Process of oxidative halogenation and optional dehydrogenation of c3-c10-hydrocarbons (options)

FIELD: petrochemical processes.

SUBSTANCE: invention relates to oxidative halogenation processes to obtain halogenated products, in particular allyl chloride and optionally propylene. Process comprises interaction of hydrocarbon having between 3 and 10 carbon atoms or halogenated derivative thereof with halogen source and optionally oxygen source in presence of catalyst at temperature above 100°C and below 600°C and pressure above 97 kPa and below 1034 kPa. Resulting olefin containing at least 3 carbon atoms and halogenated hydrocarbon containing at least 3 carbon atoms and larger number of halogen atoms than in reactant. Catalyst contains essentially iron and copper-free rare-earth metal halide or oxyhalide. Atomic ratio of rare-earth metal to iron or copper is superior to 10:1. In case of cerium-containing catalyst, catalyst has at least one more rare-earth element, amount of cerium present being less than 10 atomic % of the total amount of rare-earth elements. Advantageously, process is conducted at volumetric alkane, halogen, and oxygen supply rate above 0.1 and below 1.0 h-1, while diluent selected from group including nitrogen, helium, argon, carbon monoxide or dioxide or mixture thereof is additionally used. Halogenated product is recycled while being converted into supplementary olefin product and olefin product is recycled in order to be converted into halogenated hydrocarbon product. Optionally, allyl chloride and ethylene are obtained via interaction of propane with chlorine source in presence of catalyst.

EFFECT: increased productivity of process and improved economical characteristics.

26 cl, 1 tbl

 

The present invention relates to a method of oxidative halogenation and optional dehydrogenation of the hydrocarbon reactant contains three or more carbon atoms (hereinafter referred to as the "C3+ hydrocarbons"). Used in the description, the term "oxidative halogenoalkane and optional dehydrogenation" refers to the way in which the hydrocarbon reactant contains three or more carbon atoms, or halogenated derivative, communicates with a source of halogen atoms and, optionally, a source of oxygen with the aim of obtaining halogenated hydrocarbon product containing three or more carbon atoms and having a large number of halogen substituents compared to the hydrocarbon reactant, and optionally olefinic hydrocarbons containing three or more carbon atoms.

Olefinic C3+ hydrocarbons and halogenated C3+ hydrocarbons, for example, propene, chloropropane and chloropropene, more preferably propene, dichloropropan and allyl chloride, are widely used in various fields. Propene (or propylene) is an important olefinic feedstock to obtain such valuable products, such as polypropylene, isopropyl alcohol and cumene. Dichloropropan is a valuable fumigant and solvent. Chloride allyl serves as a precursor allyl JV the mouth and epichlorohydrin.

Although there are several ways to obtain propene by propane dehydrogenation, none of them have found practical application in commercial scale, due to the high energy intensity of these methods and a high capital costs of their implementation. Mainly propene is obtained as a byproduct in two important petrochemical processes: a vapor-phase cracking, the main products are ethylene, propene, butenes and butadiene and catalytic cracking, the main products are naphtha (gasoline), propene and butenes. Almost all the amount of propene required for today's market, is provided by the above methods. Because the demand for propene is growing faster than the market as ethylene and/or gasoline, it is very important to have a method of its production, which is not associated with the formation of the above other products.

Ecatlithuania oxidative halogenoalkane olefinic hydrocarbons containing three or more carbon atoms, e.g. propene, using chlorine with formation of the corresponding unsaturated halogenated hydrocarbons, such as chloropropene, known as "hot chlorination", described in a representative book K. Weissermel and H.-J. Arpe, Industrial Organic Chemistry", 2ndedition, VCH Verlagsgesellschaft mbH, Weinheim, pp. 291-293. Despite what I the high efficiency of this method, its implementation is the use of high temperatures.

The literature also described as non-catalytic and catalytic reactions of Halogens with saturated C3+ hydrocarbons; see, for example, Olah and Molnar "Hydrocarbon Chemistry", John Wiley & Sons, 1995, pp. 415-432, and Witcoff and Reuben "Industrial Organic Chemicals, John Wiley & Sons, 1996, pp. 338-341. About catalytic routes reactions reported Weissermel and Arpe, ibid, str. Catalytic routes are not implemented in practice as "hot chlorination is more effective and economical way. In the catalytic process hydrocarbon reagent interacts under the reaction conditions with a source of halogen and, optionally, a source of oxygen in the presence of a catalyst of oxidative halogenation. Typically, the catalyst contains a compound of copper, connection, iron, cerium oxide, optionally in the presence of one or more chlorides of alkali or alkaline earth metals, and/or optionally, in the presence of one or more compounds of rare-earth metal deposited on an inert carrier, usually on alumina, silica or aluminosilicate.

A disadvantage of the known catalytic process is the formation of unacceptable amounts vysokoorganizovannyh products, including perhalogenated products that are less desirable than monohalogenated and dihalogenoalkane products. Another disadvantage of the local methods is the formation of undesirable quantities of products of deep oxidation (CO x), mainly carbon monoxide and carbon dioxide. Getting a unvaluable highly halogenated products and undesirable oxidation products unproductive depleting hydrocarbon reserves and creates problems associated with the separation of the products and the use of waste products. Another disadvantage is the fact that many of the halides of transition metals used as catalysts for a process of this type have significant vapor pressure at the temperature of the reaction; in other words, such catalysts are volatile compounds. Such volatility usually leads to loss of catalytic activity and/or the deposition of corrosive materials on the items of technological equipment located at the outlet of the technological cycle.

As follows from the above, the catalytic oxidative halogenoalkane hydrocarbons containing three or more carbon atoms, in essence, is a non-selective process in respect of mono - and dehalogenating hydrocarbon products. Accordingly, it is necessary to increase the selectivity for mono - and dihalogenoalkane hydrocarbons. In addition, it is necessary to reduce the selectivity of the reaction for vysokoorganizovannym products, including perhalogenated products, and products of oxidized who I am. In addition, you want to increase the catalytic activity and lifetime of the catalyst. When implementing these improvements, oxidative halogenoalkane C3+ hydrocarbons with obtaining halogenated C3+ hydrocarbons, preferably mono - and dehalogenating C3+ hydrocarbons, for example, dichloropropane and allyl chloride, and optionally, obtaining unsaturated hydrocarbon products, preferably olefins, will become more attractive.

The present invention provides a new method of oxidative halogenation and optional dehydrogenation with obtaining halogenated C3+ hydrocarbon and optionally C3+ olefin hydrocarbon. A new method of the present invention involves contacting the hydrocarbon reactant contains three or more carbon atoms (C3+ hydrocarbon), or its halogenated derivative with a source of halogen and, optionally, a source of oxygen in the presence of a catalyst under conditions suitable to obtain a halogenated hydrocarbon product containing three or more carbon atom (halogenated C3+ hydrocarbon) and having a greater number of halogen substituents than the original hydrocarbon. Not necessarily, receive a second product comprising olefinic hydrocarbon content is of AMI three or more carbon atoms. In this way, it is preferable to use a source of oxygen. The catalyst used in this method includes a halide of rare earth metal or oxyhalide derived rare earth metal, almost in the absence of copper and iron, provided that in the case of the presence in the catalyst of cerium, it is also present at least one other rare earth element.

According to the present invention a new method of oxidative halogenation and optional dehydrogenation ensures the successful conversion of the hydrocarbon reactant contains three or more carbon atoms, or halogenated derivative, in the presence of a source of halogen and preferably the oxygen source in a halogenated hydrocarbon product containing three or more carbon atoms and having a greater number of halogen substituents than the hydrocarbon reactant. In an optional order in parallel may form a second hydrocarbon product containing C3+ olefin hydrocarbon. According to a preferred embodiment of the method of the present invention may be used with success for the oxidative chlorination of propane in the presence of hydrogen chloride and oxygen to obtain allyl chloride and propylene. Compared to known methods of str is about the present invention provides a highly selective preferential obtaining halogenated hydrocarbon product, preferably mono - and dehalogenating hydrocarbon product, and, optionally, the olefin product with virtually no perhalogenated halogenougljovodonika by-products and at low concentrations or complete absence of such unwanted oxygenates as carbon monoxide and carbon dioxide. Reduced selectivity for perhalogenated halogenougljovodonika and unwanted oxygendemanding products corresponds to a more efficient use of hydrocarbon reactant, higher performance as desired nitrohalogenotrienes hydrocarbon products and the optional olefin and a decrease in the number of problems associated with the separation and disposal of waste. As additional advantages may be noted that in the case of education less the desired product as olefins and halogenated product, such a product can be recycled to the oxidative halogenation order to obtain a more desirable product.

In addition to these advantages, the catalyst used in the method of the present invention does not require such a traditional medium, or substrate, as aluminum oxide or silicon oxide. Instead, the catalyst of the present invention successfully used the tsya halide of rare earth metal or oxyhalide derived rare earth metal, functions as a catalyst carrier and a source of additional catalytically active rare earth component. Unlike most of the known heterogeneous catalysts, the catalyst of the present invention on the basis of the halide of rare earth metal has good solubility in water. In accordance with the clogging particles of rare earth halogenated catalyst of various items of process equipment, such as filters, valves, circulating pipes, and small or intricate components of the reactor, designated the clogging of the catalyst particles can easily be cleaned with water with the return of the equipment in working condition. A further advantage of the catalyst of the present invention is that it is significantly less volatility than the known catalysts. Thus, rare earth halogenated and rare earth oxyhalide catalysts used in the method of the present invention provide acceptable values of the reaction rate and have a long service life and, in addition, no issues with clogging at the outlet of technological lines and equipment corrosion.

All of the above properties make the method of the present invention extremely attractive gloss of leat the boilers for the conversion of C3+ hydrocarbon or halogenated derivative in halogenated C3+ hydrocarbons, containing a greater number of halogen substituents than hydrocarbon reactant and, optionally, a C3+ olefin hydrocarbon by-product. In accordance with preferred embodiments of the present invention is implemented selective synthesis of mono - and/or dehalogenating hydrocarbon products together with the olefin. In accordance with the preferred embodiment of the method of the invention provides selective oxidative dehydrogenation and halogenoalkane propane to propene and monohalogenated propene, preferably allyl chloride or allyl bromide.

Using a new method of oxidative halogenation and optional dehydrogenation of the present invention can be selectively obtained halogenated hydrocarbon product containing three or more carbon atoms, preferably mono - or dehalogenating hydrocarbon product containing three or more carbon atoms, and an optional olefin by-product, with no significant education perhalogenated chlorophenothane product and undesirable oxygen-containing products, such as COxoxygenates (CO and CO2) are formed in small quantities. A new method of the present invention involves the contacting of the hydrocarbon, terasawa three or more carbon atoms (C3+ hydrocarbon), or its halogenated derivative with a source of halogen and, optionally, a source of oxygen in the presence of a catalyst and at reaction conditions suitable to obtain a halogenated hydrocarbon product containing three or more carbon atoms, (halogenated C3+ hydrocarbon) and having a greater number of halogen substituents than the original hydrocarbon reactant. In the process, formed the optional by-product comprising olefin containing three or more carbon atoms. According to a preferred embodiment of the invention uses a source of oxygen. The unique catalyst used for the process of oxidative halogenation and optional dehydrogenation of the present invention, includes halogenated or oxyhalide derived rare earth metal, containing no copper or iron, provided that in the presence of the catalyst of cerium in it also there is at least one rare earth element.

The term "oxidative halogenoalkane and optional dehydrogenation" in some cases will refer simply to "oxidative galogenirovannyie". The reduction of the used term is used for convenience only and in no way limits the way. The method of the present invention includes both R the action of halogenation, in which the formation of halogenated products, and reactions of dehydrogenation, in which are formed the more unsaturated hydrocarbon products (e.g., olefins), compared to the original hydrocarbon reagents (e.g., alkanes).

In accordance with a preferred embodiment of the present invention under consideration, the method provides for obtaining as a by-product of C3+ olefins, preferably propylene. Olefinic by-product can be recycled to the oxidative halogenation for further processing in halogenated hydrocarbons, such as allyl chloride.

According to another preferred embodiment of the present invention, a halogenated hydrocarbon product, such as allyl chloride, can be recycled to the oxidative halogenation with the purpose of further processing in such olefinic products, such as propylene.

According to another preferred embodiment of the method of the present invention comprises the contacting of propane with a source of halogen and, optionally, a source of oxygen in the presence of catalyst and process conditions, providing allyl chloride and propylene, the catalyst includes halogenated or oxyhalide derived rare earth metal, PRA is almost not containing copper and iron, provided that in case of the presence in the catalyst of cerium in it also there is at least one rare earth element. According to the most preferred embodiment of the source of halogen is hydrogen chloride; the resulting halogenated C3+ hydrocarbon is an allyl chloride; and side olefinic product is a propylene.

As for the catalyst, according to the preferred embodiment of the halogenated or oxyhalides rare earth catalyst is a porous material that, in accordance with the present invention means the value of the area of the surface of the catalyst, of at least 5 m2/g measured by the BET method (method of measuring surface area by the Brunauer-Emmet-Teller)method as described by S. Brunauer, P.H. Emmet and E. Teller, Journal of the American Chemical Society, 60,309 (1938). In another more preferred embodiment of the invention, the rare earth halide is a chloride, lanthanum, and oxychlorine rare earth metal is lanthanum oxychloride.

The source of the hydrocarbon reactant used in the method of oxidative halogenation of the present invention is a hydrocarbon containing three or more carbon atoms, or halogenated hydrocarbons containing three or more coal is adnych atom, able to acquire a greater number of halogen substituents in accordance with the method described in this document. Halogen Deputy halogenated hydrocarbon reactant is preferably selected from chlorine, bromine, iodine and mixtures thereof, more preferably from chlorine and bromine. The halogenated hydrocarbon may contain one, two or three halogen substituent; however, for the purposes of the present invention halogenated hydrocarbon reactant is not as perhalogenated connection, as hexachloropropane. Halogenated hydrocarbon reactant may contain different halogen substituents, such as, for example, in bramhacharya etc. Suitable examples of hydrocarbon reactants and halogenated hydrocarbon reactants, without specific limitation, and can serve as alkanes and alkenes and their halogenated derivatives, including propane, butane, pentane, chlorpropham, chlorbutol, dichlorprop, dichlorobutane, bromopropane, rambutan, dibromopropan, dibromobutan, brambleberry, etc. including their higher homologues. For this purpose, can also be used such cyclic aliphatic hydrocarbons like cyclohexane, and aromatic hydrocarbons such as benzene, ethylbenzene and cumene, including alkyl - and halogen-substituted cyclic aliphatic and aromatic Plevo the cities. Preferably the hydrocarbon reactant or halogenated hydrocarbon reactant represent a hydrocarbon With3-20more preferably the hydrocarbon With3-10. The most preferred hydrocarbon reactant selected from propane and propene. The hydrocarbon reactant may be injected into the oxidative halogenation in the form of a stream of pure reagent or as shown below, in a mixture with an inert diluent or in the form of a mixture of hydrocarbon reactants, optionally, in combination with an inert diluent.

The source of halogen used in the method of the present invention may be an inorganic or organic halogenated compound, capable to transfer the halogen atoms of the hydrocarbon reactant. Suitable examples of sources of halogen, not limiting the scope of the invention, can serve as chlorine, bromine, iodine, hydrogen chloride, hydrogen bromide, hydrogen iodide, as well as halogenated hydrocarbons containing one or more labile halogen substituents (i.e. halogen substituents capable of transfer). Examples of such substances can be perhalogenated, for example, carbon tetrachloride and chetyrehhloristy carbon and vysokoorganizovannyye hydrocarbons containing, for example, three or more carbon atomone limiting the scope of the invention examples vysokoorganizovannyh hydrocarbons, containing three or more halogen substituents, at least one of which is labile, can serve as chloroform and tribromomethane. The preferred source of halogen is the source of chlorine or bromine, more preferably hydrogen chloride or hydrogen bromide, most preferably hydrogen chloride.

The source of halogen may be introduced into the process in any amount which is effective to obtain the desired halogenated hydrocarbon product. Generally, the amount of halogen source will vary depending on the specific stoichiometry of the reaction, the reactor design and safety requirements. For example, you can use a stoichiometric amount of a source of halogen relative to the hydrocarbon reactant or with respect to oxygen, if the latter is present in the system. On the other hand, if it is desired, the source of halogen may be used in quantities more or less stoichiometric amount. In accordance with one of embodiments illustrating the invention, the propane may be subjected to oxidative chlorination chlorine with the formation of chloropropane and hydrogen chloride in accordance with the stoichiometric reaction represented by the equation (I):

CH3CH2CH3+Cl2>CH3CHClCH3 +HCl (I)

This process, which does not use oxygen, usually carried out at a stoichiometric molar ratio between chlorine and propane or upon a specific ratio higher than the stoichiometric value (molar ratio Cl2:1 CH3CH2CH3and preferably with an excess of chlorine to ensure complete conversion of propane. According to this embodiment of the present invention the molar ratio between the number of source of halogen and a number of hydrocarbon reactant has a value of more than 1/1, preferably higher than 2/1, and more preferably higher than 4/1. In accordance with this embodiment of the invention the molar ratio between the source of halogen and hydrocarbon reactant has a value less than 20/1, preferably less than 15/1, and more preferably less than 10/1.

According to another embodiment illustrating the present invention, the propane may be subjected to oxidative chlorination and dehydration using hydrogen chloride in the presence of oxygen to form allyl chloride, propylene and water in accordance with the following stoichiometric reaction represented by the equation (II):

2 CH3CH2CH3+HCl+1,5O2>CH2=CHCH3+CH2=CHCH2Cl+3H2O (II)

The embodiment of the way in which use oxygen, p is riodic this process in the category of "high Flammability", due to security considerations. The term "increased Flammability" means that oxygen is the limiting reagent and is used in molar excess of the hydrocarbon reactant relative to oxygen. Usually the molar ratio of hydrocarbon to oxygen is chosen so that to carry out the process outside the Flammability of the mixture, although this requirement is not absolute. In addition, typically use such stoichiometric molar ratio between the hydrogen chloride and oxygen (for example, 1 HCl:1,5 O2), which provides a comprehensive transformation of a source of halogen and a source of oxygen.

For the method of the present invention does not require a source of oxygen; however, the source of oxygen is preferred, especially in cases when the source contains halogen atoms of hydrogen. The oxygen source may be any oxygen-containing gas, for example, commercially available pure molecular oxygen, air, air enriched with oxygen, a mixture of oxygen with such gaseous diluent which doesn't have any undesirable effect on the reaction of oxidative halogenation as nitrogen, argon, helium, carbon monoxide, carbon dioxide, methane, and mixtures thereof. As noted above, when using oxygen in the reaction is the PR oxidative halogenation is served raw materials increased Flammability". Typically, the molar ratio between the hydrocarbon reactant and oxygen has a value of more than 2/1, preferably more than 4 : 1 and more preferably more than 5/1. Typically, the molar ratio between the hydrocarbon reactant and oxygen has a value less than 20/1, preferably less than 15/1, and more preferably less than 10/1.

As described above, the person skilled in the art will receive information to determine the molar amounts of C3+ hydrocarbon reactant, a source of halogen and a source of oxygen in the combinations of reagents other than those illustrated above.

Optionally, when necessary, raw materials, including hydrocarbon reactant, a source of halogen and, optionally, a source of oxygen may be diluted with a gaseous diluent or carrier gas, which may represent practically any directionspanel gas that do not have undesirable effects on the oxidative halogenation. Such a diluent may help to remove products and heat from the reactor and reduce unwanted side reactions. Examples of suitable diluents and not limiting the scope of the invention may serve as nitrogen, argon, helium, carbon monoxide, carbon dioxide, methane and mixtures thereof. The amount of diluent is typically sostavlenie 10 mol.%, preferably more than 20 mol.%, in calculating the total number of moles of the raw material fed to the reactor, i.e. the total number of moles of hydrocarbon reactant, a source of halogen and a source of oxygen and diluent. The diluent is usually used in amounts of less than 90 mol.%, preferably less than 70 mol.% in calculating the total number of moles of the raw material fed to the reactor.

In accordance with one aspect of the present invention, the catalyst used in the process of oxidative halogenation, contains a halide compound of rare earth metal. Rare earth elements are a group of 17 elements consisting of scandium (atomic number 21)and yttrium (atomic number 39) and lanthanoids (atomic numbers 57-71) [James B. Hedrick, U.S. Geological Survey - Minerals Information-1997, "Rare-Earth Metals"]. The term lanthanide in the context of the present description refers to an element selected from lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium, lutetium and mixtures thereof. Preferred rare earth elements for use in the process of oxidative halogenation are those items that are generally considered monovalent metals. Catalytic properties of rare earth halides on the basis of polyvalent metals inferior catalytic properties of rare earth halides OS is ove monovalent metals. Rare earth element of the present invention is preferably selected from lanthanum, praseodymium, neodymium and mixtures thereof. The most preferred rare earth element used as a catalyst is lanthanum or a mixture of lanthanum and other rare earth elements.

The preferred rare earth halide may be represented by the formula MX3in which M represents at least one rare earth element selected from the group consisting of lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium, lutetium and mixtures thereof; and each X is independently selected from chlorine, bromine and iodine. More preferably, when X is a chloride, and the preferred rare earth halide may be represented by formula MCI3where M has the above values. In the most preferred case, X is a chloride, and M is lanthanum or a mixture with other rare earth elements.

In accordance with a preferred embodiment of the halide of rare earth metal is a porous material, typically having a surface area according to BET more than 5 m2/year Preferred value of specific surface area by BET is more than 10 m2/g, more predpochtitel is but above 15 m 2/g, even more preferably above 20 m2/g and most preferably above 30 m2/year For these measurements was filmed absorption isotherm of nitrogen at 77 K, which was calculated specific surface area using a WET method, referenced above.

In accordance with another aspect of the invention is used, the catalyst includes oxychlorine rare earth metal of those seventeen elements that are listed above. The preferred rare earth oxychlorine can be represented by the formula MOX, where M represents at least one rare earth element selected from the group consisting of lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium, lutetium and mixtures thereof; and each X is independently selected from the group consisting of chloride, bromide and iodide. The preferred rare earth halide is a rare earth oxychloride, corresponding to the formula MOCl, in which M has the above values. Most preferably, when X is a chloride, and M is lanthanum or a mixture with other rare earth elements.

In accordance with a preferred embodiment of oxychlorine rare earth metal is a porous material that functions Evet surface area according to BET more than 12 m 2/year Preferred value of specific surface area by BET is over 15 m2/g, more preferably above 20 m2/g, and most preferably above 30 m2/, Typically oxychlorine rare earth metal has a specific surface area according to BET less than 200 m2/, it Should be noted that the powder x-ray (XRD) phase MOCl differ from radiographs MCl3phase.

As a rule, the presence of the catalyst metals capable of oxidation-restoration (redox), is undesirable. Redox metals usually include transition metals with more than one stable oxidation state, for example, iron, copper and manganese. A special requirement of the rare earth halide or oxyhalogenation the catalyst, is that they almost did not contain copper and iron. The term "essentially free" means that the atomic ratio of rare earth element and the redox metal, preferably iron or copper, has a value higher than 1/1, preferably higher than 10/1, more preferably higher than 15/1, and most preferably higher than 50/1. In addition, it is known that cerium related to rare earth elements of the series of lanthanides, is a catalyst for oxidation-reduction, with the ability nchod what we in the States of oxidation of the 3 +and 4+. For this reason, in the case where the rare earth metal is cerium, the catalyst of the present invention further comprises at least one rare earth metal other than cerium. In the case of cerium, it is preferable that the molar amount of the catalyst was smaller than the total number of other rare earth metals present in the catalyst. However, more preferably, when the catalyst does not contain cerium. The term "practically does not contain cerium implies that the cerium is present in the catalyst in amounts of less than 10 atomic percent, preferably less than 5 atomic percent, and still more preferably less than 1 atomic percent based on the total amount of rare earth components.

According to an alternative embodiment of the present invention described above halogenated rare earth or oxyhalides rare-earth catalyst may be bound, jointly extruded or drawn on such traditional media as aluminum oxide, silicon dioxide, a mixture of oxides of aluminum and silicon, porous aluminosilicate (zeolite), a mixture of oxides of silicon and magnesium, bauxite, magnesium oxide, silicon carbide, titanium oxide, zirconium oxide, zirconium silicate, or combinations thereof. According to this embodiment Trad the traditional media used in more than 1 wt.%, but less than 90 wt.%, preferably less than 70 wt.% more preferably less than 50 wt.% calculated on the total weight of the catalyst and catalyst carrier.

In some cases, the catalyst is advantageous to include other elements. For example, the preferred element of the additive can be an alkali and alkaline earth metals, boron, phosphorus, sulfur, germanium, titanium, zirconium, hafnium, and combinations thereof. Such elements may be present in the catalyst to change its catalytic properties or to improve the mechanical properties (e.g., abrasion resistance) of the material. According to a preferred embodiment of the elemental additive is the calcium. In accordance with another preferred embodiment of the composition element of the additive does not include aluminum or silicon. The total elemental concentration of additives in the catalyst is usually more than 0.01 wt.% and, typically, less than 20 wt.% calculated on the total weight of the catalyst.

Halogenated and oxyhalide rare earth compounds can be obtained commercially ways or methods described in the literature. The way is now considered preferable to obtain a porous rare earth oxyhalide connection (MOSS), includes the following stages: (a) preparation of a solution of a halide of rare earth element is whether the elements in the solvent or containing water, alcohol, or their mixture; (b) adding a base to form a precipitate, and (C) the collection and calcining the precipitate to obtain the MOSS. The preferred halide is a chloride rare earth metal, for example, any chloride rare earth metal produced by the industry. Usually as a reason to use nitrogen-containing base selected from ammonium hydroxide, alkylamines followed, arylamino, arylalkylamines, hydroxides of alkylamine, hydroxides of arylamine, hydroxides of arylalkylamine, and mixtures thereof. Nitrogen-containing base may also be entered into the system in the form of a mixture with other grounds, does not contain nitrogen. Preferred nitrogen-containing base is ammonium hydroxide or hydroxide, Tetra(alkyl)ammonium, more preferably a hydroxide, Tetra(C1-20alkyl)ammonium. Porous oxychloride rare earth metals can also be obtained by appropriate use of hydroxides of alkaline or alkaline earth metals, in particular in the presence of buffered nitrogen-containing base, although caution must be exercised in order to avoid preferential hydroxide or oxide of rare earth metal. At stage (a) as a solvent, it is preferable to use water. Typically, the deposition is carried out at a temperature which e above 0° C. typically, the deposition is carried out at a temperature below 200°C, preferably below 100°C. Typically, the deposition is performed at a pressure close to atmospheric, although if necessary it is possible to use increased pressure to maintain liquid phase at the temperatures used. Firing is generally carried out at temperatures above 200°C, preferably above 300°and at least 800°S, preferably less than 600°C. sharing carboxylic acid and halogenide rare earth metal can lead to the formation of oxyhalide derivatives of rare metals in the corresponding decomposition.

The preferred way for now education porous rare earth halogenated (MX3) catalyst includes the following stages: (a) preparation of a solution of a halide of rare earth element or elements in a solvent comprising water, alcohol, or their mixture; (b) adding a base to form a precipitate; (C) collection and calcining the precipitate; and (d) contacting the calcined precipitate with a source of halogen. The preferred halide of rare earth metal is a rare earth chloride of the metal, for example, any chloride rare earth metal produced by industry. As solvent and base may use the I any of the substances mentioned above in connection with obtaining the MOSS. The preferred solvent is water, and base - nitrogen-containing base. Typically, the deposition is carried out at temperatures above 0°and less than 200°C, preferably below 100°when the surrounding atmospheric pressure or an elevated pressure to maintain the system in the liquid phase. The calcination is usually carried out at temperatures above 200°C, preferably above 300°but below 800°C, and preferably below 600°C. the Preferred source of halogen is a halogen, hydrogen, as hydrogen chloride, hydrogen bromide or modesty hydrogen. Communication with a source of halogen is usually carried out at a temperature above 100°and below 500°C. Typical pressures used in contact with a source of halogen, lie in the range from ambient atmospheric pressure to pressures below 150 lbs/inch2(to 1.034 kPa).

As noted above, the rare earth oxyhalide (MOSS) connection can be turned into a rare earth halide (MH3in the processing oxyhalide source of halogen. Since according to the present invention for a method of oxidative halogenation requires a source of halogen, there is a possibility of interaction between oxyhalide rare earth metal with a source of halogen for example, with chlorine in the reactor oxidative halogenation with the formation of MH3the catalyst in situ.

According to the present invention, the oxidative halogenation and optional dehydrogenation can be carried out in a reactor of any conventional design suitable for carrying out gas-phase or liquid-phase processes, including batch reactor, the reactor with a fixed catalyst bed reactor with a fluidized bed catalyst reactor with a moving catalyst bed reactor with constant and intermittent streams of the reactants and the reactor catalytic distillation. The process conditions (for example, the molar ratio of reactants, temperature, pressure, average hourly feed rate) can vary within wide limits, provided the desired halogenated C3+ hydrocarbon product, and optionally, the desired olefin product. Usually, this process is carried out at temperatures above 100°C, preferably above 150°S, and more preferably above 200°C. Typically, the temperature of the process does not exceed 600°S, preferably 500°and more preferably 450°C. the Process can be done at atmospheric pressure; however, if desired, you can apply the raised and lowered pressure. Preferably the pressure is equal to or above 14 lbs/inch 2(97 kPa)but less than 150 lb/in2(to 1.034 kPa). Typically, General average hourly velocity (WHSV) of the feed (hydrocarbon reactant, a source of halogen, an optional source of oxygen, and optional diluent) has a value above 0.1 g of raw materials on g catalyst per hour (h-1), preferably more than 1 h-1. As a rule, General average hourly feed rate is set below 1000 h-1and preferably below 100 h-1.

During the process of oxidative halogenation and optional dehydrogenation of the above conditions are halogenated hydrocarbon product containing three or more carbon atoms and a greater number of halogen substituents than the original hydrocarbon reactant. Halogenated hydrocarbon products, successfully obtained by the method of the present invention include halogenated alkanes and halogenated alkenes, representing no particular restrictions chlorpropham, allyl chloride, dichloropropane, bromopropane, dibromopropan, allyl bromide, trichlorpropane, tribromopropane and brambleberry. Preferred halogenated C3+ hydrocarbon product contains 3-20 carbon atoms, more preferably 3-10 carbon atoms. According to another preferred embodiment of the halogenated C3+ hydrocarbon p is oduct represents a mono - and dehalogenating C3+ product. The most preferred halogenated C3+ hydrocarbon product is dichloropropan or allyl chloride. In accordance with another preferred aspect of the invention the resulting halogenated Allenby product is subjected to selective hydrogenation on the end carbon atom.

In addition to the halogenated C3+ hydrocarbon product in the method of the present invention may not necessarily be formed of one or more olefins containing three or more carbon atoms, limitiruyuschie examples of which include propene, butenes, and their higher homologues. It may cause dieny and monoolefinic. Preferred C3+ olefin product contains 3-20 carbon atoms, more preferably 3-10 carbon atoms. Preferred C3+ olefinic product is propylene.

In the method of the present invention, the number of carbon atoms in the hydrocarbon reagent is stored in a halogenated hydrocarbon product and olefinic product. However, as the length of the carbon chain of the hydrocarbon reactant increases the probability of reaction of cracking, leading to the formation of halogenated hydrocarbon products and olefins with a shorter carbon chain than in the original hydrocarbon reactant.

According to another aspect of the present invention, any olefin, contained in the stream effluent, for example, propene, can be separated from the halogenated hydrocarbon products and recycled to the oxidative halogenation for further processing with the formation of such galogenirovannyie C3+ hydrocarbons as allyl chloride. Similarly, any halogenated product, for example, allyl chloride contained in the stream effluent, can be separated from the olefin product and recycled to the oxidative halogenation for further processing with the formation of such olefinic product, as propene. Product selection subject to recycling depends on the desired final product, which must be received with maximum output.

Used in the present description, the term "conversion" refers to the molar percentage of the reagent is subjected to transformation in the process of oxidative halogenation according to the invention, in the reaction product. In this regard, you can refer to the terms "conversion of C3+ hydrocarbons"or "conversion source halogen"or "conversion of oxygen". Value conversions can vary depending on the nature of the reagent, the nature of the catalyst and process conditions. Typically, in the method of the present invention the conversion of the hydrocarbon reactant is more than 5 molar percent, suppose the equipment more than 15 molar percent, and more preferably higher than 30 molar percent. The usual method of the present invention the conversion of the source of halogen is more than 10 molar percent, preferably higher than 25 molar percent, and more preferably above 35 molar percent. The usual method of the present invention, the conversion of oxygen is more than 10 molar percent, preferably greater than 20 mole percent, and more preferably greater than 40 mole percent.

In the context of the present description, the term "selectivity" is defined as the molar percentage of hydrocarbon reactant, turned into such a specific product, such as halogenated hydrocarbon product, olefinic product or oxygenated by-product, for example, in CO or CO2. In the method of oxidative halogenation according to the present invention, the selectivity for halogenated hydrocarbon product, preferably dichloropropane or allyl chloride, typically has a value higher than 15 molar percent, preferably higher than 25 molar percent, and more preferably higher than 30 molar percent. Similarly, the selectivity to olefin is usually higher than 15 molar percent, preferably higher than 25 molar percent, and more preferably above 35 molar percent. Mostly in the way acyclical the first halogenation according to the invention are not formed perhalogenated products for example, such as hexachloropropane with low commercial value. An additional advantage of the preferred embodiment of the present invention is the fact that such oxygendemand by-products, as COx(CO and CO2), are formed in small quantities. The General reaction selectivity to carbon monoxide and carbon dioxide does not exceed 25 mole percent, preferably 20 molar percent, and more preferably 15 mole percent.

The following example is presented to illustrate the method of the present invention; it should be borne in mind that the example in no way limits the scope of the invention. Based on the above information, the person skilled in the art will be able to create alternative embodiment of the invention covered by the claims.

Example 1

Catalytic composition comprising a porous lanthanum oxychloride, was prepared as follows. Chloride lanthanum (LaCl3·7H2O, 15 g) was dissolved in deionized water (100 ml)in round bottom flask. With stirring to a solution of lanthanum chloride was added ammonium hydroxide (6 M, 20 ml). The resulting mixture was centrifuged and the excess liquid decantation with gel formation. In a separate container with deionized what ODA was dissolved calcium lactate (0,247 g, 0,0008 mol) forming a saturated solution. The solution of calcium lactate with stirring was added to the lanthanum-containing gel. The obtained gel was dried overnight at 120°C. Regenerates dry solid, which was progulivali in the air in an open vessel for 4 hours at 550°With a porous catalyst lanthanum oxychloride (6,84 g). By x-ray diffraction of the solid sample, it was determined that the quasi-crystalline form of lanthanum oxychloride. The specific area of the catalyst, measured by the method of RESPONSE was 47 m2/year

The catalyst obtained by the above method, was crushed to particle size C US mesh (0,C,43 mm) and evaluated its catalytic properties in oxidative chlorination of propane dehydrogenation in accordance with the following method. In a tubular reactor made of Nickel alloy with a ratio of length to diameter of 28.6/1 {6 inches (15.24 cm)·0,210 inches (of 0.533 cm)}, loaded catalyst (2,02 g). Into the reactor was fed a mixture of propane, hydrogen chloride and oxygen are taken in the ratios shown in the Table. The process was carried out at a temperature of 400°and atmospheric pressure. Exhaust gases were analyzed by gas chromatography. The results presented in the Table.

Table

The oxychloination propane on lanthanum catalyst with the formation of allyl chloride and propene1
Mole of soothes. Propane:HCl:About2:NoWHSV h-1CONV. Pro-panCONV. HClCONV O2Sat. Pro-foamSat.2on the allyl ClSat.2on

1-ClP
Sat. COSat on CO2
1:1:1:70,151384840351058

1. The process conditions: 400°atmospheric pressure; conversion and selectivity are given in mole percent.

2. Allyl Cl=allyl chloride; 1-ClP=1-chloropropene.

As follows from the Table, the catalyst lanthanum oxychloride able to catalyze the oxidative chlorination and dehydrogenation of propane with predominant formation of allyl chloride and propene. In the presence of such a catalyst formed reduced the number of such products of deep oxidation as carbon monoxide and carbon dioxide.

The experimental results presented in the Table illustrate the invention under the above reaction conditions and analysis. The person skilled in the art should b the th clear depending on the specific process conditions and terms of analysis can be obtained different results.

1. Method of oxidative halogenation and dehydrogenation, including interaction alkinsoderzhaschim reagent containing from 3 to 10 carbon atoms, or halogenated derivative, with a source of halogen and, optionally, a source of oxygen in the presence of a catalyst at temperatures above 100°and below 600°and at a pressure of more than 14 lb/in2(97 kPa) and less than 150 lb/in2(to 1.034 kPa), producing olefin containing three or more carbon atoms, and halogenated hydrocarbons containing three or more carbon atoms and having a greater number of halogen substituents compared to Alcantaras reagent, and used catalyst contains a halide or oxyhalide rare earth metal and essentially free of iron and copper, so that the atomic ratio between the rare earth metal and iron or copper has a value of more than 10/1, provided that in the case of the presence in the catalyst of cerium, it is also present at least one other rare earth element so that the number present cerium is less than 10 at.% from the total amount of rare earth element.

2. The method according to claim 1, in which the torus hydrocarbon reactant is a propane.

3. The method according to claim 1, wherein the source of halogen is chosen from the group consisting of Halogens, hydrogen halides and halogenated hydrocarbons having one or more labile halogen substituents.

4. The method according to claim 1, wherein the source of halogen represents chlorine, bromine and hydrogen chloride.

5. The method according to claim 1, in which the process is carried out at a molar ratio between the source of halogen and hydrocarbon reactant in the range of from more than 1/1 to less than 20/1.

6. The method according to claim 1, wherein the source of halogen is used essentially in stoichiometric amount relative to the oxygen source.

7. The method according to claim 1, wherein the source of oxygen selected from the group consisting of molecular oxygen, air or air enriched with oxygen.

8. The method according to claim 1, characterized in that the process is carried out in the range of molar ratios between the hydrocarbon reactant and oxygen source from more than 2/1 to less than 20/1.

9. The method according to claim 1, characterized in that the process includes a diluent selected from the group consisting of nitrogen, helium, argon, carbon monoxide, carbon dioxide, methane and mixtures thereof.

10. The method according to claim 9, in which the diluent is used in amounts of more than 10 mol.% and less than 90 mol.% in calculating the total number of moles of hydrocarbon reactant and diluent.

11. The method according to claim 1, in which the om halide of rare earth metal has a specific surface area according to BET more than 5 m 2/year

12. The method according to claim 1 in which the halide of rare earth metal represented by the formula MX3in which M represents at least one rare earth element selected from the group consisting of lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium, lutetium, and mixtures thereof; X represents a chloride, bromide or iodide.

13. The method according to item 12, in which X represents a chloride, and M represents a lanthanum or a mixture with other rare earth elements.

14. The method according to claim 1, in which oxychlorine rare earth metal has a specific surface area according to BET more than 12 m2/year

15. The method according to claim 1, in which oxychlorine rare earth metal corresponds to the formula MOX, where M represents at least one rare earth element selected from the group consisting of lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium, lutetium, and mixtures thereof, and in which X represents a chloride, bromide or iodide.

16. The method according to item 15, in which X represents a chloride, and M represents a lanthanum or a mixture with other rare earth elements.

17. The method according to claim 1, in which the catalyst is associated or co-extruded with the nose of the holder.

18. The method according to claim 1, characterized in that the process is carried out at temperatures above 150 and below 500°C.

19. The method according to claim 1, characterized in that the process is carried out at an average hourly space velocity of all raw materials, including hydrocarbon reactant, a source of halogen, a source of oxygen higher than 0.1 h-1but less than 1,000 h-1; or, if the diluent is present, the process is carried out at an average hourly space velocity of all raw materials, including hydrocarbon reactant, a source of halogen, a source of oxygen and a diluent, higher than 0.1 h-1but less than 1,000 h-1.

20. The method according to claim 1 in which the halogenated hydrocarbon product recycle in the process to become an olefinic product.

21. The method according to claim 1 in which the olefinic product recycle in the process, with the goal of becoming a halogenated hydrocarbon product.

22. The method of obtaining allyl chloride and propylene, including the interaction of propane with a source of chlorine and a source of oxygen in the presence of a catalyst, at temperatures above 150 and below 500°C, at a pressure of more than 14 lbs/inch2(97 kPa) and less than 150 lb/inch2(to 1.034 kPa), resulting in formation of allyl chloride and propylene as a by-product, and the catalyst contains a halide or oxyhalogenation the rare earth connection is of metal and is essentially free of iron and copper, so that the atomic ratio of rare earth metal and iron or copper has a value of more than 10/1; provided that, in case of the presence in the catalyst of cerium, it is also present at least one other rare earth element so that the amount present cerium is less than 10 at.% in the calculation of the total number of rare earth elements.

23. The method according to item 22, in which the catalyst is a chloride or oxychloride of rare earth metal.

24. The method according to item 22, in which the rare earth element represents a lanthanum.

25. The method according to item 22, which side propylene recycle to the reactor to maximize the production of allyl chloride.

26. The method according to item 22, in which allyl chloride recycle to the reactor to maximize the production of propylene.



 

Same patents:

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to perfluoroolefins production technology, notably to heaxafluorobutadiene CF2=CF-CF=CF2. Process comprises reaction of 1,2,3,4-tetrachlorohexafluorobutane with zinc in aqueous medium at 30 to 90°C. Reaction is carried out by metering 1,2,3,4-tetrachlorohexafluorobutane into reaction vessel containing zinc and water, while simultaneously desired product formed is recovered. Advantageously, process is conducted in presence of promoter selected from acids such as sulfuric acid and hydrochloric acid, soluble weak base salts such as zinc and ammonium halides, interphase transfer catalysts such as quaternary ammonium salts, quaternary phosphonium salts, tetrakis(dialkylamino)phosphonium salts, and N,N',N"-hexaalkyl-substituted guanidinium salts, or mixtures of indicated substances.

EFFECT: increased purity of heaxafluorobutadiene and simplified technology.

4 cl, 7 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing vinyl chloride monomer and to a catalyst sued in catalytic preparing vinyl chloride monomer from flows comprising ethylene. Method for preparing vinyl chloride from ethylene is carried out by the oxidehydrochlorination reaction. Method involves combining reagents including ethylene, the source of oxygen and chlorine in the catalyst-containing reactor at temperature 350-500°C and under pressure from atmosphere to 3.5 MPa, i. e. under conditions providing preparing the product flow comprising vinyl chloride and ethylene. Catalyst comprises one or some rare-earth elements under condition that the atomic ratio between rare-earth metal and oxidative-reductive metal (iron and copper) is above 10 in the catalyst and under the following condition: when cerium presents then the catalyst comprises additionally at least one rare-earth element distinctive from cerium. Ethylene is recirculated from the product flow inversely for using at stage for combining reagents. Invention proposes a variant for a method for preparing vinyl chloride. Also, invention proposes variants of a method for catalytic dehydrochlorination of raw comprising one or some components taken among ethyl chloride, 1,2-dichloroethane and 1,1,2-trichloroethane in the presence of catalyst. Catalyst represents the composition of the formula MOCl or MCl3 wherein M represents a rare-earth element or mixture of rare-earth elements taken among lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium. The catalytic composition has the surface area BET value from 12 m2/g to 200 m2/g. Invention provides simplifying technology and enhanced selectivity of the method.

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61 cl, 8 tbl, 32 ex

FIELD: chemistry of organochlorine compounds, chemical technology.

SUBSTANCE: method involves treatment of 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)-ethane with solid calcium hydroxide or a mixture of solid calcium hydroxide and solid sodium hydroxide with the content of sodium hydroxide in mixture 30%, not above, in the molar ratio 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)-ethane to alkali = 1:(1.5-1.75) at heating in the presence of catalyst. As catalysts method involves benzyltrialkyl ammonium halides, preferably, benzyltriethyl ammonium chloride or benzyltrimethyl ammonium bromide, tetraalkyl ammonium halides, preferably, tetrabutyl ammonium bromide taken in the amount 0.0005-0.005 mole. Invention provides the development of a new method for preparing 1,1-dichloro-2,2-bis-(4-chlorophenyl)-ethylene allowing to enhance ecological safety of technological process and to improve quality of the end product.

EFFECT: improved method preparing.

2 cl, 15 ex

FIELD: industrial organic synthesis.

SUBSTANCE: gas-phase thermal dehydrochlorination of 1,2-dichloroethane is conducted in presence of hydrogen chloride as promoter dissolved in feed in concentration between 50 and 10000 ppm.

EFFECT: increased conversion of raw material and reduced yield of by-products.

4 cl, 1 tbl, 8 ex

FIELD: chemical industry, in particular method for production of value monomer such as vinylchloride.

SUBSTANCE: claimed method includes passing of reaction mixture containing dichloroethane vapor trough catalytic layer providing dehydrochlorination of dichloroethane to vinylchloride. Catalyst has active centers having in IR-spectra of adsorbed ammonia absorption band with wave numbers in region of ν = 1410-1440 cm-1, and contains one platinum group metal as active component, and glass-fiber carrier. Carrier has in NMR29Si-specrum lines with chemical shifts of -100±3 ppm (Q3-line) and -110±3 ppm (Q4-line) in integral intensity ratio Q3/Q4 from 0.7 to 1.2; in IR-specrum it has absorption band of hydroxyls with wave number of ν = 3620-3650 cm-1 and half-width of 65-75 cm-1, and has density, measured by BET-method using argon thermal desorption, SAr = 0.5-30 m2/g, and specific surface, measured by alkali titration, SNa = 10-250 m2/g in ratio of SAr/SNa = 5-30.

EFFECT: method with high conversion ratio and selectivity.

3 cl, 2 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: catalyst is prepared from allyl chloride production wastes comprising 30-50% 1,3-dichloropropenes, 30-60% 1,2-dichloropropane, and 3-5% 1,2,3-trichloropropane, which are treated at 5-10°C with 30-50% dimethylamine aqueous solution in such amount as to ensure stoichiometric ratio of dimethylamine with respect to 1,3-dichloropropenes. Resulting mixture is held at 20-25°C for 0.5-1.0 h and then 40-44 sodium hydroxide solution is added in stoichiometric amount regarding dimethylamine, after which clarified waste is added to dimethylamine at 60-70°C and stirring in amount ensuring stoichiometric ratio of dimethylamine to 1,3-dichloropropenes contained in clarified waste. Mixture is aged for 2-3 h, organic phase is separated, and remaining interaction phase is supplemented by C1-C4-alcohol or benzyl alcohol at alcohol-to-dimethylamine molar ratio 1:(1-3).

EFFECT: reduced expenses on starting materials.

2 cl, 3 ex

The invention relates to cleaning and getting 1,1-dottorato, which is used for foaming plastics or as a propellant in aerosols

The invention relates to a method of processing organochlorine waste by method of hydrogenolysis
The invention relates to a method for vinylidenechloride aqueous-alkaline dehydrochlorination 1,1,2-trichloroethane in the presence of a catalyst and an alcohol additive
The invention relates to a method for vinylidenechloride aqueous-alkaline dehydrochlorination 1,1,2-trichloroethane by the action of aqueous NaOH in the presence of a catalyst

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing vinyl chloride monomer and to a catalyst sued in catalytic preparing vinyl chloride monomer from flows comprising ethylene. Method for preparing vinyl chloride from ethylene is carried out by the oxidehydrochlorination reaction. Method involves combining reagents including ethylene, the source of oxygen and chlorine in the catalyst-containing reactor at temperature 350-500°C and under pressure from atmosphere to 3.5 MPa, i. e. under conditions providing preparing the product flow comprising vinyl chloride and ethylene. Catalyst comprises one or some rare-earth elements under condition that the atomic ratio between rare-earth metal and oxidative-reductive metal (iron and copper) is above 10 in the catalyst and under the following condition: when cerium presents then the catalyst comprises additionally at least one rare-earth element distinctive from cerium. Ethylene is recirculated from the product flow inversely for using at stage for combining reagents. Invention proposes a variant for a method for preparing vinyl chloride. Also, invention proposes variants of a method for catalytic dehydrochlorination of raw comprising one or some components taken among ethyl chloride, 1,2-dichloroethane and 1,1,2-trichloroethane in the presence of catalyst. Catalyst represents the composition of the formula MOCl or MCl3 wherein M represents a rare-earth element or mixture of rare-earth elements taken among lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium. The catalytic composition has the surface area BET value from 12 m2/g to 200 m2/g. Invention provides simplifying technology and enhanced selectivity of the method.

EFFECT: improved conversion method.

61 cl, 8 tbl, 32 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing vinyl chloride monomer from ethane and ethylene. Method involves generating the outlet flow from reactor by catalytic interaction in common of ethane, ethylene, oxygen and at least one chlorine source taken among hydrogen chloride, chlorine or chlorohydrocarbon wherein the mole ratio of indicated ethane to indicated ethylene is in the range from 0.02 to 50. At the indicated stage of catalytic interaction method involves using a catalyst comprising component of rare-earth material under condition that catalyst doesn't comprise iron and copper practically and under additional condition that when component of rare-earth material represents cerium then catalyst comprises additionally at least one more rare-earth material but not cerium. Indicated outlet flow from reactor is cooled and condensed to form flow of crude product comprising the first part of hydrogen chloride and flow of crude cooled hydrogen chloride comprising the second part of indicated hydrogen chloride. Then method involves separation of indicated flow of crude product for vinyl chloride monomer as the flow product and flow of light fractions comprising the indicated first part of indicated hydrogen chloride. Then indicated flow of light fractions is recycled for catalytic interaction in common with indicated ethane, indicated ethylene, indicated oxygen and indicated chlorine source at indicated generating stage. Also, invention proposes variants of a method for producing vinyl chloride from ethane and ethylene. Invention provides preparing vinyl (chloride) from ethane and ethylene by the complete extraction of hydrogen chloride from the reactor outlet flow.

EFFECT: improved producing method.

40, 9 tbl, 3 dwg, 31 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing vinyl chloride monomer. Method involves generating outlet flow from reactor by catalytic interaction in common ethane, ethylene, oxygen and at least one source of chlorine taken among hydrogen chloride, chlorine or chlorohydrocarbon wherein the mole ratio of indicated ethane to indicated ethylene is in the range from 0.02 to 50. At this stage of catalytic interaction method involves using a catalyst comprising component of rare-earth material under condition that catalyst has no iron and copper practically and under additional condition that when component of rare-earth material represents cerium then catalyst comprises additionally at least one more component of rare-earth material being except for cerium. Indicated outlet flow from reactor is quenched to form flow of crude product that doesn't comprise hydrogen chloride practically. Flow of crude product is separated for vinyl chloride monomer flow and light fractions flow and the latter flow is recycled for catalytic interaction in common with indicated ethane, indicated ethylene, indicated oxygen and indicated chlorine source at the indicated generating stage. Also, invention proposes variants of a method in producing vinyl chloride. Invention provides the complete extraction of hydrogen chloride from the reactor outlet flow after conversion of ethane/ethylene to vinyl (chloride).

EFFECT: improved producing method.

30 cl, 5 dwg, 9 tbl, 30 ex

The invention relates to the production of the monomer is vinyl chloride from ethane

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing vinyl chloride monomer. Method involves generating outlet flow from reactor by catalytic interaction in common ethane, ethylene, oxygen and at least one source of chlorine taken among hydrogen chloride, chlorine or chlorohydrocarbon wherein the mole ratio of indicated ethane to indicated ethylene is in the range from 0.02 to 50. At this stage of catalytic interaction method involves using a catalyst comprising component of rare-earth material under condition that catalyst has no iron and copper practically and under additional condition that when component of rare-earth material represents cerium then catalyst comprises additionally at least one more component of rare-earth material being except for cerium. Indicated outlet flow from reactor is quenched to form flow of crude product that doesn't comprise hydrogen chloride practically. Flow of crude product is separated for vinyl chloride monomer flow and light fractions flow and the latter flow is recycled for catalytic interaction in common with indicated ethane, indicated ethylene, indicated oxygen and indicated chlorine source at the indicated generating stage. Also, invention proposes variants of a method in producing vinyl chloride. Invention provides the complete extraction of hydrogen chloride from the reactor outlet flow after conversion of ethane/ethylene to vinyl (chloride).

EFFECT: improved producing method.

30 cl, 5 dwg, 9 tbl, 30 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing vinyl chloride monomer from ethane and ethylene. Method involves generating the outlet flow from reactor by catalytic interaction in common of ethane, ethylene, oxygen and at least one chlorine source taken among hydrogen chloride, chlorine or chlorohydrocarbon wherein the mole ratio of indicated ethane to indicated ethylene is in the range from 0.02 to 50. At the indicated stage of catalytic interaction method involves using a catalyst comprising component of rare-earth material under condition that catalyst doesn't comprise iron and copper practically and under additional condition that when component of rare-earth material represents cerium then catalyst comprises additionally at least one more rare-earth material but not cerium. Indicated outlet flow from reactor is cooled and condensed to form flow of crude product comprising the first part of hydrogen chloride and flow of crude cooled hydrogen chloride comprising the second part of indicated hydrogen chloride. Then method involves separation of indicated flow of crude product for vinyl chloride monomer as the flow product and flow of light fractions comprising the indicated first part of indicated hydrogen chloride. Then indicated flow of light fractions is recycled for catalytic interaction in common with indicated ethane, indicated ethylene, indicated oxygen and indicated chlorine source at indicated generating stage. Also, invention proposes variants of a method for producing vinyl chloride from ethane and ethylene. Invention provides preparing vinyl (chloride) from ethane and ethylene by the complete extraction of hydrogen chloride from the reactor outlet flow.

EFFECT: improved producing method.

40, 9 tbl, 3 dwg, 31 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing vinyl chloride monomer and to a catalyst sued in catalytic preparing vinyl chloride monomer from flows comprising ethylene. Method for preparing vinyl chloride from ethylene is carried out by the oxidehydrochlorination reaction. Method involves combining reagents including ethylene, the source of oxygen and chlorine in the catalyst-containing reactor at temperature 350-500°C and under pressure from atmosphere to 3.5 MPa, i. e. under conditions providing preparing the product flow comprising vinyl chloride and ethylene. Catalyst comprises one or some rare-earth elements under condition that the atomic ratio between rare-earth metal and oxidative-reductive metal (iron and copper) is above 10 in the catalyst and under the following condition: when cerium presents then the catalyst comprises additionally at least one rare-earth element distinctive from cerium. Ethylene is recirculated from the product flow inversely for using at stage for combining reagents. Invention proposes a variant for a method for preparing vinyl chloride. Also, invention proposes variants of a method for catalytic dehydrochlorination of raw comprising one or some components taken among ethyl chloride, 1,2-dichloroethane and 1,1,2-trichloroethane in the presence of catalyst. Catalyst represents the composition of the formula MOCl or MCl3 wherein M represents a rare-earth element or mixture of rare-earth elements taken among lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium. The catalytic composition has the surface area BET value from 12 m2/g to 200 m2/g. Invention provides simplifying technology and enhanced selectivity of the method.

EFFECT: improved conversion method.

61 cl, 8 tbl, 32 ex

FIELD: petrochemical processes.

SUBSTANCE: invention relates to oxidative halogenation processes to obtain halogenated products, in particular allyl chloride and optionally propylene. Process comprises interaction of hydrocarbon having between 3 and 10 carbon atoms or halogenated derivative thereof with halogen source and optionally oxygen source in presence of catalyst at temperature above 100°C and below 600°C and pressure above 97 kPa and below 1034 kPa. Resulting olefin containing at least 3 carbon atoms and halogenated hydrocarbon containing at least 3 carbon atoms and larger number of halogen atoms than in reactant. Catalyst contains essentially iron and copper-free rare-earth metal halide or oxyhalide. Atomic ratio of rare-earth metal to iron or copper is superior to 10:1. In case of cerium-containing catalyst, catalyst has at least one more rare-earth element, amount of cerium present being less than 10 atomic % of the total amount of rare-earth elements. Advantageously, process is conducted at volumetric alkane, halogen, and oxygen supply rate above 0.1 and below 1.0 h-1, while diluent selected from group including nitrogen, helium, argon, carbon monoxide or dioxide or mixture thereof is additionally used. Halogenated product is recycled while being converted into supplementary olefin product and olefin product is recycled in order to be converted into halogenated hydrocarbon product. Optionally, allyl chloride and ethylene are obtained via interaction of propane with chlorine source in presence of catalyst.

EFFECT: increased productivity of process and improved economical characteristics.

26 cl, 1 tbl

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to processes for the oxidative halogenation reaction of hydrocarbons, in particular, for synthesis of haloidmethanes, their following processing to value chemical compounds. Method involves contacting methane, halogenated methane or their mixture with halogen source and oxygen source in the presence of catalyst to yield halogenated C1-hydrocarbon having more amount of halogen substitutes as compared with the parent hydrocarbon, Process is carried out at temperature above 200°C but less 600°C and under pressure 97 kPa or above but less 1.034 kPa and at the volume rate of raw feeding above 0.1 h-1 but less 100 h-1. Catalyst comprises rare earth metal halide or oxyhalide no containing iron and copper. The atomic ratio of rare-earth element to iron or copper exceeds 10:1 under condition that if catalyst comprises cerium in the amount less 10 atomic percent of the total amount of rare-earth components then catalyst comprises also one additional rare-earth element. Reacting hydrocarbon is chosen from the group consisting of methane, chloromethane, bromomethane, iodomethane, dichloromethane, dibromomethane, diiodomethane, chlorobromomethane and their mixtures. The molar ratio of hydrocarbon to halogen is above 1;1 but less 20:1 and that to oxygen is above 2:1 but less 20:1. The reaction mixture comprises additionally a diluting agent as nitrogen, helium, argon, carbon monoxide or dioxide or their mixtures. Formed methyl chloride or methyl bromide can be fed to the hydrolysis step to yield methyl alcohol or used in process of catalytic condensation to form light olefins and/or gasolines. It is possible contacting methyl halide with the condensation catalyst to form ethylene and the following preparing vinyl halide monomer, for example, vinyl chloride or acetic acid under carbonylation conditions. Invention provides enhancing output of the process at the expense of using the effective modified catalyst based on rare-earth elements.

EFFECT: improved halogenation method.

33 cl, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalytic methods of processing methane through direct and/or oxidative chlorination. For oxychlorination of methane, hydrogen chloride is taken in volume ratio to methane equal to 0.5-1:1, oxygen is taken in total volume ratio to hydrogen chloride in the range of 0.58-0.68:1 and at the oxidative chlorination step of the process in mass ratio of 3.5-4:1 to unreacted hydrogen chloride. Water is added, through which unreacted hydrogen chloride in the composition of the formed hydrochloric acid is returned into the process to the methane oxychlorination step. The process also includes the following steps: pyrolysis of methyl chloride obtained at the methane chlorination and/or oxychlorination step to obtain lower olefins, mainly ethylene, oxidative chlorination of the obtained ethylene to dichloroethane, thermal dehydrochlorination of the obtained dichloroethane to vinyl chloride. The catalyst for direct and/or oxidative chlorination of methane used is a mixture of copper, potassium and lanthanum chlorides in molar ratio of 1:1:0.3, deposited in amount of 3-30 wt % on a porous support with specific surface area of 1-60 m2/g. Pyrolysis of methyl chloride is carried out in a reactor with a fluidised bed of a silicoalumophosphate catalyst of the SAPO-34 type at pressure of 2-5 atm and temperature of 400-500C.

EFFECT: design of a chlorine-balanced method of processing natural gas to obtain methyl chloride, lower olefins, mainly ethylene, dichloroethane and vinyl chloride.

7 cl, 1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: method for oxidative halogenation involves bringing C1 reacting hydrocarbon selected from methane, halogenated C1 hydrocarbon or mixture thereof, into contact with a halogen source and an oxygen source in a reactor in the presence of a catalyst. Molar ratio of the C1 reacting hydrocarbon to the halogen source in the raw material for the reactor is greater than 23/1; or molar ratio of the C1 reacting hydrocarbon to the oxygen source in the raw material for the reactor is greater than 46/1; or in both raw materials for the reactor, the molar ratio of the C1 reacting hydrocarbon to the halogen source is greater than 23/1 and the molar ratio of the C1 reacting hydrocarbon to the oxygen source is greater than 46/1. Contact takes place under conditions of the method which are sufficient for obtaining a halogenated C1 product, having at least one extra halogen substitute compared to the reacting hydrocarbon. Conditions of the method include temperature higher than approximately 375C and lower than approximately 700C and pressure higher than approximately 14 psia (97 kPa) and lower than approximately 150 psia (1034 kPa); the catalyst contains a halide of a rare-earth element or an oxyhalide of a rare-earth element and the atomic ratio of the rare-earth element to iron and copper is greater than 10/1, provided that when cerium is present in the catalyst, at least one other rare-earth element is also present in the catalyst, where cerium is present in the catalyst in amount less than approximately 10 atomic % of the total amount of the rare-earth components. The invention also relates to a method of producing a halogenated C1 product, involving: (a) feeding a stream of a halogen source into a reactor containing a catalyst, where the catalyst contains a halide of a rare-earth element or an oxyhalide of a rare-earth element, and the atomic ratio of the rare-earth element to iron and copper is greater than 10/1, provided that when cerium is present in the catalyst, at least one other rare-earth element is also present in the catalyst, where cerium is present in the catalyst in amount less than approximately 10 atomic % of the total amount of the rare-earth components; (b) cutting the flow of the halogen source to the reactor; (c) adding a mixture into the reactor, where the mixture contains a C1 reacting hydrocarbon selected from a group comprising methane, a halogenated C1 hydrocarbon or mixture thereof, and an oxygen source, such that the concentration of the halogen source in the said stream is less than 0.5 vol. % and molar ratio of the C1 reacting hydrocarbon to the halogen source is greater than 23/1, under conditions of the method sufficient for obtaining a halogenated C1 product, having at least one extra halogen substitute compared to the reacting hydrocarbon, where conditions of the method include temperature higher than approximately 375C and lower than approximately 700C and pressure higher than approximately 14 psia (97 kPa) and lower than approximately 150 psia (1034 kPa); (d) cutting the flow of the mixture containing the C1 reacting hydrocarbon and the oxygen source to the reactor and (e) repeating steps (a) to (d) in a varying way.

EFFECT: high efficiency, complete conversion of a halogen source and an oxygen source, avoiding catalyst deactivation.

3 tbl, 4 ex

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