Method for producing vinyl chloride from ethane and ethylene (variants)

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 present invention is directed to a device and method for the production of vinyl chloride monomer (VSM) of ethane and ethylene. In particular, the present invention is directed to methods of production of vinyl chloride monomer, where (1) a significant number of both ethane and ethylene are present in the input streams in the associated reactor, and (2) hydrogen chloride, located in the output stream from the reactor, is almost completely removed from the output stream when the first node after the stage or stages of reaction conversion of ethane/ethylene to vinyl.

The vinyl chloride is the most important material in modern trade, and most of the methods used at the present time, a vinyl chloride from 1,2-dichloroethane (EDC), where EDC is first derived from ethylene; thus, according to known literature data system is used only at least three operations (obtaining ethylene from primary hydrocarbons, mainly by thermal cracking; the conversion of ethylene to EDC; and then the conversion of EDC to VCM). Industry inherent long-term need to move to such decisions, in which the vinyl chloride is obtained from the primary hydrocarbon in a more direct way and more economically, without the need for pre-production and purification of ethylene, and inherent in this approach is the economic benefit stimulated a significant number of developments.

As the first General areas for development the production of vinyl ethane is of interest for a number of firms involved in the production of vinyl chloride, and is currently available is a significant amount of literature on this topic. The following sections give an overview of the main works related to the embodiments presented in new developments under this description.

Patent UK 1039369, entitled "CATALYTIC CONVERSION OF ETHANE TO VINYL CHLORIDE", which issued on August 17, 1966, describes the use of catalysts containing polyvalent metals, preferably iron and cerium, in the production of vinyl chloride from ethane. This patent discloses a method of catalytic interaction of ethane, oxygen, and chlorine source and describes the use of certain catalysts, provided that "pairs available chlorine and oxygen are used in specific controlled relationship. The described system operates at temperatures in the range between 500 and 750°C. Available chlorine in the described technologies optionally includes 1,2-dichloroethane. However, this patent does not mention that together with ethane need to make ethylene. It also does not mention that in the process must be set to a specific molar ratio of ethane to ethylene, does not describe the recycling of ethylene, and instead is only indicated, Thu the ethylene reacts with the formation of polymers or ethylene dichloride or ethylchloride.

Patent UK 1492945, entitled "PROCESS FOR PRODUCING VINYL CHLORIDE", which issued on November 23, 1977 in the name of John Lynn Barclay, describes a method for the production of vinyl chloride with the use of lanthanum in the catalyst for the conversion of ethane to vinyl on the basis of copper. As the authors describe, lanthanum is present to the favorable changes in the volatility of copper at elevated temperatures, need to work. The examples demonstrate the advantages of an excess of hydrogen chloride in an appropriate reaction.

Patent UK 2095242, entitled "PREPARATION OF MONOCHLORO-OLEFINS BY OXYCHLORINATION OF ALKANES", which issued on September 29, 1982 in the name of David Roger Pyke and Robert Reid, describes "a method for obtaining monochloropropane olefins, which comprises bringing into interaction at elevated temperature gaseous mixture containing alkane, a source of chlorine and molecular oxygen, in the presence of a catalyst containing metallic silver and/or its connection, and one or more compounds of manganese, cobalt or Nickel. As the authors state, the catalyst can be fed a mixture of ethane and ethylene. No examples are not given, and the specific advantages of mixtures of ethane/ethylene are not described.

Patent UK 2101596 entitled "OXYCHLORINATION OF ALKANES TO MONOCHLORINATED OLEFINS", which issued on January 19, 1983 in the name of Robert Reid and David Pyke, describes "a method for the production of angloromani olefins, which includes bringing in the interaction at a high temperature gaseous mixture containing alkane, a source of chlorine and molecular oxygen, in the presence of a catalyst containing compounds of copper, manganese and titanium, and is suitable for use in the production of vinyl chloride from ethane". In addition, as the authors describe, "the reaction products, in one of the embodiments, the isolated and used as is, or in one of the embodiments, recyclart... reactor... to increase the output monochloropropane olefins". As the authors state, the catalyst can pogatsa mixture of ethane and ethylene. No examples are not given, and the specific advantages of mixtures of ethane/ethylene are not described.

U.S. patent 3629354 entitled "HALOGENATED HYDROCARBONS", which issued on December 21, 1971 in the name of William Q. Beard, Jr., describes a method for the production of vinyl chloride and joint production of ethylene from ethane in the presence of hydrogen chloride and oxygen. The preferred catalyst is copper or iron on the substrate. One of the examples in this patent shows an excess of hydrogen chloride (HCl) relative to ethane in the reaction mixture. The ratio of ethane to chlorine hydrogen one to four is used to obtain a stream containing 38,4 percent of ethylene (which does not require HCl to obtain) and 27.9 percent vinyl chloride (which is first required to obtain only one mole of HCl per mole of vinyl chloride).

U.S. patent 3658933, entitled "ETHYLENE FROM ETHANE, HALOGEN AND HYDROGEN HALIDE THROUGH FLUIDIZED CATALYST", which issued on April 25, 1972 in the name of William Q. Beard, Jr., describes the method of production of vinylchloride in the system of the three reactors, uniting the reactor for oxidisation, the reactor for oxyhalogenation and reactor for dehydrohalogenation. The authors show that (hydroxy)halogenation ethane in some cases enhanced by adding a halogen and hydrogen halide. As in the U.S. patent 3629354 obtained ethylene gives VCM by conventional oxyhalogenation (oxychlorination process) and cracking. HCl produced during the cracking operation, is returned to the reactor halogenation.

U.S. patent 3658934, entitled "ETHYLENE FROM ETHANE AND HALOGEN THROUGH FLUIDIZED RARE EARTH CATALYST", which issued on April 25, 1972 in the name of William Q. Beard, Jr., and U.S. patent 3702311 entitled "HALODEHYDROGENATION CATALYST", which issued November 7, 1972 in the name of William Q. Beard, Jr., describe both the method for the production of vinylchloride in the system of the three reactors, uniting the reactor halogenation, the reactor oxyhalogenation and the reactor dehydrohalogenation. The authors describe galogenangidridy ethane with obtaining ethylene for subsequent transformation into EDC by oxyhalogenation (oxychlorination process) with the subsequent receipt of VCM by conventional thermal cracking. HCl received the th during the operation of cracking, return to the reactor oxyhalogenation in '934 and the reactor halogenation in the '311. As shown in the latter patent, the advantages of excess chlorine in the form of HCl and Cl2increases the yield of desired products.

U.S. patent 3644561 entitled "OXYDEHYDROGENATION OF ETHANE", which issued on February 22, 1972 in the name of William Q. Beard, Jr., and U.S. patent 3769362 entitled "OXYDEHYDROGENATION OF ETHANE", which issued on October 30, 1973 in the name of William Q. Beard, Jr., closely connected with the above patents describe methods of oxidisation of ethane to ethylene in the presence of excess amounts of hydrogen halide. The patent describes a catalyst from a halide or copper, or iron, optionally stabilized with rare earth halide element, where the ratio of the halide of rare earth element to the halide of copper or iron is higher than 1:1. The patent describes the use of a significant excess of HCl relative to the molar amount of ethane, HCl and is not consumed in the reaction.

U.S. patent 4046823, entitled "PROCESS FOR PRODUCING 1,2-DICHLOROETHANE", issued September 6, 1977 in the name Ronnie D. Gordon and Charles M. Starks, describes a method for the production of EDC, where the ethane and chlorine react in the gas phase over a catalyst containing copper.

U.S. patent 4100211, entitled "PROCESS FOR PREPARATION OF ETHYLENE AND VINYL CHLORIDE FROM ETHANE, which you is an 11 July 1978 in the name of Angelo Joseph's magistro, describes the regeneration of a catalyst based on iron for a method where the ethane is converted as in ethylene and VCM in the mixture. This patent describes that the source of chlorine is present in an amount of from 0.1 mol to 10 mol per mole of ethane. As a rule, with increasing ratio of hydrogen chloride to ethane yield of vinyl chloride and other chlorinated products also increased, even when the reduction of yield of ethylene.

U.S. patent 4300005, entitled "PREPARATION OF VINYL CHLORIDE", issued November 10, 1981 in the name of Tao, R. Li, provides a catalyst based on copper for the production of VCM in the presence of excess HCl.

U.S. patent 5097083, entitled "PROCESS FOR THE CHLORINATION OF ETHANE", which issued on March 17, 1992 in the name of John E. Stauffer, describes chloropeta as a source of chlorine for the conversion of ethane to VCM. This patent describes the ways in which the chlorohydrocarbons can be used to capture HCl for later use in obtaining vinyl.

EVC Corporation is very active in the field of the technologies of converting ethane to vinyl, and the following four patents are a consequence of their development efforts.

European patent EP 667,845 entitled "OXYCHLORINATION CATALYST", which issued on January 14, 1998 in the name of Ray Hardman and lan Michael Clegg, describes a catalyst based on copper with a stabilizing package designed for catalysis pre the treatment of ethane to vinyl. This catalyst, obviously, applies to the subsequent technology, described in the following three U.S. patents.

U.S. patent 5663465, entitled "BY-PRODUCT RECYCLING IN OXYCHLORINATION PROCESS", issued September 2, 1997 in the name of lan Michael Clegg and Ray Hardman, describes a method of catalytic conversion of ethane to VCM, which combine the ethane and chlorine source in the reactor for the oxychlorination process with an appropriate catalyst; recyclery by-products in the reactor for the oxychlorination process; process the by-products of unsaturated chlorinated hydrocarbons, under hydrogenation to convert them to their saturated analogs and send them back to the reactor; and glorious by - product of ethylene to 1,2-dichloroethane for recycling.

U.S. patent 5728905, entitled "VINYL CHLORIDE PRODUCTION PROCESS", issued March 17, 1998 in the name of lan Michael Clegg and Ray Hardman, describes the production of vinyl from ethane in the presence of excess HCl, using a catalyst based on copper. This patent describes a method for the catalytic oxychlorination process ethane in the presence of ethane, oxygen source and a source of chlorine, in the presence of a catalyst containing copper and alkali metal. HCl fed into the reactor for the oxychlorination process in excess relative to the stoichiometric requirements based on chlorine.

U.S. patent 5763710 entitled "OXYCHLORINATION PROCESS", issued June 9, 1998, is the name of lan Michael Clegg and Ray Hardman, discusses the catalytic oxychloination ethane to VCM by combining ethane and chlorine source in the reactor for the oxychlorination process in the presence of the catalyst for oxychlorination process (reaction conditions are selected to maintain an excess of HCl); Department of VCM products; and recycling of by-products in the reactor.

Turning now to the field of production of vinyl chloride from ethylene, in most commercial methods for the production of VCM using ethylene and chlorine as a key source of nutrients. Ethylene is brought into contact with chlorine in the liquid 1,2-dichloroethane containing the catalyst in the reactor direct chlorination. 1,2-Dichloroethane are then subjected to cracking at elevated temperatures with getting VCM and hydrogen chloride (HCl). Get HCl, in turn, is introduced into the reactor for the oxychlorination process, where it interacts with ethylene and oxygen to obtain additional quantities of 1,2-dichloroethane. This 1,2-dichloroethane also served on thermal cracking with the aim of obtaining VCM. This method is described in U.S. patent 5210358, entitled "CATALYST COMPOSITION AND PROCESS FOR THE PREPARATION OF ETHYLENE FROM ETHANE, which issued may 11, 1993 in the name of Angelo J.'s magistro.

Three separate process (direct chlorination process, oxychlorination process, and thermal cracking) in most of the currently used commercial methods are often referred to in combination as "sblanc the line" for EDC, although additional sources of chlorine (HCl) in one of the embodiments also included in these advanced systems. The overall stoichiometry "balanced" setup is as follows:

4C2H4+2Cl2+O2->4C2H3Cl+2H2O

The cost of ethylene represents a significant share of the total value of production of VCM and requires significant production costs. Ethane is less expensive than ethylene and VCM production of ethane should, therefore, significantly reduce the cost of production of VCM in comparison with the cost of production of VCM, when it is produced primarily from purified and dedicated ethylene.

Commonly called the conversion of ethylene, oxygen and hydrogen chloride in 1,2-dichloroethane oxychloination. Catalysts for the production of 1,2-dichloroethane by oxychlorination process of ethylene have many common to all such catalysts characteristics. Catalysts capable of this chemical reaction are classified as modified catalysts of the deacon (Deacon) [Olah, G. A., Molnar, A., Hydrocarbon Chemistry, John Wiley & Sons (New York, 1995), pp. 226]. The chemical mechanism of the process of the deacon comes to the reaction of deacon - oxidation of HCl with obtaining elemental chlorine and water. Other authors proposed that this oxychloination was used for the purpose of using HCl on what I chlorination and HCl to oxidative turned in C12 through a process of deacon [Selective Oxychlorination hydrocarbons: A Critical Analysis, Catalytica Associates, Inc., Study 4164A, October 1982, page 1]. Thus, the catalysts for the oxychlorination process defined by their ability to produce free chlorine (Cl2). In fact, process, oxychlorination process alkanes associated with the production of free chlorine in the system [Selective Oxychlorination hydrocarbons: A Critical Analysis, Catalytical Associates, Inc., Study 4164A, October 1982, page 21, and references therein]. These catalysts are used, the metals on the carrier capable of receiving more than one stable oxidation state, such as copper and iron. In the conventional technology oxychloination is an oxidative addition of two atoms of chlorine to ethylene from HCl or other source of the recovered chlorine.

Production of vinyl ethane can be done by oxychlorination process with the proviso that there are catalysts that are capable of producing free chlorine. Such catalysts will convert ethylene into 1,2-dichloroethane at low temperatures. At higher temperatures 1,2-dichloroethane will be subjected to thermal cracking with getting hydrochloric acid and vinyl chloride. Catalysts for oxychlorination process hairout olefinic substances to chloropeta with a higher degree of chlorination. Thus, just as the ethylene is converted to 1,2-dichloroethane, vinyl chloride is converted in 1,1,2-trichloroethane. Processes using catalysts of oxychloro the Finance inherent in the formation of by-products with a higher degree of chlorination. This is explored in great detail in the patents company EVC (European patent EP 667845, U.S. patent 5663465, U.S. patent 5728905 and U.S. patent 5763710), in which it is shown, that are produced when using the catalyst for oxychlorination process high levels repeatedly chlorinated by-products. Considering the above, we can conclude that many of the concepts relating to the use of ethane for the production of VCM, were clearly described previously. Used catalysts are often modified catalysts of the deacon, operating at temperatures significantly higher (>400° (C)than those required for the implementation of the ethylene oxychlorination process (<275°). The catalysts used for the production of VCM from ethane, often stabilized against migration of transition metals of the first row, as described and reviewed in the United Kingdom patent 1492945; patent UK 2101596; U.S. patent 3644561; U.S. patent 4300005 and U.S. patent 5728905.

Using chloropeta as sources of chlorine in the way of the conversion of ethane to VCM described in the patent UK 1039369; patent UK 2101596; U.S. patent 5097083; U.S. patent 5663465 and U.S. patent 5763710. Patent UK 1039369 requires that the reactor system was introduced water. In the United Kingdom patent 2101596 use of specific catalysts on the base is ve copper. U.S. patent 5663465 describes a method that uses the phase of direct chlorination for the conversion of ethylene to EDC before its introduction into the reactor VCM.

The source of the prior art EP 0162457 describes a method of producing vinyl chloride by dehydrochlorination of ethylene dichloride (EDC→Ministry of amelioration+HCl). This source refers to a different process, different from the claimed here chemical process "oxidehydrogenation".

New approaches to methods of manufacture of vinyl chloride would consist in the development and use of catalysts suitable for the conversion of significant amounts of ethane and ethylene in the monomer vinyl chloride. However, among the reaction products formed hydrogen chloride. In this regard, the management of flows of hydrogen chloride (and related hydrochloric acid) in the process is a major task that must be solved when using the system catalysts, able to turn as ethane and ethylene in the monomer vinyl chloride. When constructing a plant for producing vinyl chloride there is also a need to give the opportunity to the maximum extent possible to use the previously used equipment, though some existing equipment may have the opportunity to work with hydrogen chloride, and another part of them is the existing equipment does not have the ability to work with hydrogen chloride. The present invention provides embodiments to meet these needs due to the fact that offers the device and how to work with hydrogen chloride produced by the reactor for the production of vinyl from the ethane/ethylene, by almost completely removed from the output stream of the reactor in the process of the first node following stage or stages of the reaction of obtaining vinyl ethane/ethylene.

The present invention provides a method for the production of vinyl chloride using stages:

generating the output stream from the reactor through catalytic interaction together ethane, ethylene, oxygen and at least one chlorine source selected from hydrogen chloride, chlorine or chloropetalum, where the molar ratio of ethane to ethylene is in the range from 0.02 to 50;

damping of the output stream from the reactor with a stream of the crude product, containing no hydrogen chloride/split stream of raw product stream, a product of vinyl chloride monomer and the flow of light fractions; and

recycling flow of light fractions to catalytic interaction together with ethane, ethylene, oxygen and a source of chlorine being generated.

The present invention also provides a method for the production of vinyl chloride, on the expectation stage:

generating the output stream from the reactor through catalytic interaction together ethane, ethylene, oxygen and at least one chlorine source selected from hydrogen chloride, chlorine or chloropetalum, where the molar ratio of the indicated ethane to the specified ethylene is in the range from 0.02 to 50;

clearing the specified output stream from the reactor with a stream of the crude product, containing no hydrogen chloride;

split the specified stream of raw product stream, a product of vinyl chloride monomer and the flow of light fractions; and

recycling the specified stream of light fractions to catalytic interaction together with the specified ethane, specified ethylene specified by the oxygen and the specified source of chlorine at this stage of generation.

The present invention further provides a method for the production of vinyl chloride, comprising the stage of:

generating the output stream from the reactor effluent from the reactor, through catalytic interaction together ethane, ethylene, oxygen and at least one chlorine source selected from hydrogen chloride, chlorine or chloropetalum, where the molar ratio of the indicated ethane to the specified ethylene is in the range from 0.02 to 50;

clearing the specified output stream from Rea the Torah education chilled raw stream of hydrogen chloride and the crude product stream, containing no hydrogen chloride;

split the specified stream of raw product stream of light fractions, the flow of the product - water flux product of vinyl chloride monomer, the flow ethylchloride, mixed flow CIS-1,2-dichloroethylene and TRANS-1,2-dichlorethylene, a stream of 1,2-dichloroethane and the flow of heavy fractions;

extraction of flow of the diluted solution of hydrogen chloride and a stream of anhydrous hydrogen chloride from the specified stream raw cooled hydrogen chloride;

recycling the specified stream dilute solution of hydrogen chloride in the specified output stream from the reactor;

recycling the specified stream of anhydrous hydrogen chloride in the specified reactor; and

absorption and recycling in the specified reactor stream S2 from the specified stream of light fractions.

The present invention further provides a method for the production of vinyl chloride, comprising the stage of:

generation in the reactor outlet stream from the reactor through catalytic interaction together ethane, ethylene, oxygen and at least one chlorine source selected from hydrogen chloride, chlorine or chloropetalum, where the molar ratio of the indicated ethane to the specified ethylene is in the range from 0.02 to 50;

clearing the specified output stream from the reactor with the formation of flux is as raw cooled hydrogen chloride and the crude product stream, containing no hydrogen chloride;

split the specified stream of raw product stream of light fractions, the flow of the product - water flux product of vinyl chloride monomer, the flow ethylchloride, mixed flow CIS-1,2-dichloroethylene and TRANS-1,2-dichlorethylene, a stream of 1,2-dichloroethane, and the flow of heavy fractions;

hydrogenation of the specified mixed flow CIS-1,2-dichloroethylene and TRANS-1,2-dichlorethylene to create recycled raw stream in the specified reactor;

extraction of flow of the diluted solution of hydrogen chloride and a stream of anhydrous hydrogen chloride from the specified stream raw cooled hydrogen chloride;

recycling the specified stream dilute solution of hydrogen chloride in the specified output stream from the reactor;

recycling the specified stream of anhydrous hydrogen chloride in the specified reactor; and

absorption and recycling in the specified reactor stream S2 from the specified stream of light fractions.

The present invention further provides a device for the production of vinyl chloride, containing:

a reactor for generating the output stream from the reactor through catalytic interaction together ethane, ethylene, oxygen and at least one chlorine source selected from hydrogen chloride, chlorine or chloropetalum, the de molar ratio of the indicated ethane to the specified ethylene is in the range from 0.02 to 50;

means for damping the specified output stream from the reactor with a stream of the crude product, containing no hydrogen chloride;

means for dividing the specified stream of raw product stream, a product of vinyl chloride monomer and the flow of light fractions; and

means for recycling the specified stream of light fractions in the specified reactor.

The present invention further provides a device for the production of vinyl chloride, containing:

a reactor for generating the output stream from the reactor through catalytic interaction together ethane, ethylene, oxygen and at least one chlorine source selected from hydrogen chloride, chlorine or chloropetalum, where the molar ratio of the indicated ethane to the specified ethylene is in the range from 0.02 to 50;

means for damping the specified output stream from the reactor with a stream of raw cooled hydrogen chloride and the crude product stream, containing no hydrogen chloride;

means for dividing the specified stream of raw product stream of light fractions, the flow of the product - water flux product of vinyl chloride monomer, the flow ethylchloride, mixed flow CIS-1,2-dichloroethylene and TRANS-1,2-dichlorethylene, a stream of 1,2-dichloroethane and the flow of heavy fractions;

means is for extracting a flow of the diluted solution of hydrogen chloride and a stream of anhydrous hydrogen chloride from the specified stream raw cooled hydrogen chloride;

means for recycling the specified stream dilute solution of hydrogen chloride in the specified output stream from the reactor;

means for recycling the specified stream of anhydrous hydrogen chloride in the specified reactor; and

means for absorption and recycling in the specified reactor stream S2 from the specified stream of light fractions.

The present invention further provides a device for the production of vinyl chloride, containing:

a reactor for generating the output stream from the reactor through catalytic interaction together ethane, ethylene, oxygen and at least one chlorine source selected from hydrogen chloride, chlorine or chloropetalum, where the molar ratio of the indicated ethane to the specified ethylene is in the range from 0.02 to 50;

means for damping the specified output stream from the reactor with a stream of raw cooled hydrogen chloride and the crude product stream, containing no hydrogen chloride;

means for dividing the specified stream of raw product stream of light fractions, the flow of the product - water flux product of vinyl chloride monomer, the flow ethylchloride, mixed flow CIS-1,2-dichloroethylene and TRANS-1,2-dichlorethylene, a stream of 1,2-dichloroethane and the flow of heavy fractions;

means for hydrogenation in azannyh mixed flows CIS-1,2-dichloroethylene and TRANS-1,2-dichlorethylene to create a recycled stream to the specified reactor;

means for extracting a flow of the diluted solution of hydrogen chloride and a stream of anhydrous hydrogen chloride from the specified stream raw cooled hydrogen chloride;

means for recycling the specified stream dilute solution of hydrogen chloride in the specified output stream from the reactor;

means for recycling the specified stream of anhydrous hydrogen chloride in the specified reactor; and

means for absorption and recycling in the specified reactor stream S2 from the specified stream of light fractions.

The present invention further provides a vinyl chloride produced using a method comprising steps:

generating the output stream from the reactor through catalytic interaction together ethane, ethylene, oxygen and at least one chlorine source selected from hydrogen chloride, chlorine or chloropetalum, where the molar ratio of the indicated ethane to the specified ethylene is in the range from 0.02 to 50;

clearing the specified output stream from the reactor with a stream of the crude product, containing no hydrogen chloride;

split the specified stream of raw product stream, a product of vinyl chloride monomer and the flow of light fractions; and

recycling the specified stream of light fractions for ka is eliticism interaction together with the specified ethane, the specified ethylene specified by the oxygen and the specified source of chlorine at this stage of generation.

The present invention further provides a vinyl chloride produced using a method comprising steps:

generating the output stream from the reactor through catalytic interaction together ethane, ethylene, oxygen and at least one chlorine source selected from hydrogen chloride, chlorine, or chloropetalum, where the molar ratio of the indicated ethane to the specified ethylene is in the range from 0.02 to 50;

clearing the specified output stream from the reactor with a stream of raw cooled hydrogen chloride and the crude product stream, containing no hydrogen chloride;

split the specified stream of raw product stream of light fractions, the flow of the product - water flux product of vinyl chloride monomer, the flow ethylchloride, mixed flow CIS-1,2-dichloroethylene and TRANS-1,2-dichlorethylene, a stream of 1,2-dichloroethane, and the flow of heavy fractions;

extraction of flow of the diluted solution of hydrogen chloride and a stream of anhydrous hydrogen chloride from the specified stream raw cooled hydrogen chloride;

recycling the specified stream dilute solution of hydrogen chloride in the specified output stream from the reactor;

re is claroline specified stream of anhydrous hydrogen chloride in the specified reactor; and

absorption and recycling in the specified reactor stream S2 from the specified stream of light fractions.

The present invention further provides a vinyl chloride produced using a method comprising steps:

generating the output stream from the reactor, through catalytic interaction together ethane, ethylene, oxygen and at least one source of chlorine from hydrogen chloride, chlorine or chloropetalum, where the molar ratio of the indicated ethane to the specified ethylene is in the range from 0.02 to 50;

clearing the specified output stream from the reactor with a stream of raw cooled hydrogen chloride and the crude product stream, containing no hydrogen chloride;

split the specified stream of raw product stream of light fractions, the flow of the product - water flux product of vinyl chloride monomer, the flow ethylchloride, mixed flow CIS-1,2-dichloroethylene and TRANS-1,2-dichlorethylene, a stream of 1,2-dichloroethane and the flow of heavy fractions;

hydrogenation of the specified mixed flow CIS-1,2-dichloroethylene and TRANS-1,2-dichlorethylene with education being recycled stream to the specified reactor;

extraction of flow of the diluted solution of hydrogen chloride and a stream of anhydrous hydrogen chloride from the specified stream crude chloride cooled water is ode;

recycling the specified stream dilute solution of hydrogen chloride in the specified output stream from the reactor;

recycling the specified stream of anhydrous hydrogen chloride in the specified reactor; and

absorption and recycling in the specified reactor stream S2 from the specified stream of light fractions.

Additional features and advantages of the present invention become more apparent when reading the detailed description of the preferred embodiments and the accompanying drawings, in which:

Figure 1 shows a schematic description, to the maximum possible extent that it can be represented on the basis of earlier publications, the proposed method of conversion of ethane to vinyl chloride using a catalyst capable of converting ethane to VCM.

Figure 2 illustrates how the conversion of ethane/ethylene to vinyl chloride using a catalyst capable of converting ethane and ethylene to VCM using oxidehydrogenation.

The figure 3 shows a modified method of oxidehydrogenation in figure 2 to demonstrate additional hydrogenation flows CIS-dichloroethylene and TRANS-dichlorethylene to 1,2-dichloroethane.

Figure 4 shows the main part of the method of conversion of ethane/ethylene vinyl on figure 2, where almost all of the HCl in the reactor by what has been transforming during the reaction.

Figure 5 shows how the conversion of ethane/ethylene vinyl on figure 4, where the EDC generated in the process, turn to vinyl chloride in a traditional oven, and HCl formed in the subprocess in the furnace, is introduced as a source of chlorine in the reactor for oxidehydrogenation.

As noted in the discussion section of the BACKGROUND of the present description process, oxychlorination process is usually considered as oxidative addition of two atoms of chlorine to ethylene from HCl or other source of the recovered chlorine. Catalysts capable of implementing this chemical process, are classified as modified catalysts of deacon [Olah, G. A., Molnar, A., Hydrocarbon Chemistry, John Wiley & Sons (New York, 1995), pp. 226]. The chemical mechanism of the process of deacon associated with the deacon reaction is the oxidation of HCl with obtaining elemental chlorine and water.

In contrast to oxychloination, in the preferred method described here, it is preferable to use oxidehydrogenation when prevrawenie acanadarhh and atlantageorgia flow in the VCM with high selectivity. Oxidehydrogenation represents the conversion of the hydrocarbon with oxygen and a source of chlorine in the chlorinated hydrocarbon, where the carbon atoms or retain their original valence or valency is reduced (i.e. sp3carbon atoms which become sp 3or converted to sp2a sp2the carbon atoms remain sp2or converted to sp). This differs from the usual definition of the oxychlorination process, where the ethylene is converted to 1,2-dichloroethane, using oxygen and a source of chlorine, with a General increase in the valency of carbon atoms (i.e. sp2the carbon atoms are converted to sp3carbon atoms). When the ability of the catalyst to prevrawenie ethylene in the vinyl chloride is advantageous to recycle the ethylene produced in the reaction of the oxide hydrochlorination, back into the reactor. By-products produced in the reactor oxide hydrochlorination include ethylchloride, 1,2-dichloroethane, CIS-1,2-dichloroethylene and TRANS-1,2-dichlorethylene. Catalyst oxidehydrogenation is also an active catalyst for the elimination of HCl from saturated chlorohydrocarbons. Recycling ethylchloride and 1,2-dichloroethane in some cases, the benefit is used in the production of vinyl chloride. Other significant chlorinated organic by-products are dichlorethylene. These substances in one of the embodiments hydronauts obtaining 1,2-dichloroethane. 1,2-Dichloroethane (EDC) is a chemical produced in large quantities, and either sold or recycled. In an alternative embodiment EDC fully hydronaut Poluchenie ethane and HCl. Hydrogenation under conditions of intermediate stringency gives a mixture of 1,2-dichloroethane, ethane, ethylchloride and HCl; such mixtures are also suitable for recycling to the reactor oxidehydrogenation.

Let us now turn to figure 1. In relation to the conversion of ethane to vinyl, to the extent that it may best be understood from the earlier publications, the method 100 of the conversion of ethane to VCM shows a scheme of the proposed method of conversion of ethane to vinyl chloride using a catalyst capable of prevrawenie ethane to VCM; in this regard, the method does not involve input of significant amounts of ethylene or of recyclorama flows either from the input streams into the reactor for the conversion of ethane to VCM (Ethane Reactor 102). It should also be noted that because the system of production of vinyl ethane in the corresponding normal scale production, to the authors ' knowledge, not yet constructed, the proposed solution for the method are the only sources for the development of incarnations that were previously formulated in the form of concepts. In this regard, the Method 100 represents a unified and simplified approach to methods, jointly reviewed in several publications related to research and development EVC Corporation: Vinyl Chloride/Ethylene Bichloride 94/95-5 (August, 1996; Chemical Systems, Inc.; Tarrytown, New York);European patent EP 667845; U.S. patent 5663465; U.S. patent 5728905; and U.S. patent 5763710.

When considering the details presented on figure 1, you can see that Ethane Reactor 102 provides an output fluid flow in the Column of Damping 106, where HCl is extinguished in the output stream from the reactor. Column Blanking 106 directs the flow of highly concentrated aqueous solution of the crude HCl in the Phase Separation Subsystem 108. The Phase Separation subsystem 108 provides an output fluid flow in the Subsystem Extract Anhydrous HCl 110, where an aqueous solution of hydrogen chloride (hydrochloric acid), anhydrous HCl and water extracted from the stream of highly concentrated aqueous solution of the crude HCl.

Subsystem Extract Anhydrous HCl 110 provides the output Stream 130 for recycling anhydrous hydrogen chloride to Ethane Reactor 102 and Subsystem Extract Anhydrous HCl 110 provides output water (for future use and for disposal as waste). Subsystem Extract Anhydrous HCl 110 returns relatively dilute stream of an aqueous solution of HCl (hydrochloric acid) using a Stream 128 in the Column of Damping 106. Column Blanking 106 also provides an output fluid flow in the Column Selection Light Fractions 114, where the flow of light fractions containing ethylene, optionally removed from the product stream leaving the reactor.

Column Selection Lung f the shares 114 produces a stream of light fractions in the Reactor Direct Chlorination 112, where chlorine (Stream 126) add to the direct chlorination of ethylene in the stream of light fractions to EDC (1,2-dichloroethane). EDC is extracted in the Column to Retrieve EDC 116 for recycling in Ethane Reactor 102, and a number of remaining gaseous light ends recyclery in Ethane Reactor 102 in the form of a Stream 134, and devices for the determination of CO (carbon monoxide) in the composition provide measurement (not shown) for use in determining a control system (not shown) corresponding portion of the remaining gaseous light ends processing using Node Oxidation Waste 118, with the generation of the waste stream to remove CO, CO2and other impurities from the system.

The output from the Column Selection Light Fractions 114, which does not enter the Reactor Direct Chlorination 112, is sent (a) a first Subsystem Drying 120 to remove water; (b) then in the Column Purification VCM 122 for selecting product - VCM (vinyl chloride monomer); and then (C) optionally, in the Column Removal of Heavy Fractions 124 for the removal of heavy fractions and generation of Stream 132. Stream 132 is a mixed fluid CIS-1,2-dichloroethylene and TRANS-1,2-dichloroethylene, 1,2-dichloroethane, ethylchloride and other chlorinated organics. In the alternative the proposed embodiment, based on the review of literature, P is Sistema Drying 120 removes the water in front of the Column Selection Light Fractions 114, while carrying VCM output from the Column Selection Light Fractions 114 is directed (a) in the Column for Purification of the VCM 122, to highlight product - VCM (vinyl chloride monomer), and then (b) in addition to the Column Removal of Heavy Fractions 124 for the removal of heavy fractions and generation of Stream 132.

Finally, the Thread 132 is sent to the Hydrogenation Reactor RCl (chlorinated organics) 104, where the addition of hydrogen produces recyclery stream to the Ethane Reactor 102.

We now turn to a consideration of figure 2 in accordance with the preferred embodiments according to the present description. The method 200 Oxidehydrogenation ethane to VCM demonstrates a method of producing vinyl chloride from ethane/ethylene using a catalyst capable of prevrawenie ethane and ethylene to VCM by oxidehydrogenation; in this regard, the method requires the input of significant quantities of ethane and ethylene, or from recyclorama flows, either from the input flow in reactor (Reactor 202 Oxidehydrogenation Ethane/Ethylene to VCM). At the reactor inlet 202 Oxidehydrogenation Ethane/Ethylene to VCM act (a) input streams: an Input Stream of Ethane 222, an Input Stream of HCl 224, an Input Stream of Oxygen 226 and the Input Stream of Chlorine 228, and (b) recyclorama flows: the Flow of Ethylchloride 230, the Flow of Hydrogen Chloride (HCl) 266 and the Thread re clearwimax Light Fractions 248, and part of the Flow EDC 262, when the EDC is advantageously used for recycling in accordance with market conditions and work conditions at a specific point in production.

As reflected in the application Dow No. 44649 from Mark E. Jones, Michael M. Olken, and Daniel A. Hickman, entitled "A PROCESS FOR CONVERSION OF ETHYLENE TO VINYL CHLORIDE, AND NOVEL CATALYST COMPOSITIONS USEFUL FOR SUCH PROCESS", filed October 3, 2000, United States Receiving Office, Express Mail Mailing Number EL636832801US, the catalyst used in the Reactor 202 to Oxidehydrogenation Ethane/Ethylene to VCM, contains at least one rare earth material. 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 C. Hedrick, U.S. Geological Survey - Minerals Information - 1997, "Rare-Earth Metals"]. The catalyst may be present either in the form of a porous, three-dimensional material, or it can be deposited on an appropriate substrate. The preferred rare earth materials are those, which are based on lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium. The most preferred rare earth materials for use in the above method of obtaining VCM are those that have as the basis of such rare earth elements, which are usually systems which are as materials with only one constant valency. Catalytic properties of materials with variable valency be less desirable than those that have a single fixed value. For example, cerium is known to be a catalyst for the oxidation-reduction, having the opportunity to be in the 3+and 4+stable oxidation States. This is one of the reasons why if rare earth material has as a basis the cerium, the catalyst additionally contains at least one rare earth element other than cerium. Preferably, if one of rare earth elements used in the catalyst is a cerium, cerium is present in a molar ratio that is less than the total number of other rare earth materials present in the catalyst. More preferably, however, to cerium in essence was not in the catalyst. The phrase "essentially no cerium" means that the cerium is in an amount less than 33 atomic percent of the rare earth components, preferably less than 20 atomic percent, and most preferably less than 10 atomic percent.

Rare earth material for the catalyst preferably has as the basis of lanthanum, neodymium, praseodymium, or a mixture thereof. Most prepost the tion, at least one of rare earth elements used in the catalyst, is a lanthanum. In addition, for atlantabased input stream in the method of obtaining a VCM according to the present invention, the catalyst essentially does not contain iron and copper. As a rule, the presence of materials which are capable of oxidation-restoration (redox)is undesirable for the catalyst. Preferred catalyst is that it essentially does not contain other transition metals that have more than one stable oxidation state. For example, manganese is a transition metal, which is preferably stripped from the catalyst. Under the expression "not substantially contain" means that the atomic ratio of rare earth element to the redox metal in the catalyst is greater than 1, preferably higher than 10, more preferably higher than 15, and most preferably higher than 50.

As indicated above, the catalyst may be deposited on an inert substrate. Preferred inert substrates include alumina, silica gel, silica - alumina, silica - magnesia, bauxite, magnesium oxide, silicon carbide, titanium oxide, zirconium oxide, zirconium silicate, and combinations thereof. Od is ako in the preferred embodiment the substrate is a zeolite. When used as an inert substrate, the rare earth component of the material of the catalyst generally ranges from 3 mass percent (mass.) up to 85 weight percent of the total mass of the catalyst and the substrate. The catalyst may be applied to the substrate using methods already known in this field.

It may also be advantageous to include other elements in the catalyst, in the form as a porous, three-dimensional material, and the material deposited on the substrate. For example, the preferred additive elements include rare earth elements, boron, phosphorus, sulfur, silicon, germanium, titanium, zirconium, hafnium, aluminum, and combinations thereof. These elements may be present to modify the catalytic characteristics of the composition or to improve the mechanical properties (e.g., resistance to friction) material.

Before combining atlantabased input stream, the source of oxygen and a source of chlorine in the reactor for a variant of the method of obtaining a VCM according to the present invention, for the composition of the catalyst is desirable that it contained salt, at least one rare earth element, provided that the catalyst essentially does not contain iron and copper, and with the additional proviso that when cerium, the catalyst further comprises at least one redcot the land element, other than cerium. Salt, at least one rare earth element is preferably selected from oxychloride rare earth elements, chlorides of rare earth elements, oxides of rare earth elements and combinations thereof, provided that the catalyst essentially does not contain iron and copper, and with the additional proviso that when cerium, the catalyst additionally contains at least one rare earth element other than cerium. More preferably, the salt comprises oxychloride rare earth element of the formula MOCl, where M represents at least one rare earth element selected from lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium, lutetium, or mixtures thereof, with the proviso that when cerium is present, then there is at least one rare earth element other than cerium. Most preferably the salt is a porous, three-dimensional material of lanthanum oxychloride (LaOCl). As already mentioned, the best material that does not undergo large changes (e.g., fractures), when chlorinated in situ in this way, and provides an additional advantageous property of water solubility in the context of this method, after a period of use (LaOCl original which is insoluble in water), so if you need to remove spent catalyst from the reactor with the liquefied layer, the fixed layer or from other equipment or containers in this way, it can be done without hydroblasting or conventional labor-intensive mechanical methods, by simply draining the used catalyst from the reactor together with water.

Typically, when salt is an oxychloride of rare earth element (MOCl), it has a surface area according to BET of at least 12 m2/g, preferably at least 15 m2/g, more preferably at least 20 m2/g, and most preferably at least 30 m2/g, As a rule, surface area by BET is less than 200 m2/year For these above measurements adsorption isotherm of nitrogen measured at 77 K, and the surface area is calculated according to the isotherms using the BET method (Brunauer, S., Emmett, P.M., and Teller, E., J. Am. Chem. Soc., 60, 309 (1938)). In addition, it is seen that the phase MOCl have a characteristic diffraction pattern by x-ray on the powders (XRD), which differ from the phases MCl3.

It is also possible, as in some cases stated previously, obtaining mixtures of rare earth elements ("M") in the composition MOCl. For example, M may be a mixture of at least two redatam the selected elements, selected from lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium. Similarly it is also possible to obtain mixtures of various compositions MOCl, where M is different for each song MOCl in the mixture.

As soon as atlantagay the input stream, the source of oxygen and a source of chlorine combined in the reactor, the catalyst is formed from a salt of at least one rare earth element in situ. In this respect it is assumed that formed in situ catalyst contains a rare earth chloride component. An example of such a chloride MCl is3where M represents a rare earth component selected from lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium, lutetium and mixtures thereof, with the proviso that when cerium is present, the catalyst additionally contains at least one rare earth element other than cerium. Typically, when salt is a chloride rare earth element (MCl3), it has a surface area according to BET of at least 5 m2/g, preferably at least 10 m2/g, more preferably at least 15 m2/g, more preferably at least 20 m2/g is most preferably at least 30 m2/year

In the light of the present description, the person skilled in the art will undoubtedly provide alternative means of obtaining usable compositions of the catalysts. The method, which, as the authors suggest, is preferred for forming a composition containing oxychloride rare earth element (MOCl), includes the following stages: (a) preparation of a solution of chloride salt of rare earth element or elements in a solvent containing either water or alcohol, or a mixture thereof; (b) adding a nitrogen-containing base for the formation of a precipitate; and (C) collecting, drying and calcination of the precipitate to form material MOCl. Typically, the nitrogen-containing base selected from ammonium hydroxide, alkylamine, arylamine, arylalkylamine, hydroxide of alkylamine, hydroxide of arylamine, hydroxide of arylalkylamine and mixtures thereof. Nitrogen-containing base may also be provided in the form of a mixture of nitrogen-containing base to other bases that do not contain nitrogen. Preferably nitrogen-containing base is a hydroxide of tetraalkylammonium. The solvent at the stage of (a) preferably represents water. Drying suitable as catalyst composition can be produced by any method, including spray drying, drying in the oven with the purge and the other known methods. For the currently favored mode in the liquefied layer is preferred catalyst is dried by atomization.

The method considered in the present preferred to form the catalyst composition containing chloride rare earth element (MCl3), includes the following stages: (a) preparation of a solution of chloride salt of rare earth element or elements in a solvent containing either water or alcohol, or a mixture thereof; (b) adding a nitrogen-containing base for the formation of a precipitate; (C) collecting, drying and calcination of the precipitate; and (d) bringing into contact the calcined precipitate with a source of chlorine. For example, one application of this method (using La for illustration) may be the deposition of LaCl3from the solution with nitrogen-containing bases, it is dried, add it to the reactor, heating it to 400°in the reactor to effect the calcination, and then bringing into contact the calcined precipitate with a source of chlorine, with the formation of the composition of the catalyst in situ in the reactor. The preferred catalysts for use will be further refined by consideration of the examples presented in the next section of the present description.

In the Reactor 202 Oxide hydrochlorination Ethane/Ethylene to VCM catalytically interact together this is n, ethylene, hydrogen chloride, oxygen and chlorine, along with at least one recycled stream, to obtain the Output 232 from the Reactor; and you must specifically be noted that the molar ratio of ethane to ethylene, calculated for all input streams of the reactor 202 oxidehydrogenation Ethane/Ethylene to VCM, is in the range from 0.02 to 50 (note that a particular working relationship at any time is determined by the requirements workflow status) without long-term degradation of functional properties of the catalyst. Depending on market conditions and working conditions at a specific point in the production of ethylene is added to the Reactor 202 in the Flow of Ethylene 289. In this regard, the preferred molar ratio of ethane to ethylene, calculated for all input streams to the Reactor 202 Oxidehydrogenation Ethane/Ethylene to VCM, is in the range from 0.5 to 4, in this variation depends on local conditions, the service life of the catalyst and the composition of the recycle stream (Stream 248). Even if the output stream from the Reactor 202 (Stream 232) is generated by the catalytic interaction of ethane, ethylene, oxygen together and at least one chlorine source selected from hydrogen chloride, chlorine or a busy chloropetalum, it should be noted that the selectivity of the catalyst in prevrawenie e is their threads in the VCM wins first of all, by pre-conditioning catalysts based on lanthanides using elemental chlorine. The selectivity of the catalyst in prevrawenie these threads in the VCM using catalysts based on lanthanides also improves when elemental chlorine (Stream 228) included as part of the composition of the source of chlorine in the Reactor 202. It should also be noted that all other systems of catalysts that demonstrate the ability to prevrawenie as ethane and ethylene to VCM, can also be profitably used in alternative embodiments described here together with a method and apparatus for producing VCM.

Sources of chlorine (selected from hydrogen chloride, chlorine and busy chloropetalum), namely the Input Stream HCl 224, an Input Stream of Chlorine 228, any part of the FLOW EDC 262 selected for recycling, and any other recycled or input streams of raw materials containing, without limitation, at least one substance selected from chlorinated methane, or the chlorinated ethane (for example, without limitation, carbon tetrachloride, 1,2-dichloroethane, ethylchloride, 1,1-dichloroethane and 1,1,2-trichloroethane) collectively put chlorine in the reaction oxidehydrogenation; these streams individually change from one moment to another when working in real time is provided for the I stoichiometric amount of chlorine, necessary for the conversion of obtaining VCM. With regard to EDC from the Stream EDC 262, market conditions affecting the possibility of direct sale, determine the appropriate number or for recycling to the Reactor 202, either directly for sale. Additional opportunity to use part of the Flow EDC 262 depending on the specific features is the introduction of the raw material into the furnace conversion in VCM. In this regard, operation of the Method 200 alternative is carried out in such a way that (a) 1,2-dichloroethane, generated in the Reactor 202, clear for sale, (b) 1,2-dichloroethane, generated in the Reactor 202, cleaned for recycling to the Reactor 202, and/or (C) 1,2-dichloroethane, generated in the Reactor 202, cleanse for cracking in the furnace to obtain the vinyl. It should also be noted that sometimes advantageous to buy EDC as a source of chlorine.

The reactor 202 Oxidehydrogenation Ethane/Ethylene to VCM generates the Output Stream 232 to supply as the supply of raw materials in the column of Damping 204. Column Blanking 204 processes the Output Stream 232, so as to almost completely remove residual HCl by blanking the output stream from the reactor to obtain a crude product stream (pair), containing no hydrogen chloride; this thread crude product (pair) is a Stream 240. The flow of the raw ohlord the frame (water) hydrogen chloride (Stream 234) also comes from the Column of Damping 204; Stream 234 is transported in a Subsystem 206 Phase Separation to remove any remaining organic compounds from raw chilled HCl. Subsystem 206 Phase Separation represents in alternative embodiments of the sump, desorber or a combination sump and desorber. From Subsystem 206 Phase Separation, deleted organic materials (mainly in the liquid phase) is transferred to the Column 210 Selection of Light Fractions using a Stream 242, and a dedicated chilled raw (mostly liquid aqueous solution) HCl is transferred in the form of a Stream 236 in the Subsystem 208 Extraction Anhydrous HCl. Subsystem 208 Extraction Anhydrous HCl also returns a stream of HCl (hydrochloric acid) through the Stream 238 in the Column of Damping 204. Eventually Subsystem 208 Extraction Anhydrous HCl provides the functions of (a) extraction (1) flow of diluted hydrogen chloride and (2) stream of anhydrous hydrogen chloride (pair) from a stream of raw cooled hydrogen chloride, and (b) recycling of flow of the diluted solution of hydrogen chloride in the exit stream from the reactor (in the column to absorb 204). Subsystem 208 Extraction Anhydrous HCl also recyclery stream of anhydrous hydrogen chloride (pair) into the reactor. As should be obvious to experts in this field, there are other methods to highlight betwo the aqueous HCl mixtures of water and HCl.

Column Blanking 204 also provides a Stream 240 (pair)coming in Column 210 Selection of Light Fractions, where the flow of light fractions (steam Flow 244)containing ethylene, optionally removed from the product stream output from the reactor. Note that in contrast to the discussed system, shown in figure 1, the ethylene from the Column 210 Selection of Light Fractions for the most part is returned as recycle to the Reactor 202 Oxidehydrogenation Ethane/Ethylene to VCM without becoming EDC:(1,2-dichloroethane).

After separation of HCl and flow of light fractions (Flow 244) from the output stream from the reactor. Column 210 Selection of Light Fractions directs the Flow 252 to separate the flow of the product - water flux product of vinyl chloride monomer (Stream 254), flow ethylchloride (Stream 230), mixed flow CIS-1,2-dichloroethylene and TRANS-1,2-dichlorethylene (Stream 260), flow 1,2-dichloroethane (Stream 262) and heavy fractions (Flow 264). The method of implementation of these end offices is obvious to the person skilled in the art, and a significant number used in the classical ways of nodes can be used in different configurations to achieve these divisions. Subsystem 216 Drying Column 218 for Cleaning VCM and the Column 220 Removal of Heavy Fractions is convenient to designate, therefore, as a General systems division (and so is new they should have the term "column", interpreted as a "virtual column"representing at least one physical column, although one of the proposed embodiments, each column may be a separate physical column) for separation of the Water Flow 256, the flow of Product VCM 254, Flow Ethylchloride 230, the Flow of CIS/TRANS-1,2-dichlorethylene 260 and Flow EDC 262, Flow Heavy Fractions 264 as organic material for destruction in the furnace for incineration of organic waste or for use in the corresponding product, where total Flow properties of Heavy Fractions 264 are acceptable. In the alternative the proposed embodiment of the Subsystem 216 Drying removes the water in front of the Column 210 Selection of Light Fractions, whereby the output stream from the Column 210 Selection of Light Fractions is sent to the Column 218 VCM Purification. Again note that in relation to EDC from the Stream EDC 262 market conditions affect the ability of its direct sales, determining the appropriate number or for recycling to the Reactor 202 or for direct sale. In this regard, the work of the Pillars 218 VCM Purification and Columns 220 Removal of Heavy Fractions produced alternately, so that (a) 1,2-dichloroethane is cleared for sale, (b) 1,2-dichloroethane cleared for recycling to the Reactor 202, and/or (C) 1,2-dichloroethane cleared for cracking in the furnace to obtain the vinyl is.

Let us turn now to Flow 244, as it emerges from the Column 210 Selection of Light Fractions. Stream 244 is divided into the first part of the stream which is sent directly in the Stream 248 in the Reactor 202 Oxidehydrogenation Ethane/Ethylene to VCM, and the second part of the flow directed into the Columns 212 Absorption and separation of C2. Column ABSORPTION AND separation of C2 212 absorb and separate the C2-materials (ethane and ethylene) directed from the second part of the flow from the Stream 244 and provide recycling C2-materials in the Reactor 202 through the Stream 246 Recycling C2, which in combination with the first part flow of the Flow 244 forms a Stream 248. Columns 212 Absorption and separation of C2 also yield a purge flow entering the Node 214 Oxidation of Waste, which provides a Waste Stream 250, and (water) Stream 274 in the Subsystem 208 Extraction Anhydrous HCl. Device for control of CO (carbon monoxide) in the composition provides a measurement (not shown) for use by the control system (not shown) in determining the appropriate part of the residual gaseous light ends processing using Columns 212 Absorption and separation of C2 and Node 214 Oxidation of Waste with the purpose of generating a Waste Stream 250 so that WITH not accumulate to levels unacceptable in the process.

Model relative velocity flows and HDMI is the flow for a method of Oxidehydrogenation ethane to VCM 200 clear from consideration of table 1. The data in table 1 (unit mass/unit time) use is made in the laboratory measurement of the operating characteristics of the catalyst for lanthanum oxychloride at 400°C and at a pressure essentially the environment; additional details of the preferred catalyst is clear from the study "A PROCESS FOR THE CONVERSION OF ETHYLENE TO VINYL CHLORIDE, AND NOVEL CATALYST COMPOSITIONS USEFUL FOR SUCH PROCESS". Table 1 shows some of the threads as zero, in the context of data generation in the simulation, but this numerical value is not intended to indicate a complete lack of flow or lack of need in the stream. Table 1 shows the input Stream of Ethylene 289; in this respect, and, repeating the previous reasoning, when the market and working conditions at a specific point of production, the most preferred mode for the flow of Ethylene 289 is zero flow. However, under certain conditions, the Flow of Ethylene 289 provides a cost-effective stream.

Table 1
The MASS BALANCE conversion of ETHANE/ETHYLENE TO vinyl CHLORIDE TO METHOD 200
streamWith2H6With2H4O2HClCl2ArCOCOsub> 2EDCEtClVCMDCEH2Oonly
222573000000000000573
22400000000000000
226005390050000000545
228000063900000000639
2300000000004500045
232895 32732042709129163451000954994798
24440120456001315731428874941709
23600045600000000494950
24085544432276042708126614572853089
24240120P0013of 1.5731,428870760
2448954563227604270912900 0002541
2461094300000000000152
2488893490241037618113000002247
2500000050183000013202
252000000001634510009501303
25400000000001000001000
25600000 000000055
2600000000000095095
262000000005340000534
26400000000000000
266000491000000000491
268000000000000494494
2780 00350000000075111
28489535103042709129371000682568
2880003000000006870
2908953510004270912937100002498
294000000003710000371

Let us now turn to figure 3. The process 300 Oxidehydrogenation Ethane to VCM with CIS/TRANS Recycling modifies the process 200 Oxidehydrogenation with the conversion of Ethane to VCM for the em Site 280 Hydrogenation DCE (dichloroethylene) for (a) hydrogenation of CIS-1,2-dichloroethylene and TRANS-1,2-dichlorethylene from the Stream 260 CIS/TRANS-1,2-dichlorethylene and (b) recycling of the output stream to the Reactor 202. In an alternative embodiment the Threads 230, 260, and 262 are separated as a single mixed stream in the column 220 Removal of Heavy Fractions, and this one mixed flow recyclery Node 280 Hydrogenation DCE.

Figure 4 shows a process 400 full conversion of Ethane/Ethylene Vinyl in the reactor, where almost all of the HCl is converted in the Reactor 202. Column Blanking 204 processes the Output 232 from the Reactor to the almost complete removal of residual HCl by blanking the output stream from the reactor, creating a stream of crude product, containing no hydrogen chloride. The flow of raw cooled hydrogen chloride Stream 234) goes from the Column Blanking 204; Stream 234 is transported in a Subsystem 206 Phase Separation to remove organic compounds from the raw chilled HCl. Deleted organic matter is transported to the Column 210 Selection of Light Fractions through the Stream 242. An aqueous solution of HCl recyclery of Subsystem 206 Phase Separation, and the Neutralizer 298 handles waste produced by using sodium hydroxide or other neutralizing compounds with the formation of the waste stream from the outlet to the waste Subsystem 206 Phase Separation.

Figure 5 demonstrates supplemented by microwave Process 500 receiving VCM conversion of the ethane/ethylene in the vinyl where the EDC generated inthe 400 in response oxidehydrogenation, turn in the vinyl chloride in a traditional oven 293 to obtain the VCM, and anhydrous HCl, extracted from the system 295 Final Processing VCM, is introduced into the Reactor 202.

Table 2 presents further details on the components indicated on the figures.

Cooling and cleanup
Table 2
Details about the components
The drawing elementNameDescription
102ReactorEthane reactor with the liquefied layer. A vertically oriented reactor with a gas inlet at the bottom and exit at the top. Vertical cooling tubes in the layer and inner cyclones (up to 3 in series), located in the upper part. Typical diameters of up to 20 feet. The height of the liquefied layer 30-50 feet, with a total height of 80 feet. The temperature of the reactor >400°requires that the alloy was used for construction with high Nickel content.
104Hydrogenation RCLThe hydrogenation reactor for the conversion of unsaturated compounds (most of them are chlorinated, e.g., CIS-1,2 dichloroethylene or TRANS-1,2 dichloroethylene) in their saturated derivatives for recycling to the reactor.
106The gaseous product from the reactor is cooled and the condensate is separated from the steam. The condensate contains both the aqueous phase with concentrated HCl, and the organic phase.

108Phase separationSeparation under the force of gravity of the aqueous and organic phases from the Refrigerator 106 preferably is achieved by means of a horizontal tank with internal baffles to give the ability to remove heavy phase (most often, the water/acid phase, but the nature of the phases depends on the composition of organic substances in phases) from one end of the vessel. The lighter phase flows over the baffle into the second half of the vessel for removal. Then, in some embodiments, the aqueous phase is clear from organic substances.
110Removing the model HC1The flow of aqueous HCl solution from the separator is recovered in the form of anhydrous HCl for recycle to the reactor using traditionally used approaches that are obvious to a person skilled in this field.
112Direct chlorinationThe reactor chlorination of ethylene. Typically, this is achieved by introducing chlorine and ethylene in the bottom is part of the capacity, containing EDC. Reagents form the EDC; the entire product is removed as a vapor above the surface of the liquid phase. Heat of reaction provides the driving force for evaporation.
114Separation of the productsThe separation column with a cooled condenser at the top, enabling the separation of light fractions for recycling chlorinated organic substances
116Removing EDCStandard distillation column for purification of EDC.
118Waste managementWaste management is achieved through a device for burning intended for oxidation of organic compounds (including chlorinated organic substances) to water vapor, carbon dioxide and hydrogen chloride. Gaseous waste is washed with water to extract HCl in the form of relatively dilute (10-20% HCl) flow for other applications. This site is typical among those used in the chemical industry, and should be obvious to specialists in this field.

120DryingBefore final separation of VCM from other products of water are removed in the drying column. Pressure and temperature regulation is : thus, that water is removed from the bottom of the column, and the dry product is removed from the top.
122Columns for purification VCMThe final product cleaning VCM is carried out, as is customary in the industry.
124Column for recycled Oia productsDistillation column to effect the separation of CIS - and TRANS-1, 2 dichloroethylene and EDC from the heavier (higher molecular weight) components. The extracted components are fed into the hydrogenation reactor before recycling it to the reactor.
202ReactorThe reactor oxidehydrogenation ethylene/ethane. Variant of the reactor with the liquefied layer (preferred) is a vertically oriented system reactor with a gas inlet at the bottom and exit at the top. Vertical cooling tubes are located in the layer and the inner cyclones (up to 3 in series) are located in the upper part. The typical diameter of the reactor is less than 20 feet. The height of the liquefied layer is in the range between 30 feet and 50 feet, with a total height of the reactor 80 feet. Variant of the reactor with the liquefied layer is a catalytic reactor with a vertical exchanger with tubes from 1 to 1.5 inches. The temperature of the reactor >400C requires that d is I design was used alloy with high Nickel content.
204DampingThe gas leaving the reactor is cooled using a heat exchanger with graphite blocks and graphite tubes, and the cooled gas is absorbed in the absorption tower. The condensate contains concentrated HCl in the aqueous phase and organic phase.

206Phase SeparationSeparation under the force of gravity of the aqueous and organic phases from the stage 204 is preferably achieved by means of a horizontal tank with internal baffles to give the ability to remove heavy phase (most often, the water/acid phase, but the nature of the phases depends on the composition of organic substances in phases) from one end of the vessel. The lighter phase flows over the baffle into the second half of the vessel for removal. Then, in some embodiments, the aqueous phase is purified from organic substances.
208Removing the model HC1The flow of aqueous HCl solution from the separator is recovered in the form of anhydrous HCl for recycle to the reactor using traditionally used approaches that are obvious to a person skilled in this field.
210Separation of the products212The absorption and separation of the C2The extraction of ethane and ethylene in the purge stream is achieved by absorption in the hydrocarbon or other absorbent liquid in the absorber, with the operation of the branch in the second column. The extracted hydrocarbons then get recycled back into the main recyclery stream and then into the reactor.
214Waste managementWaste management is achieved through a furnace for burning intended for oxidation of organic compounds (including chlorinated organic substances) to water vapor, carbon dioxide and hydrogen chloride. Gaseous waste is washed with water to extract HCl in the form of relatively dilute (10-20% HCl) flow for other applications. This site is typical among those that find application in the chemical industry, and should be obvious to specialists in this field.

216DryingBefore final separation of the VCM from the other product is in the water are removed in the drying column. The pressure and temperature regulate so that water is removed from the bottom of the column, and the dry product is removed from the top.
218Columns to obtain VCMThe final product cleaning VCM is as customary in the industry and is obvious to a person skilled in this field.
220Column to Remove TagliabracciHeavy fraction separated using distillation columns, engaged Department (a) CIS - and TRANS-1,2-dichloroethylene, and (b) the EDC from the heavier (higher molecular weight) components.
280HydrogenationThe hydrogenation is carried out in the reactor for the conversion of unsaturated compounds (most of them are chlorinated, for example CIS - and TRANS-1,2-dichlorethylene) in their saturated derivatives for recycling to the reactor.
293FurnaceThey represent a high-temperature furnace, heated by the combustion gas to the cracking of EDC to VCM. EDC evaporates and passes through the tubes inside the furnace at temperatures of approximately 600°With the transformation of a part of EDC to VCM and HCl. It is typical for furnaces currently used in industry.
295Final processing is as VCM and remove HCl Final processing of the VCM and the model HC1 removal is achieved using a column or drum quenching and separation columns, which are used in industry at the present time to retrieve unconverted EDC, recover and recycle HCl, and cleaning products VCM.
296The second stage reactorIt is an optional secondary reactor for almost complete interaction residual HCl. In the context of the contemplated alternatives, the reactor is either fixed or liquefied layer; and in some possible embodiments, it contains a standard commercially available catalyst for the oxychlorination process.

298Neutralization of residual HClWith virtually prevrawenie HCl in the reactor, removing the remainder is not provided. The aqueous solution is neutralized using any available alkaline material (caustic soda, calcium hydroxide, calcium carbonate, ammonia, and the like). The output stream is then sent to waste treatment. This process is best done in a closed vessel with stirrer. Depending on the amount of residual HCl, may need support through the chilled the I recycle stream.
299DampingComing out of the reactor, the gas is cooled using a heat exchanger with graphite blocks and graphite tubes, and the cooled gas is absorbed in the absorption tower, the condensate contains both the aqueous phase with concentrated HCl, and the organic phase.

Examples

Specific features of the catalysts additionally explained by considering the following examples, which are purely explanatory.

Example 1

To demonstrate the production of vinyl chloride from a stream containing ethylene, prepare porous, refractory composition comprising lanthanum. The solution LaCl3in water prepared by dissolving one part of commercially available hydrated lanthanum chloride (get from J.T. Baker Chemical Company) in 8 parts of deionized water. Add dropwise with stirring, ammonium hydroxide (get from Fisher Scientific, certified ACS specification) to obtain a neutral pH (universal indicator paper) causes the formation of gel. The mixture is centrifuged and the solution decanted from the solid product. Add approximately 150 ml of deionized water and gel vigorously stirred for dispersion of solid product. The resulting solution was centrifuged and the solution decanted. This stud is Yu wash is repeated two additional times. Assembled the washed gel is dried for two hours at 120°C, and then calcined at 550°C for four hours in air. The obtained solid product is ground and sieved to obtain particles suitable for further investigation. This method gives a solid product with x-ray diffraction pattern analysis of the powder corresponding to LaOCl.

Particles are placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the ethylene, ethane, HCl, O2and inert gas (a mixture of No and Ar) can be typed into the reactor. The function of argon is to serve as an internal standard for analysis of the substances in the reactor and coming out of it, using gas chromatography. Contact time (volume) is calculated as the amount of catalyst divided by the volumetric flow rate at standard conditions. Feed speed correspond to the molar relationship. In the system of the reactor is fed directly ethane-containing stream with a stoichiometry of one ethane, one of HCl and one oxygen. It provides a balanced stoichiometry for the production of VCM from ethylene.

Table 3 below presents the results of a research reactor using this composition.

Column 1 of table 3 shows a high selectivity to vinyl chloride, the catalyst for the W ethylene under oxidative conditions in the presence of HCl. The composition comprises helium to simulate reactor operating with air as the oxidizing gas.

Column 2 of table 3 shows high selectivity to vinyl chloride, the catalyst is ethylene under oxidative conditions in the presence of HCl. Now the composition of the enriched fuel to address the limitations imposed by flammable, and contains no helium.

Column 3 of table 3 shows high selectivity to vinyl chloride and ethylene, the catalyst serves ethane under oxidative conditions in the presence of HCl. Composition simulates the reactor using air as the oxidizing gas. Ethylene in the input stream is not present. The ethylene present in the reactor is the product of partial oxidation of ethane.

Column 4 of table 3 shows the result for the case when administered as ethane and ethylene. The reactor operates in such a way that the amount of ethylene introduced into the reactor and leaving the reactor are equal. When working thus ethylene acts as an inert diluent, and becomes only the ethane. The results show a high yield of vinyl chloride and 1,2-dichloroethane.

Argon is used as an internal standard to ensure that the flow of ethylene, part of the reactor, and the flow leaving reacto is, were equal. The relationship of the areas under the chromatographic peaks of ethylene and argon are identical for input and output stream from the reactor. In this way the recycling of ethylene is modeled inside the reactor device.

Table 3
Molar relationship at the input
With2H423.703
With3H60012
HCl2212.5
O21111
Inert substances6.8040
T °C401400401419
Contact time (sec)12.35.021.812.4
Conversion of O2(%)47.353.754.893.9
Selectivity (%)
With2H4-- 44.7-
With2H4Cl210.714.00.112.8
VCM76.678.134.568.5

Example 2

To further demonstrate the use of a composition of the ethylene oxidation is converted into a vinyl chloride using a variety of sources of chlorine. The solution LaCl3in water prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Avocado Research Chemicals Ltd.) 6.6 parts of deionized water. Quick add with stirring 6M ammonium hydroxide in water (diluted certified ACS reagent receive from Fisher Scientific) causes the formation of gel. The mixture is filtered to collect the solid product. The collected gel dried at 120°before calcination at 550°C for four hours in air. The obtained solid product is ground and sieved. The sieved particles are placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the reactor can enter ethylene, HCl, oxygen, 1,2-dichloroethane, carbon tetrachloride and helium. Contact time (volume) is calculated as the amount of catalyst divided by the volumetric flow rate at standard temperature and pressure. Speed of the input pot is Cove correspond to the molar relationship. The composition is heated to 400°and is treated with a mixture of 1:1:3 HCl:O2:He for 2 hours before starting work.

The obtained composition in the production of vinyl chloride by feeding ethylene, source of chlorine and oxygen at 400°C. the Following table shows the data flow received between 82 and 163 hours using different sources of chlorine. Chlorine is served in the form of HCl, carbon tetrachloride and 1,2-dichloroethane. VCM denotes the vinyl chloride. Contact time (volume) is calculated as the amount of catalyst divided by the volumetric flow rate at standard temperature and pressure. The reactors operate at atmospheric pressure at the reactor outlet. As ethylene and 1,2-dichloroethane are referred to as particles C2.

Table 4
Molar relationship at the input
With2H42,02,02,02,0
With2H60,00,00,00,0
CCl40,50,50,00,0
With2H4Cl20,00,01,80,0
HCl 0,00,00,01/9
O21,01/01,01/0
Not+Ar8,99,08,96,7
T °400399401400
Contact time (sec)8,04,08,6a 4.9
Porcelina the degree of conversion (%)
With2H440,427,018,720,1
With2H60,00,00,00,0
CCl494,878,40,00,0
With2H4Cl20,00,098,30,0
HCl0,00,00,044,7
O268,842,055,2of 37.8
Selectivity with respect to the moles converted With2
VCMto 59.6of 56.486,078,5
With2H4 Cl214,830,70,02,2
C2H5Cl0,60,40,21,6

These data show that many sources of chlorine can be used in oxidative obtaining vinyl. When using carbon tetrachloride, 1,2-dichloroethane and HCl all they give a vinyl chloride as the dominant product.

Example 3

The solution LaCl3in water prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Avocado Research Chemicals Ltd.) in 6,67 parts deionized water. Quick add with stirring 6M ammonium hydroxide in water (diluted certified ACS reagent receive from Fisher Scientific) causes the formation of gel and gives the final value of pH cent to 8.85. The mixture is filtered to collect the solid product. The collected material is calcined in air at 550°C for four hours. The obtained solid product is ground and sieved. The sieved particles are placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the reactor could be introduced ethylene, ethane, HCl, oxygen and inert (a mixture of helium and argon) gas.

Table 5 shows the data where the input streams into the reactor should be installed so that the flow of telena (mol/min), included in the reactor, and the flow of ethylene leaving the reactor are essentially the same. In the same way. Input streams into the reactor, similarly, are regulated so that the flow of HCl that is included in the reactor and leaving it, are essentially the same. The degree of conversion of oxygen is set slightly less than complete conversion to make it possible to monitor the activity of the catalyst. When working in this mode power consumption input substances are ethane, oxygen, and chlorine. As ethylene, HCl and act as substances that are not produced and not consumed. The contact time is calculated as the amount of catalyst divided by the volumetric flow rate at standard temperature and pressure. This example additionally illustrates the use of chlorine gas as a source of chlorine in the production of vinyl chloride.

Table 5
Molar relationship at the input
With2H42,1
With2H64,5
Cl20,5
HCl2,4
O21,0
Not+Ar7,4
T°C) 400
Contact time (sec)9,4
Porcelina the degree of conversion (%)
With2H41,8
With2H627,3
Cl299,8
HClof-1.4
O296,4
Selectivity (%)
VCM79,0
With2H4Cl27,2
C2H5Cl1,7
COx5,1
With2H40,5

As in all the examples, VCM here refers to the vinyl chloride. With2H4Cl2is only 1,2-dichloroethane. COxis a combination of CO and CO2.

Example 4 - example 11

Example 4 - example 11 illustrates the generation of multiple rare earth compositions, each of which contains only one rare earth material. Data illustrating the performance characteristics of these compositions are presented in table 6.

Example 4

The solution LaCl3in water prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Aldrich Chemical Company) in 6,67 h the STI deionized water. Quick add with stirring 6M ammonium hydroxide in water (diluted certified ACS reagent, Fisher Scientific) causes the formation of gel. The mixture is centrifuged to collect the solid product. The solution is decanted from the gel and drop. The gel is re-suspended in 6,66 parts deionized water. Centrifugation allows you to collect the gel. The collected gel dried at 120°before calcination at 550°C for four hours in air. The obtained solid product is ground and sieved. The sieved particles are placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the ethylene, ethane, HCl, oxygen and inert (a mixture of helium and argon gas can be introduced into the reactor. X-ray diffraction analysis of the powder shows that the material is a LaOCl. The measured surface area by BET is 42,06 m2/year Specific data on the performance specifications for this example are presented below in table 6.

Example 5

The solution NdCl3in water prepared by dissolving one part of commercially available hydrated neodymium chloride (Alfa Aesar) in 6,67 parts deionized water. Quick add with stirring 6M ammonium hydroxide in water (diluted certified ACS reagent, Fisher Scientific) causes the formation of gel. The mixture Phil is trout, to collect the solid product. The collected gel dried at 120°before calcination in air at 550°C for four hours. The obtained solid product is ground and sieved. The sieved particles are placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the reactor could be introduced ethylene, ethane, HCl, oxygen and inert (a mixture of helium and argon) gas. X-ray diffraction analysis of the powder shows that the material is a NdOCl. The measured surface area by BET is 22,71 m2/year Specific data on the performance specifications for this example are presented below in table 6.

Example 6

The solution PrCl3in water prepared by dissolving one part of commercially available hydrated praseodymium chloride (Alfa Aesar) in 6,67 parts deionized water. Repeat adding with stirring 6 M ammonium hydroxide in water (diluted certified ACS reagent, Fisher Scientific) causes the formation of gel. The mixture is filtered to collect the solid product. The collected gel dried at 120°before calcination in air at 550°C for four hours. The obtained solid product is ground and sieved. The sieved particles are placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the reactor could b the th introduced ethylene, ethane, HCl, oxygen and inert (a mixture of helium and argon) gas. X-ray diffraction analysis of the powder shows that the material is a PrOCl. The measured surface area by BET is 21,37 m2/year Specific data on the performance characteristics for this sample are presented in the table below

Example 7

The solution SmCl3in water prepared by dissolving one part of commercially available hydrated samarium chloride (Alfa Aesar) in 6,67 parts deionized water. Quick add with stirring 6M ammonium hydroxide in water (diluted certified ACS reagent, Fisher Scientific) causes the formation of gel. The mixture is filtered to collect the solid product. The collected gel dried at 120°before calcination at 500°C for four hours. The obtained solid product is ground and sieved. The sieved particles are placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the reactor could be introduced ethylene, ethane, HCl, oxygen and inert (a mixture of helium and argon) gas. X-ray diffraction analysis of the powder shows that the material is a SmOCl. The measured surface area by BET is 30,09 m2/year Specific data on the performance characteristics for this sample are presented in the table below

Example 8

A solution of HoCl3 in water prepared by dissolving one part of commercially available hydrated holmium chloride (Alfa Aesar) in 6,67 part deionizovannoy water. Quick add with stirring 6M ammonium hydroxide in water (diluted certified ACS reagent, Fisher Scientific) causes the formation of gel. The mixture is filtered to collect the solid product. The collected gel dried at 120°before calcination at 500°C for four hours. The obtained solid product is ground and sieved. The sieved particles are placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the reactor could be introduced ethylene, ethane, HCl, oxygen and inert (a mixture of helium and argon) gas. The measured surface area by BET is 20,92 m2/year Specific data on the performance specifications for this example are presented below in table 6.

Example 9

The solution ErCl3in water prepared by dissolving one part of commercially available hydrated erbium chloride (Alfa Aesar) in 6,67 parts deionized water. Quick add with stirring 6M ammonium hydroxide in water (diluted certified ACS reagent, Fisher Scientific) causes the formation of gel. The mixture is filtered to collect the solid product. The collected gel dried at 120°before calcination at 500°With those who tell four hours. The obtained solid product is ground and sieved. The sieved particles are placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the reactor could be introduced ethylene, ethane, HCl, oxygen and inert (a mixture of helium and argon) gas. The measured surface area by BET is 19,80 m2/year Specific data on the performance specifications for this example are presented below in table 6.

Example 10

The solution YbCl3in water prepared by dissolving one part of commercially available hydrated ytterbium chloride (Alfa Aesar) in 6,67 parts deionized water. Quick add with stirring 6 M ammonium hydroxide in water (diluted certified ACS reagent, Fisher Scientific) causes the formation of gel. The mixture is filtered to collect the solid product. The collected gel dried at 120°before calcination at 500°C for four hours. The obtained solid product is ground and sieved. The sieved particles are placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the reactor could be introduced ethylene, ethane, HCl, oxygen and inert (a mixture of helium and argon) gas. The measured surface area by BET is 2,23 m2/so Specific data on the performance specifications for this example are presented below in table 6.

Example 11

The solution YCl3in water prepared by dissolving one part of commercially available hydrated yttrium chloride (Alfa Aesar) in 6,67 parts deionized water. Quick add with stirring 6M ammonium hydroxide in water (diluted certified ACS reagent, Fisher Scientific) causes the formation of gel. The mixture is filtered to collect the solid product. The collected gel dried at 120°before calcination at 500°C for four hours. The obtained solid product is ground and sieved. The sieved particles are placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the reactor could be introduced ethylene, ethane, HCl, oxygen and inert (a mixture of helium and argon) gas. The measured surface area by BET is 29,72 m2/year Specific data on the performance specifications for this example are presented below in table 6.

Table 6:
Compositions based oxychloride rare earth elements, used for the production of vinyl chloride
Example56789101112
Molar relationship at the input
With2H43,64,23,73,63,63,64,23,6
HCl2,02,32,02,02,02,02,32,0
O21,01,01,01,01,01,01,01,0
Not+Ar0,20,20,20,20,20,20,20,2
T (deg. C)399403401400400400400399

Contact time (sec)8,721,311/417, 617,722,823,121,3
Porcelina the degree of conversion (%)
With2H423,713,222,814,7a 12.715,43,313,8
HCl47,624,9of 40.9 20,815,922,45,019,8
O258,8to 59.455,053,448,148,8of 21.247,8
Selectivity (%)
VCM75,374,474,261,033,344,06,135,0
C2H4Cl211,32,96,12,914,5of 17.58,818,8
C2H5Cl3,56,94,410,616,812,837,016,5
COx4,811,8the 9.722,4to 33.823,126,427,5

These data demonstrate the suitability of bulk compositions containing rare earth elements, for the conversion of atlantageorgia flows in the vinyl chloride.

Example 12 example 16

Example 12 example 16 illustrate various compositions based on rare earth elements, each of which contains a mixture of rare earth materials. Data, Illus Ryuusei performance characteristics of these samples, presented in table 7.

Example 12

The solution LaCl3and NdCl3in water prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Spectrum Quality Products) and 0.67 part of commercially available hydrated neodymium chloride (Alfa Aesar) in 13,33 parts deionized water. Quick add with stirring 6M ammonium hydroxide in water (diluted certified ACS reagent, Fisher Scientific) causes the formation of gel. The final measured pH value is 8,96. The mixture is centrifuged to collect the solid product. The solution is decanted from the gel and drop. The collected gel dried at 80°before calcination in air at 550°C for four hours. The obtained solid product is ground and sieved. The sieved particles are placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the reactor could be introduced ethylene, ethane, HCl, oxygen and inert (a mixture of helium and argon) gas. The measured surface area by BET is 21,40 m2/year Specific data on the performance specifications for this example are presented below in table 7.

Example 13

The solution LaCl3and SmCl3in water prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Spectrum Quality Products) and 0.7 part of commercially available hydrated samarium chloride (Alfa Aesar) in 13,33 parts deionized water. Quick add with stirring 6M ammonium hydroxide in water (diluted certified ACS reagent, Fisher Scientific) causes the formation of gel. The final measured pH value is 8,96. The mixture is centrifuged to collect the solid product. The solution is decanted from the gel and drop. The collected gel dried at 80°before calcination in air at 550°C for four hours. The obtained solid product is ground and sieved. The sieved particles are placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the reactor could be introduced ethylene, ethane, HCl, oxygen and inert (a mixture of helium and argon) gas. The measured surface area by BET is 21,01 m2/year Specific data on the performance specifications for this example are presented below in table 7.

Example 14

The solution LaCl3and YCl3in water prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Spectrum Quality Products) and 0.52 part of commercially available hydrated yttrium chloride (Alfa Aesar) in 13,33 parts deionized water. Quick add with stirring 6M ammonium hydroxide in water (diluted certified ACS reagent, Fisher Scientific) causes the formation of gel. The final measured pH value is 8,96 SMEs centrifuged, to collect the solid product. The solution is decanted from the gel and drop. The collected gel dried at 80°before calcination in air at 550°C for four hours. The obtained solid product is ground and sieved. The sieved particles are placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the reactor could be introduced ethylene, ethane, HCl, oxygen and inert (a mixture of helium and argon) gas. The measured surface area by BET is 20,98 m2/year Specific data on the performance specifications for this example are presented below in table 7.

Example 15

The solution LaCl3and HoCl3in water prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Spectrum Quality Products) and one part of commercially available hydrated holmium chloride (Alfa Aesar) in 13,33 parts of deionized water. Quick add with stirring 6M ammonium hydroxide in water (diluted certified ACS reagent, Fisher Scientific) causes the formation of gel. The final measured pH value is 8,64. The mixture is centrifuged to collect the solid product. The solution is decanted from the gel and drop. The collected gel dried at 80°before calcination in air at 550°C for four hours. The obtained solid product is pulverized and sieved. The sieved particles are placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the reactor could be introduced ethylene, ethane, HCl, oxygen and inert (a mixture of helium and argon) gas. The measured surface area by BET is 19,68 m2/year Specific data on the performance specifications for this example are presented below in table 7.

Example 16

The solution LaCl3and HoCl3in water prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Spectrum Quality Products) and 0.75 part of commercially available hydrated ytterbium chloride (Alfa Aesar) in 13,33 parts deionized water. Quick add with stirring 6M ammonium hydroxide in water (diluted certified ACS reagent, Fisher Scientific) causes the formation of gel. The final measured pH value is 9,10. The mixture is centrifuged to collect the solid product. The solution is decanted from the gel and drop. The collected gel dried at 80°before calcination in air at 550°C for four hours. The obtained solid product is ground and sieved. The sieved particles are placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the reactor could be introduced ethylene, ethane, HCl, oxygen and inert (a mixture of helium and argon) gas. ISM is accidental surface area by BET is 20,98 m 2/so Specific data on the performance specifications for this example are presented below in table 7.

Table 7:
Performance of compositions containing DV rare earth material
Example1314151617
Molar relationship at the input
With2H43,73,63,63,63,6
HCl2,02,02,02,02,0
O21,01/01,01,01/0
Not+Ar0,20,20,20,20,2
T°)401401400399400
Contact time (sec)3,715,713,716,920,6

Porcelina the degree of conversion (%)
With2H416,8% 12,512,49,2
HCl36,013,118,111,915,9
O245,9to 47.252,247,138,7
Selectivity (%)
VCM75,851,051,428,911,1
C2H4Cl2the 9.77,512,414,520,6
With2H5Cl4,111,88,9of 17.023,8
COx6,927,525,838,943,8

These data demonstrate the suitability of the volume containing rare earth elements compositions, which contain a mixture of rare earth materials, for turning atlantageorgia flows in the vinyl chloride.

Example 17 example 24

Example 17 example 24 is a composition containing rare earth materials in the presence of other additives.

Example 17

The solution LaCl3in water prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Aldrich Chemical Company) in order to 6.67 parts of deionized water. 0,48 parts ammonium hydroxide (Fisher Scientific) is added to 0.35 part powder CeO2received already prepared from commercial sources (Rhone-Poulenc). Containing lanthanum and cerium mixture is added together with stirring to form a gel. The resulting containing gel mixture is filtered, and the collected solid product calcined in air at 550°C for 4 hours. The obtained solid product is ground and sieved. The sieved particles are placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the reactor could be introduced ethylene, ethane, HCl, oxygen and inert (a mixture of helium and argon) gas. Specific data on the performance specifications for this example are presented below in table 8.

Example 18

Composition comprising lanthanum, prepared using the method of example 5, ground using a mortar and pestle with the formation of fine powder. One part of the crushed powder combine from 0.43 parts of powder BaCl2and additionally crushed using a mortar and pestle to form a homogeneous mixture. Containing lanthanum and barium mixture is pressed for the formation of lumps. Pieces calcined at 800°C in air for 4 hours. The resulting material is placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the button in the reactor could be introduced ethylene, ethane, HCl, oxygen and inert (a mixture of helium and argon) gas. Specific data on the performance specifications for this example are presented below in table 8.

Example 19

The dried silica Grace Davison Grade 57 dried at 120°C for 2 hours. A saturated solution of LaCl3formed in the water using commercially available hydrated lanthanum chloride. The dried silica impregnated to the point of emergence of moisture by using a solution LaCl3. The impregnated silica leave to air dry for 2 days at ambient temperature. It further dried at 120°C for 1 hour. The resulting material is placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the reactor could be introduced ethylene, ethane, HCl, oxygen and inert (a mixture of helium and argon) gas. Specific data on the performance specifications for this example are presented below in table 8.

Example 20

The solution LaCl3in water prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Spectrum Quality Products) to 6.67 parts of deionized water. Quick add with stirring 6M ammonium hydroxide in water (diluted certified ACS reagent, Fisher Scientific) causes the formation of gel. The mixture is centrifuged to SOBR is to be a solid product. The solution is decanted from the gel and drop. The gel is re-suspended 12.5 parts of acetone (Fisher Scientific), centrifuged, and the liquid is again decanted and discarded. Stage washing with acetone addition is repeated 4 times, with the use of 8.3 parts of acetone. The gel is re-suspended 12.5 parts of acetone and add to 1.15 parts of hexamethyldisilazane (purchased from Aldrich Chemical Company), and the solution is stirred for one hour. The mixture is centrifuged to collect the gel. Collect the gel allow to dry in air at ambient temperature before calcination in air at 550°C for four hours. The obtained solid product is ground and sieved. The sieved particles are placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the reactor could be introduced ethylene, ethane, HCl, oxygen and inert (a mixture of helium and argon) gas. The measured surface area by BET is 58,82 m2/year Specific data on the performance specifications for this example are presented below in table 8.

Example 21

The solution LaCl3in water prepared by dissolving one part of commercially available hydrated lanthanum chloride (Alfa Aesar) and 0,043 part of commercially available HfCl4(bought from Acros Organics) in 10 parts of deionized water. Quick add with stirring M ammonium hydroxide in water (diluted certified ACS reagent, receive from Fisher Scientific) causes the formation of gel. The mixture is centrifuged to collect the solid product. The solution is decanted from the gel and drop. The collected gel dried at 80°during the night before calcination at 550°C for 4 hours. Specific data on the performance specifications for this example are presented below in table 8.

Example 22

The solution LaCl3in water prepared by dissolving one part of commercially available hydrated lanthanum chloride (Alfa Aesar) and 0,086 part of commercially available HfCl4(bought from Acros Organics) in 10 parts of deionized water. Quick add with stirring 6M ammonium hydroxide in water (diluted certified ACS reagent, Fisher Scientific) causes the formation of gel. The mixture is centrifuged to collect the solid product. The solution is decanted from the gel and drop. The collected gel dried at 80°during the night before calcination at 550°C for 4 hours. Specific data on the performance specifications for this example are presented below in table 8.

Example 23

The solution LaCl3in water prepared by dissolving one part of commercially available hydrated lanthanum chloride (Alfa Aesar) and 0,043 part of commercially available ZrOCl2(buy from Acres Organics) in 10 parts of deionized water. Quick adding of paramasivan and 6M ammonium hydroxide in water (diluted certified ACS reagent, receive from Fisher Scientific) causes the formation of gel. The mixture is centrifuged to collect the solid product. The solution is decanted from the gel and drop. The gel is re-suspended in 6,67 parts of deionized water and subsequently centrifuged. The solution is decanted and discarded. The collected gel calcined at 550°C for 4 hours. Specific data on the performance specifications for this example are presented below in table 8.

Example 24

The solution LaCl3in water prepared by dissolving commercially available hydrated lanthanum chloride in deionized water to obtain M solution. Commercially produced zirconium oxide (get from Engelhard) dried at 350°With during the night. One part of zirconium oxide impregnated with 0.4 parts of a solution LaCl3. The sample is dried in air at room temperature, and then calcined in air at 550°C for 4 hours. The obtained solid product is ground and sieved. The sieved particles are placed in a reactor made of pure Nickel (alloy 200). The reactor is configured so that the reactor could be introduced ethylene, ethane, HCl, oxygen and inert (a mixture of helium and argon) gas. Specific data on the performance specifications for this example are presented below in table 8.

/tr>
Table 8:
Composition of rare earth elements with additional components
Example1819202122232425
Molar relationship at the input
With2H43,73,63,73,73,73,73,63,7
HCl2,02,02,02,02,02,02,02,0
O21,01,01,01,01,01,01,01,0
Not+Ar0,20,20,20,20,20,20,20,2
T°)400401400399401400400401
The contact time4,820,36,73,67,97,812,816,7

(s)
Porcelina the degree of conversion (%)
With2H418,211/714,124,618,516,518,715,2
HCl34,622,124,457,1of 40.938,235,221,1
O255,633,248,052,050,347,450,9of 56.4
Selectivity (%)
VCM64,554,653,656,076,471,873,255,1
C2H4Cl211,515,210,0of 31.49,6a 12.75,27,3
With2H5Cl5,010,07,42,94,0a 4.9a 4.912,4
COx10,818,6 26,66,07,68,813,624,1

These data demonstrate vinyl chloride from Atlanterra flows using catalysts based on lanthanum, which contain other elements or deposited on a substrate.

Example 25 - 30

Example 25 example 30 to show some of the modifications that are possible to change the preparation of compositions of rare earth elements suitable for use.

Example 25

The solution LaCl3in water prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Spectrum Quality Products) in 10 parts of deionized water. Quick add with stirring 6M ammonium hydroxide in water (diluted certified ACS reagent, Fisher Scientific) causes the formation of gel. The mixture is centrifuged to collect the solid product. The solution is decanted from the gel and drop. Prepare a saturated solution of 0.61 part of benzyltriethylammonium chloride (purchased from Aldrich Chemical Company) in deionized water. The solution is added to the gel and mix. The collected gel calcined at 550°C for 4 hours. Specific data on the performance specifications for this example are presented below in table 9. This example illustrates the use of added alyamani to change the preparation of compositions with rare earth elements.

Example 26

The solution LaCl3in water prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Spectrum Quality Products) in 10 parts of deionized water. Quick add with stirring 6M ammonium hydroxide in water (diluted certified ACS reagent, Fisher Scientific) causes the formation of gel. The mixture is centrifuged to collect the solid product. Add one part glacial acetic acid to the gel, and the gel is re-dissolved. Adding a solution of 26 parts of acetone causes the formation of sludge. The solution is decanted, and the solid product calcined at 550°C for 4 hours. Specific data on the performance specifications for this example are presented below in table 9. This example demonstrates the preparation of compositions with lanthanum, suitable for use by decomposition products of the addition of chlorine to carboxylic acids containing compounds of rare earth elements.

Example 27

The solution LaCl3in water prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Spectrum Quality Products) in 10 parts of deionized water. Quick add with stirring 6M ammonium hydroxide in water (diluted certified ACS reagent, Fisher Scientific) causes the formation of gel. See the camping centrifuged, to collect the solid product. The collected gel re-suspended at 3.33 parts of deionized water. Then add 0,0311 part of the reagent phosphoric acid (purchased from Fisher Scientific) does not produce visible changes in suspended gel. The mixture is again centrifuged, and the solution decanted from the containing phosphorus gel. The collected gel calcined at 550°C for 4 hours. The calcined solid product has a surface area according to BET 33,05 m2/year Specific data on the performance specifications for this example are presented below in table 9. This example demonstrates the preparation of compositions of rare earth elements, also containing phosphorus as phosphate.

Example 28

The solution LaCl3in water prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Acros Organics) in 6,66 parts deionized water. The solution is formed by mixing of 0.95 parts of a commercially available DABCO, or 1,4-diazabicyclo[2,2,2]octane (purchased from ICN Pharmaceuticals), dissolved in 2.6 parts of deionized water. Rapid mixing of two solutions with stirring causes the formation of gel. The mixture is centrifuged to collect the solid product. The collected gel re-suspended in 6,67 parts deionized water. The mixture is again centrifuged, and the solution decanted from the gel. Assembled the gel calcined for 4 hours at 550° C. the Calcined solid product has a surface area according to BET 38,77 m2/year Specific data on the performance specifications for this example are presented below in table 9. This example demonstrates the suitability of the alkylamine in the preparation of the composition of rare earth elements suitable for use.

Example 29

The solution Lads in water is prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Acros Organics) in 10 parts of deionized water. To this solution is quickly added to 2.9 parts of a commercially available tetramethyl ammonium hydroxide (purchased from Aldrich Chemical Company) with stirring, causing the formation of a gel. The mixture is centrifuged, and the solution decanted from the gel. The collected gel re-suspended in 6,67 parts deionized water. The mixture is again centrifuged, and the solution decanted from the gel. The collected gel calcined for 4 hours at 550°C. the Calcined solid product has a surface area according to BET 80,35 m2/year Specific data on the performance specifications for this example are presented below in table 9. This example demonstrates the suitability of the alkyl ammonium hydroxide in the preparation of the composition of rare earth elements suitable for use.

Example 30

The solution LaCl3in water prepared by dissolving one frequent is commercially available hydrated lanthanum chloride (purchased from Avocado Research Chemicals Ltd.) in 6,67 parts deionized water. To this solution quickly and with stirring, add 1,63 part of commercially available 5 n NaOH solution (Fisher Scientific), causing the formation of a gel. The mixture is centrifuged, and the solution decanted from the gel. The collected gel calcined for 4 hours at 550°C. the Calcined solid product has a surface area according to BET 16,23 m2/year Specific data on the performance specifications for this example are presented below in table 9. This example demonstrates the suitability does not contain nitrogen bases for the formation of catalytically interesting materials. Although they are potentially functional, study materials, apparently, are inferior to those that are produced with the use of nitrogen-containing bases.

Table 9:
Additional methods of preparation for the lanthanum-containing compositions
Example262728293031
Molar relationship at the input
With2H43,63,73,63,73,73,7
HCl2,02,02,0 2,02,02,0
About21,01,01,01,01,01,0
Not+Ar0,20,20,20,20,20,2

T°)401400400399400401
Contact time (sec)8,620,8the 4.78,76,220,0
Porcelina the degree of conversion (%)
C2H418,88,7the 15.617,421,09,3
HCl35,87,720,041,548,422,3
O253,032,648,850,656,817,9
Selectivity (%)
VCM73,426,072,1of 76.877,6of 17.5
With2H4Cl28,711,9/td> 7,17,37,846,2
With2H5Cl3,522,75,64,22,925,6
COx9,838,6a 12.77,66,39,1

The present invention is described in an illustrative manner. In this regard, it is evident that the person skilled in the art, as only he will understand the advantages according to the preceding description, will be able to make modifications described herein specific embodiments, without deviating from the essence of the present invention. Such modifications should be considered within the framework of the present invention, which is limited only by the scope and essence of the attached claims.

1. Method for the production of vinyl chloride, including stage

generating the output stream from the reactor through catalytic interaction together ethane, ethylene, oxygen and at least one chlorine source selected from hydrogen chloride, chlorine or chloropetalum, where the molar ratio of the indicated ethane to the specified ethylene is in the range from 0.02 to 50, and where at this stage catalytic interaction using the catalyst containing the component redkozemel the first material, provided that the catalyst contains almost no iron and copper, and with the additional proviso that when component rare earth material is cerium, the catalyst additionally contains at least one component of rare earth material other than cerium;

clearing the specified output stream from the reactor with a stream of the crude product, containing no hydrogen chloride;

split the specified stream of raw product stream, a product of vinyl chloride monomer and the flow of light fractions and

recycling the specified stream of light fractions to catalytic interaction together with the specified ethane, specified ethylene specified by the oxygen and the specified source of chlorine at this stage of generation.

2. The method according to claim 1, characterized in that the rare earth material selected from lanthanum, neodymium, praseodymium and mixtures thereof.

3. The method according to claim 2, characterized in that the rare earth material is a lanthanum.

4. The method according to claim 1, characterized in that the molar ratio is in the range from 0.1 to 10.

5. The method according to claim 1, characterized in that the molar ratio is in the range from 0.5 to 4.

6. The method according to claim 1, characterized in that one of these sources of chlorine in baraut, at least one substance from the group comprising chlorinated methane and chlorinated ethane.

7. The method according to claim 1, characterized in that one of these sources of chlorine select at least one of chlorinated organic compounds, including carbon tetrachloride, 1,2-dichloroethane, ethylchloride, 1,1-dichloroethane and 1,1,2-trichloroethane.

8. The method according to claim 1, characterized in that the 1,2-dichloroethane generated in this stage of the reaction, purified for sale.

9. The method according to claim 1, characterized in that the 1,2-dichloroethane generated in this stage of the reaction, purified for recycling in the specified reactor.

10. The method according to claim 1, characterized in that the 1,2-dichloroethane generated in this stage of the reaction, purified to cracking in the furnace to obtain the vinyl.

11. Method for the production of vinyl chloride, including stage

generating the output stream from the reactor through catalytic interaction together ethane, ethylene, oxygen and at least one chlorine source selected from hydrogen chloride, chlorine or chloropetalum, where the molar ratio of the indicated ethane to the specified ethylene is in the range from 0.02 to 50, and where at this stage catalytic interaction using a catalyst containing a rare earth component of the material, provided that the catalyst is practically not contain iron and copper, and with the additional proviso that when component rare earth material is cerium, the catalyst additionally contains at least one component of rare earth material other than cerium;

clearing the specified output stream from the reactor with a stream of raw cooled hydrogen chloride and the crude product stream, containing no hydrogen chloride;

split the specified stream of raw product stream of light fractions, the flow of the product - water flux product of vinyl chloride monomer, the flow ethylchloride, mixed flow CIS-1,2-dichloroethylene and TRANS-1,2-dichlorethylene, a stream of 1,2-dichloroethane and the flow of heavy fractions; extraction of flow of the diluted solution of hydrogen chloride and a stream of anhydrous hydrogen chloride from the specified stream raw cooled hydrogen chloride;

recycling the specified stream dilute solution of hydrogen chloride in the specified output stream from the reactor;

recycling the specified stream of anhydrous hydrogen chloride in the specified reactor and

absorption and recycling in the specified reactor flow C2 containing ethane and ethylene from the specified stream of light fractions.

12. The method according to claim 11, characterized in that the rare earth material selected from lanthanum is, neodymium, praseodymium and mixtures thereof.

13. The method according to item 12, characterized in that the rare earth material is a lanthanum.

14. The method according to claim 11, characterized in that the molar ratio is in the range from 0.1 to 10.

15. The method according to claim 11, characterized in that the molar ratio is in the range from 0.5 to 4.

16. The method according to claim 11, characterized in that one of these sources of chlorine choose at least one substance from the group comprising chlorinated methane and chlorinated ethane.

17. The method according to claim 11, characterized in that one of these sources of chlorine select at least one of chlorinated organic compounds, including carbon tetrachloride, 1,2-dichloroethane, ethylchloride, 1,1-dichloroethane and 1,1,2-trichloroethane.

18. The method according to claim 11, characterized in that the 1,2-dichloroethane generated in this stage of the reaction, purified for sale.

19. The method according to claim 11, characterized in that the 1,2-dichloroethane generated in this stage of the reaction, purified for recycling in the specified reactor.

20. The method according to claim 11, characterized in that the 1,2-dichloroethane generated in this stage of the reaction, purified to cracking in the furnace to obtain the vinyl.

21. Method for the production of vinyl chloride, including stage

generation in the reactor output stream treactor through catalytic interaction together ethane, ethylene, oxygen and at least one chlorine source selected from hydrogen chloride, chlorine or chloropetalum, where the molar ratio of the indicated ethane to the specified ethylene is in the range from 0.02 to 50, and where at this stage catalytic interaction using a catalyst containing a rare earth component of the material, provided that the catalyst contains almost no iron and copper, and with the additional proviso that when component rare earth material is cerium, the catalyst additionally contains at least one component of rare earth material other than cerium;

clearing the specified output stream from the reactor with a stream of raw cooled hydrogen chloride and the crude product stream, containing no hydrogen chloride;

split the specified stream of raw product stream of light fractions, the flow of the product - water flux product of vinyl chloride monomer, the flow ethylchloride, mixed flow CIS-1,2-dichloroethylene and TRANS-1,2-dichlorethylene, a stream of 1,2-dichloroethane and the flow of heavy fractions;

hydrogenation of the specified mixed flow CIS-1,2-dichloroethylene and TRANS-1,2-dichlorethylene with education being recycled stream to the specified reactor;

the extract stream is diluted rest the RA hydrogen chloride and a stream of anhydrous hydrogen chloride from the specified stream raw cooled hydrogen chloride;

recycling the specified stream dilute solution of hydrogen chloride in the specified output stream from the reactor;

recycling the specified stream of anhydrous hydrogen chloride in the specified reactor and

absorption and recycling in the specified reactor flow C2 containing ethane and ethylene from the specified stream of light fractions.

22. The method according to item 21, characterized in that the rare earth material selected from lanthanum, neodymium, praseodymium and mixtures thereof.

23. The method according to item 22, characterized in that the rare earth material is a lanthanum.

24. The method according to item 21, characterized in that the molar ratio is in the range from 0.1 to 10.

25. The method according to item 21, characterized in that the molar ratio is in the range from 0.5 to 4.

26. The method according to item 21, wherein one of the specified sources of chlorine choose at least one substance from the group comprising chlorinated methane and chlorinated ethane.

27. The method according to item 21, wherein one of the specified sources of chlorine select at least one of chlorinated organic compounds, including carbon tetrachloride, 1,2-dichloroethane, ethylchloride, 1,1-dichloroethane and 1,1,2-trichloroethane.

28. The method according to item 21, wherein the 1,2-dichloroethane generated by the th at the specified stages of the reaction, cleanse for sale.

29. The method according to item 21, wherein the 1,2-dichloroethane generated in this stage of the reaction, purified for recycling in the specified reactor.

30. The method according to item 21, wherein the 1,2-dichloroethane generated in this stage of the reaction, purified to cracking in the furnace to obtain the vinyl.

Signs of paragraphs 1, 11 and 21, with the exception of signs, separately listed below, and all signs points 2, 3, 6, 7, 9, 12, 13, 16, 17, 19, 22, 23, 26, 27 and 29 have priority from 22.11.1999 according to claim US 60/166, 897.

The following characteristics:

the ratio of ethane and ethylene is involved in the catalytic interaction (applies to claims 1 to, 4, 5, 11, 14, 15, 21, 24, 25);

the damping of the output stream from the reactor (11, 21);

recover and recycle flow of the diluted solution of hydrogen chloride (11, 21);

an additional indication of the destination options (future use) obtained in inventive ways 1,2-dichloroethane, namely the "for sale" and "for cracking in the furnace to obtain a vinyl (p, 10, 18, 20, 28, 30), have priority 06.10.2000 according to the application PCT/US 00/27700.



 

Same patents:

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 technology, in particular method for vinylchloride production.

SUBSTANCE: claimed method includes fast gas cooling in quenching column followed by separation of pyrolysis products. Quenching and separation are carried out by barbotage through the layer of liquid concentrated by-products of these gases in quenching column cube. Then steam/gas mixture is brought into contact with returning condensate in regular filling layer of rectification tower with simultaneous purification of steam/gas mixture in rectification zone upstream. Liquid concentrated by-products are additionally rectified in vacuum with isolating and recovery of products having boiling point higher than the same for dichloroethane and distillate recycling. Method of present invention also makes it possible to produce perchloroethylene and tricloroethylene.

EFFECT: vinylchloride of high quality; reduced effort and energy consumption.

2 tbl, 4 dwg, 2 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: chemical industry, in particular method for production of value products from lower alkanes.

SUBSTANCE: claimed method includes passing of gaseous reaction mixture containing at least one lower alkane and elementary chlorine through catalytic layer. Used catalyst represents geometrically structured system comprising microfiber with diameter of 5-20 mum. 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 of increased yield.

3 cl, 4 ex

The invention relates to the production of parameningeal by alkylation of phenol, alpha-methylstyrene and the catalyst for this process
The invention relates to a technology for chlorohydrocarbons by the chlorination of olefins and subsequent separation of the products of chlorination on target and by-products, in particular to a method of rectification of a mixture of chlorinated propylene with obtaining allyl chloride of high purity
The invention relates to a technology for chlorohydrocarbons by the chlorination of olefins and subsequent separation of the products of chlorination on target and by-products, in particular to a method of rectification of a mixture of chlorinated propylene with obtaining allyl chloride of high purity

The invention relates to the processing of the products of oxidative pyrolysis gas metadatareader
The invention relates to the chemical industry and plastics

The invention relates to the production of vinyl chloride

The invention relates to the industrial catalyst, its acquisition and its use, especially for the production of 1,2-dichloroethane (EDC) oxychloination of ethylene in the reactor with a fluidized bed or in a reactor with a fixed layer

The invention relates to a method for producing 1,2-dichloroethane by reacting Athena with hydrogen chloride and oxygen or oxygen-containing gas on copper-containing catalyst in the fluidized bed

The invention relates to methods for organochlorine products and can be used in the chemical industry for the improvement of the production of vinyl chloride from ethylene

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. 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

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