mixed oxides of silicon and aluminum (silicon-aluminum-oxide), barium carbonate, barium sulfate and/or diatomaceous earth.

Hydrogenation of 2,7-octadiene residue in 2-octillery the rest is known from the literature. Examples of homogeneous catalytic hydrogenation can be found in Chemistry Letters 1977, 1083-1084, and in Bull. Chem. Soc. Jap. 1968, 41, 254-255. In U.S. patent US 5118837 describes the use of heterogeneous catalysts.

Hydrogenation is conducted at temperatures from 0 to 400°C, preferably between 20 and 200°C. the Pressure is between 0.01 and 300 bar, preferably between 0.1 and 125 bar, particularly preferably between 1 and 64 bar.

The hydrogenation in the liquid phase, similarly catalyzed homogeneous or heterogeneous, can be carried out without or in the presence of additional solvents. Examples of suitable solvents are aliphatic and cycloaliphatic hydrocarbons, such as alkanes from 3-16 carbon atoms, mixtures of lower or higher alkanes (from 3-20 carbon atoms), cyclohexane, cyclooctane, ethylcyclohexane; alcohols, such as methanol, ethanol, propanol, isopropanol, n-butanol, Isobutanol, 2-ethylhexanol, isononanol and isotridecanol; polyols (polyhydric alcohols)such as ethylenglycol is, propylene glycol, 1,3-propandiol and 1,4-butanediol; esters of carboxylic acids, such as ethyl ester of acetic acid; ethers, such as DIPROPYLENE ether, diethyl ether, dimethyl ether, methyl tert-butyl ether, methylotrophy ether, 3-metaxiotis, dioxane, tetrahydrofuran, alkalemia ethers of ethylene glycol, diethylene glycol and polyethylene glycol; sulfolane, dimethylsulfoxide, ethylene carbonate resulting, propylene carbonate and water. The solvents can be used alone or as mixtures of different solvents.

When the hydrogenation in the liquid phase may be present also several liquid phases. This method is especially preferred if the catalyst and the product are in different phases, since the catalyst can be simply separated by phase separation. Often one of the liquid phases form water. But also used perfluorinated hydrocarbons, ionic liquids and supercritical carbon dioxide (for ionic liquids cf. P. Wasserscheid, W. Keim, Angew. Chem., Int. Ed. 2000, 39, 3772-3789). A review on water as the phase of the carrier for catalyst can be found, for example, in Century Cornils, W.A. Herrmann (Eds.) "Aqueous-Phase Organometallic Catalysis", Wiley-VCH, Weinheim, New York, Chichester, Brisbane, Singapore, Toronto, 1998.

When the hydrogenation in the gas phase along with hydrogen and the substrate can be other gases. For example, can be added nitrogen is/or argon, as well as gaseous under the conditions of hydrogenation alkanes, such as methane, propane or butane.

For hydrogenation in the gas phase and in the liquid phase is assumed that one or more component of stage 1 of the proposed method can be fully or partially. When this happens, these components under the conditions of hydrogenation are also restored. So, for example, formed as a by-product of 1.7-octadien substituted in 3-position, at least partially hereroense, 1,3,7-octatriene also formed, at least, less unsaturated or saturated products (octadiene, octane, octane).

The hydrogenation in stage 2 of the proposed method can be done continuously, semi-continuous or periodic manner. Preferred is a continuous process.

Preferably in stage 2 of the proposed method is achieved, the full conversion of compounds according to General formula II. But it is also possible after partial conversion to terminate the reaction and after separation from the other components to return the amount of unreacted compound (II) at stage 2 or, if necessary, differently.

The product of General formula III with stage 2 in the third stage, turn in 1-octene and other fission products. For this purpose, when the necessity is, it is advisable to pre clean the product of General formula III physical methods. Basically can be used all of the methods or combination of methods by which by-products totally or in part can be separated from the compounds of General formula III. The preferred separation method is distillation. For distillative branch can be used all the available technical means, such as disc columns, columns with square columns with a dividing wall, extractive distillation, thin-film evaporators and vertical thin-film evaporator. Distillative separation can occur in one or several stages and depends on the boiling points of the components contained in a mixture of products.

At stage 3 the proposed method the compound of General formula III decompose, forming a 1-octene. Other fission products depend on the telogen used in stage 1. When used in stage 1 of the proposed method as telogen methanol is formed, for example, formaldehyde, when using ethanol - acetaldehyde, in the case of butanol - Butyraldehyde and in the case of diethylamine - ethylethylenediamine.

The cleavage can be carried out in liquid phase and in the gas phase. The cleavage can be carried out in the presence of any kolichestvakh substances, which in terms of splitting inert, rather inert to a large extent. For example, can be added nitrogen or argon, and water, water vapor or alkanes, such as methane, propane or butane.

The temperature at which there is a decomposition of compounds of General formula III, lies between 100 and 800°C, preferably between 150 and 600°S, particularly preferably between 250 and 500°C.

The pressure is from 0.05 to 300 bar, preferably from 1 to 125 bar, particularly preferably from 1 to 64 bar.

The cleavage reaction can be carried out without or in the presence of heterogeneous catalysts. It is preferable to use catalysts with the centers for type Lewis acids, such as amorphous aluminosilicate, alumina, silica, silicic acid, aluminium-containing silicic acid, alumina and zeolites.

Cleavage at stage 3 of the proposed method can be carried out continuously, semi-continuous or periodic manner.

Another variant of this method is the splitting of compounds of General formula III with simultaneous separation of the cleavage products. The separation of the cleavage products may occur, for example, via the gas phase. Technically this is implemented, for example, using distillation; in the lower, warmer part of the distillation the compound of General formula III is cleaved, arr is soumise 1-octene, and, if necessary, other fission products separated in the form of the head of the faction.

The cleavage of a compound of General formula III is converted completely or partially. In case of partial conversion of the cleavage product still contains unreacted starting material of General formula III. After separation of the resulting 1-octene, and, if necessary, other products of the cleavage it can be returned back to splitting. However it is also possible to separate only 1-octene, and, if necessary, of the products of cleavage, and allotted to the stream to return to a pre-cleaning before the splitting.

Separation of 1-octene from other components of the product cleavage occurs by known methods, such as phase separation, extraction, washing, distillation and precipitation. It strongly depends on the telogen used in telomerization. Thus, the cleavage of 1-methoxy-2-octene formed formaldehyde may be separated from 1-octene just by extraction with water. If the cleavage of 1-methoxy-2-octene is added to water or water vapor, when processing is also formed aqueous solution of formaldehyde. In both cases, then the organic phase, which contains 1-octene, may be purified further, for example, via distillation. If in contrast, at the stage telomerases and as telogen use, for example, butanol, then the splitting 1 butoxy-2-octene formed among Butyraldehyde. In this case, the fission products can be divided into separate components, for example, via distillation.

The splitting of compounds of General formula III, along with 1-octene there are also other fission products with unsaturated bonds (double and/or triple bonds), which in the present description are referred to as cleavage products IV. A variant of the present invention is the hydrogenation of these products hydrogen. Specified hydrogenation may occur during the breakdown at the end of the splitting or after partial or complete separation of the product from stage 3 of the proposed method. The product of hydrogenation, if necessary, after cleaning, fully or partially, can be used in stage 1 as telogen. If, for example, as telogen use ethanol, then in stage 3 of the proposed method arises acetaldehyde, which after hydrogenation of the newly formed ethanol, butanol formed respectively Butyraldehyde, which can be again gidrirovanny in butanol, etc.

The hydrogenation products of the cleavage IV carried out catalytically in one or several stages. In the individual stages of the hydrogenation can be carried out in the gas or liquid fasion to use homogeneous dissolved or heterogeneous catalysts. Preferably the use of heterogeneous catalysts. For example, for the hydrogenation products of the cleavage IV as catalysts for use transition metals. In particular, it should be called copper, chromium and VIII metals of the side group of the Periodic system.

In the case of heterogeneous catalysts of the above metals can be modified by other metals or moderators (moderators) [substances regulating the speed of the reaction]. To the copper catalyst is added, for example, often a certain amount of chromium.

The use of catalysts on carriers usually preferred, as they require small amounts of metals and through media properties can be further affect the properties of the catalyst. As carriers are selected, for example, activated angle, aluminum oxide, silicon oxide, a mixed oxide of silicon and aluminum (silicon-aluminum-oxide), barium carbonate, barium sulfate and/or diatomaceous earth.

The hydrogenation products of the cleavage IV, if it does not occur in the conditions of the splitting is carried out at temperatures from 0 to 400°C, preferably between 50 and 250°C. the Pressure PI that lies between 0.01 and 300 bar, preferably between 0.1 and 125 bar, particularly preferably between 1 and 64 bar.

As reactors can be used known standard reactors degidrirovaniya, for example reactors with irrigation catalyst layer. The heat released in the reaction, is given by known methods, for example, using internal or external coolers (cooling devices). Specifically, this may mean using Novotrubny reactors (reactor tube bundle), reactor cooled traps, coils or radiators or cooling of the exhaust stream (reactor circulation, recirculation).

If the splitting of compounds of General formula III and the hydrogenation products of the cleavage IV is carried out in one stage, it can be used in conjunction with each other heterogeneous catalysts, already used in the respective reactions. For it is possible to use catalysts which catalyze both reactions, such as transition metals on the media type Lewis acids. In this case, the cleavage reaction should be carried out in the presence of hydrogen.

The hydrogenation in the liquid phase, indifferent - catalyzed homogeneous or heterogeneous, can be carried out without or in the presence of additional solvents. Examples of suitable solvents are water, aliphatic and cycloaliphatic hydrocarbons, such as alkanes from 3-16 carbon atoms, mixtures of lower or higher alkanes (from 3-20 carbon atoms), cyclohexane, cyclooctane, ethylcyclohexane; with arty, for example, such as methanol, ethanol, propanol, isopropanol, n-butanol, Isobutanol, 2-ethylhexanol, isononanol and isotridecanol; polyols, such as ethylene glycol, propylene glycol, 1,3-propandiol and 1,4-butanediol; esters of carboxylic acids, such as ethyl ether, acetic acid, ethers, such as DIPROPYLENE ether, diethyl ether, dimethyl ether, methyl tert-butyl ether, methylotrophy ether, 3-metaxiotis, dioxane, tetrahydrofuran, alkalemia ethers of ethylene glycol, diethylene glycol and polyethylene glycol; sulfolan, dimethylsulfoxide, ethylene carbonate resulting, propylene carbonate and water. The solvents can be used alone or as mixtures of different solvents.

When splitting along with octene can form small amounts of other olefins with up to 8 carbon atoms. So, due to the isomerization of 1-octene can be formed 2-octene, 2-octene may form 3-octene, etc. can Also be formed octane and octadiene. Therefore, to obtain 1-octene very high purity (>97%) may be necessary to leave a portion of these components with 8 carbon atoms. This can be done using distillatively cleaning. It can occur with or without separation of other products of the cleavage stage (and the best products of the hydrogenation mixture p is the FL splitting IV) or separately as clearing pre-selected fraction with 8 carbon atoms.

The following examples shall disclose the invention but not to limit its scope, which is derived from the description and claims.

Examples

Example 1 (methanol as the telogen, 1-methoxy-2,7-octadiene)

70 l autoclave was heated up to 80°14 kg of methanol, 21 kg of 1,3-butadiene, 7.5 g palladium (II)acetate, 85 g of triphenylphosphine and 160 g of triethylamine without access to water and oxygen. This should be the increase of pressure up to 8 bar. Under these conditions, started the reaction. With the beginning of the reaction of 1,3-butadiene pressure was again reduced. After 24 hours, the autoclave was cooled to room temperature and reset the residual pressure. According to GC-analysis of the degree of conversion of 1,3-butadiene was 98%.

As the main products were obtained:

ComponentCAS No.Share in %
Methanol67-56-132,3
1,3,7-Octatriene1002-35-39,3
4 Vinylcyclohexane100-40-30,2
3-Methoxy-1,7-octadien20202-62-47,8
1-Methoxy-2,7-octadien14543-49-848,8
Rest1,6

p> When processing the reaction discharge was separated by distillation under conditions of periodic process at 80 mbar for the remainder of the catalyst and distilled.

Example 2 (homogeneous catalytic hydrogenation)

In a 3 l autoclave company Büchi were placed 1,000 g of 1-methoxy-2,7-octadiene, 500 ml of tetrahydrofuran and 500 ml of ethanol and 2.5 g of Tris-(triphenylphosphine)-ruthenium(II)-chloride. The temperature was set at 30°and created the hydrogen pressure is 30 bar. The reaction was controlled by the absorbed amount of hydrogen and by GC-analysis. After 6 hours the reaction was stopped. According to GC analysis, the degree of transformation of 1-methoxy-2,7-octadiene was 98% with a selectivity of 89% education 1-methoxy-2-octene (CIS and TRANS). 1-Methoxy-2-octene distillative was separated from the solvent and catalyst.

Example 3 (heterogeneous catalytic hydrogenation)

Free gradients differential reactor with circulation company Xytel were placed 15 g of a heterogeneous ruthenium catalyst. To immobilize the catalyst was in the basket of wire fabric. Weight part of ruthenium on the media γ-Al2About3was 1 wt%. Before reaction, the catalyst was restored in an atmosphere of hydrogen at 200°C. After recovery in a differential reactor with circulation filed 900 ml of a mixture consisting of TRANS--methoxy-2,7-octadiene and CIS-1-methoxy-2,7-octadiene in a mass ratio of 96: 4. At a partial hydrogen pressure of 10 bar, the reaction mixture was first made in the conditions of periodic way process. According to GC-analysis at 40°observed following the course of the reaction: (CIS-MY = CIS-1-methoxy-2-octene, TRANS-MY = TRANS-1-methoxy-2-octene, CIS-FASHION = CIS-1-methoxy-2,7-octadiene, TRANS-MODE = TRANS-1-methoxy-2-octadien)

Space Velocity LHSV-1kg h/lCIS-MY % mass.TRANS-MY % mass.CIS-FASHION % of the mass.TRANS-FASHION % of the mass.The rest % of the mass.
0,00830,131,336,2591,251,04
0,01670,131,996,1690,331,38
0,02500,183,056,2088,402,17
0,03330,234,116,01of 87, 971,68
0,04170,33to 5.575,9586,122,04
0,05000,40to 6.805,7785,041,99
0,06670,508,71the ceiling of 5.6082,11is 3.08
0,08330,64 11,17the 5.4580,262,48
0,10830,8113,875,2477,392,69
0,13331,0016,95equal to 4.9774,023,05
0,15831,1819,874,7470,873,35
0,37502,9852,012,2436,086,69
0,40003,2657,11to 1.8630,09of 7.69
0,42503,4861,011,5925,528,40
0,4500to 3.6765,011,2821,558,49
0,49174,0372,130,8013,479,58
0,52504,2076,20,548,67accounted for 10.39

The above series of experiments again conducted under the same experimental conditions, but at 50°C. As expected, the reaction rate increased with temperature. According to GC-analysis, at 50°observed following the course of the reaction.

TRANS-FASHION % of the mass. 0,4333
Space Velocity LHSV-1kg h/lCIS-MY % mass.CIS-FASHION % of the mass.TRANS-FASHION % of the mass.The rest % of the mass.
0,00830,122,773,8090,332,99
0,01670,164,16of 3.7789,14was 2.76
0,02500,236,013,7187,202,85
0,03330,317,83of 3.6484,243,98
0,04170,369,013,6383,13a 3.87
0,05830,4811,843,5579,634,50
0,09170,7017,083,3173,205,70
0,11670,8821,373,1668,216,38
0,36673,0664,301,0917,8713,68
0,38333,2867,720,8813,9714,15
0,40003,4470,270,7210,8214,75
0,41673,5971,530,718,0116,16
1,2874,290,445,5218,48
0,46673,9175,770,301,5118,51

Example 4 (cleavage with the formation of 1-octene)

100 l-free gradients differential reactor with circulation continuously served gaseous mixture consisting of 1-methoxy-2-octene (CIS and TRANS) [CAS 60171-33-7] and nitrogen. Total served number was 60 NML/min, the Proportion of inert gas in the feed stream was equal to 83%. At atmospheric pressure and temperature range of 375-450°passed the cleavage of 1-methoxy-2-octene 1-octene and formaldehyde. Per 1-methoxy-2-octene in the incoming gas, time spent in the system, equal to 40 C, was observed following shares conversion of 1-methoxy-2-octene, respectively selectivity, education octene:

Temperature [°]375400425
The degree of conversion of methyl-2-oktanovogo ester [%]a 4.8316,736,7
The selectivity of the formation of 1-octene [%]89,777,775,7

1. The way to obtain 1-octene, characterized in that 1) 1,3-butadiene in the presence of a catalyst is and telomerization subjected to interaction with telogen General formula H-X-Y-H, where X represents an oxygen, nitrogen, sulfur or phosphorus, Y is a carbon, nitrogen or silicon, and X and Y, depending on the valency may have substituents, with the formation of telomere General formula H2C=CH-CH2-CH2-CH2-CH=CH-CH2-X-Y-H, 2) telomere hydronaut 1-substituted 2-octene formula H3C-CH2-CH2-CH2-CH2-CH=CH-CH2-X-Y-H and 3) 1-substituted 2-octene decompose with the formation of 1-octene.

2. The way to obtain 1-octene according to claim 1, characterized in that the substituents at X and/or Y represent hydrogen, alkyl residues with 1-50 carbon atoms, aryl residues with 6-50 carbon atoms and/or heteroaryl residues, the substituents may be identical or different and, for its part, can be substituted group is an alkyl, aryl, -F, -Cl, -Br, -I, -CF3, -OR, -COR, -CO2R, -OCOR, -SR, -SO2R, -SOR, -SO3RR, -SO2NR2, -NR2, -N=CR2, -NH2where R means hydrogen, substituted or unsubstituted, aliphatic or aromatic hydrocarbon residue with 1 to 25 carbon atoms.

3. The way to obtain 1-octene according to claim 1 or 2, characterized in that as telogen use monohydroxy alcohol, diatomic alcohol, primary amine or secondary amine.

4. The way to obtain 1-octene one of claims 1 to 3, distinguishing the I, as telogen use methanol, ethanol, n-propanol, isopropanol, allyl alcohol, n-butanol, ISO-butanol, octanol, 2-ethylhexanol, isononanol, benzyl alcohol, cyclohexanol, Cyclopentanol, 2,7-octadien-1-ol, ethylene glycol, 1,2-propandiol, 1,3-propandiol, 1,4-butanediol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol or esters α-hydroxyoctanoic acid.

5. The way to obtain 1-octene one of claims 1 to 3, characterized in that as telogen use methylamine, ethylamine, Propylamine, butylamine, octylamine, 2,7-octadienal, dodecylamine, Ethylenediamine, hexamethylenediamine were, dimethylamine, diethylamine, N-methylaniline, bis-(2,7-octadiene)-amine, dicyclohexylamine, methylcyclohexylamine, pyrrolidine, piperidine, morpholine, piperazine or hexamethylenimine.

6. The way to obtain 1-octene according to one of claims 1 to 5, characterized in that in stage 1) per mole of active hydrogen atom of telogen used from 0.001 mole to 10 moles of 1,3-butadiene.

7. The way to obtain 1-octene according to one of claims 1 to 6, characterized in that the unreacted in stage 1) telogen Recuperat and again served on phase 1).

8. The way to obtain 1-octene according to one of claims 1 to 7, characterized in that in stage 1) as catalyst telomerization use the transition metal VIII the side group of the Periodic system.

9. The way to obtain 1-octene by A8, characterized in that in stage 1) as catalyst telomerization use palladium.

10. The way to obtain 1-octene according to one of claims 1 to 9, characterized in that in stage 1) use serves as a ligand compound with a trivalent atom of phosphorus, arsenic, antimony or nitrogen.

11. The way to obtain 1-octene of claim 10, characterized in that in stage 1) as a ligand is used phosphine, postit, phosphonic or phosphinic.

12. The way to obtain 1-octene according to one of claims 1 to 11, characterized in that in stage 1) in addition use basis.

13. The way to obtain 1-octene according to one of claims 1 to 12, characterized in that used in stage 1) catalyst telomerization Recuperat and completely or partially return in the process.

14. The way to obtain 1-octene according to one of claims 1 to 12, characterized in that the catalyst telomerization with stage 1) do not return to stage 1).

15. The way to obtain 1-octene according to claim 1, characterized in that in stage 2) use hydrogen and homogeneous catalytic hydrogenation.

16. The way to obtain 1-octene according to claim 1, characterized in that in stage 2) using hydrogen and a heterogeneous catalyst for the hydrogenation.

17. The way to obtain 1-octene indicated in paragraph 15 or 16, characterized in that in stage 2) using a hydrogenation catalyst which contains copper, chromium and/or VIII transition metal FOB is offered by the groups of the Periodic system.

18. The way to obtain 1-octene in one of the preceding paragraphs, characterized in that the 1,3,7-octatriene generated in stage 1) as a by-product, in whole or in part hydronaut in stage 2).

19. The way to obtain 1-octene according to claim 1, characterized in that substituted in 3-position 1,3,7-octatriene generated in stage 1 as a by-product, in whole or in part hydronaut in stage 2).

20. The way to obtain 1-octene according to claim 1, characterized in that the cleavage stage 3) is carried out at temperatures between 150°and 600°C.

21. The way to obtain 1-octene according to claim 1, characterized in that applied to stage 3) stream for splitting contains less than 5% of hydrocarbons having 8 carbon atoms.

22. The way to obtain 1-octene according to claim 1, characterized in that in stage 3) substituted in the 1-position 2-octene reacts only partially.

23. The way to obtain 1-octene according to claim 1, characterized in that the unreacted substituted in 1-position 2-octene is separated from the rest of the product of stage 3) and completely or partially return to the step 3).

24. The method according to one of claims 1 to 23, characterized in that substituted in 1-position 2-octene return on purification step prior to stage 2).

25. The way to obtain 1-octene according to one of claims 1 to 24, characterized in that it further formed at stage 3) about UKTI with unsaturated bonds hydronaut hydrogen, when the hydrogenation takes place during cleavage, immediately after splitting or after partial or complete separation of the products stage 3).

26. The way to obtain 1-octene according to one of claims 1 to 25, characterized in that in stage 3) cleavage with the formation of 1-octene carried out simultaneously with the separation of 1-octene and in addition products formed from unsaturated bonds from the fed to stage 3) substances.

27. The way to obtain 1-octene according to one of claims 1 to 26, characterized in that the cleavage stage 3) is carried out in the presence of water or water vapor.

28. The way to obtain 1-octene according to one of claims 1 to 27, characterized in that the cleavage stage 3) is carried out in the presence of a catalyst.



 

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