Method for conversion of ethylene to vinyl chloride and novel catalytic compositions useful in indicated method

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

 

The vinyl chloride monomer (including infrastructure) are increasingly used as a monomer when receiving large amounts of polyvinyl chloride (PVC) resins, plastic materials and multi-use. Here, the invention relates to a method and catalyst for catalytic obtain the Ministry of amelioration of streams containing ethylene. In the method using a new catalyst that allows direct production of Ministry of amelioration in one reaction system. As additional benefits as raw material in this reaction system can also enter ethane.

Currently, the Ministry of amelioration and most often produced from ethylene and chlorine first by the chlorination of ethylene with obtaining 1,2-dichloroethane. 1,2-Dichloroethane is then thermally dihydrochloride thus the Ministry of amelioration and hydrogen chloride (HCl) as a by-product. HCl formed in the reactor dehydrocorydaline, usually captured and fed into the reactor for the oxychlorination process. The process of oxychlorination process catalytically converts ethylene, HCl and oxygen in 1,2-dichloroethane, which is also dihydrochloride obtaining Ministry of amelioration. Hence, the above method typically includes three separate sections of the reactor section of the direct chlorination, section oxychlorination process and section dehydrocorydaline. In installation, functioning thus introducing ethylene, chlorine and oxygen and remove obrazovaniia the merits of the Ministry of amelioration and water. The complexity of the three sections of the reactor led to the search for ways to obtain directly from the Ministry of amelioration and hydrocarbons in one section of the reactor.

In addition, obtaining ethylene require large investments and the cost of ethylene is usually a significant factor in the total cost of obtaining Ministry of amelioration and in accordance with the above method. It is because of the last-described drawback of the conventional balanced technologies have long attempted to make a profitable way to obtain the Ministry of amelioration of ethane as the source material.

The next disadvantage of direct receipts Ministry of amelioration and methods on the basis of ethane and ethylene, refers to less than required, the selectivity of education Ministry of amelioration (often less than 30 percent). Specified less than desired, the selectivity in respect of the Ministry of amelioration and to a large extent can be attributed to the formation of by-products in the reaction oxychlorination process. Most products are either formed from the products of combustion generated in the oxidation of hydrocarbons such as ethane, with the formation of mainly CO and CO2(the combination of which is called COx), or by-products are various chlorinated derivatives of hydrocarbons (usually, ethylchloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trial RATAN, 1,1-dichloroethylene, CIS-1,2-dichloroethylene, TRANS-1,2-dichloroethylene, trichloroethylene and perchloroethylene). The formation of tri-, Tetra-, Penta - and hexachloropropane compounds are particularly undesirable because of their toxicity and physical properties. Previously it was proposed to handle these by-products mainly by either ventilation and removal or selective separation and management of some of the chlorinated by-products back into the reactor for the oxychlorination process. Usually for recyclization require multiple stages of purification and transformation before disposing recyclebank products in the reactor oxychlorination process. For example, unsaturated chlorinated hydrocarbons usually transform in saturated form on the stage of the hydrogenation.

The present invention is devoid of the disadvantages existing in the known methods of production including infrastructure, as described above. In the first aspect of the present invention, a method for receiving including infrastructure, simplified in comparison with "a balanced way including infrastructure", in which the Ministry of amelioration can be obtained from ethylene, ethane and ethylene or essentially of ethane with recycling of ethylene from the product stream. The method of producing vinyl chloride in accordance with the first aspect includes a main stages: (a) mixing of reactants comprising ethylene, a source of oxygen and a source of chlorine, in the enjoyment of the Torah, containing catalyst, under conditions sufficient for the formation of a product stream comprising vinyl chloride, ethylene and hydrogen chloride; and (b) the management of ethylene in the product stream back to use on stage. Ethylene, need for stage (a), can be supplemented with ethane as an additional hydrocarbon source material, and it can only consist of ethylene, recyclebank from the product stream, so Ethan is really only used during the required C2-hydrocarbons. The catalyst used for the method in the preferred implementation, can be characterized as a porous material containing a rare earth element ("REE material")provided for this specific implementation, the catalyst essentially does not contain iron and copper, with the following proviso that when cerium is present, the catalyst additionally contains at least one rare earth metal in addition to cerium.

In a second related aspect of the present invention proposed a composition that can be used as a catalyst in the above way. The composition has the formula MOCl, where M represents at least one rare earth element selected from lanthanum, cerium, neodymium, praseodymium, di is prose, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium, lutetium, or mixtures thereof, with the proviso that when cerium is present, there is also at least one rare earth element, in addition to cerium. The way to obtain this composition includes the following stages: (a) obtaining a solution of the chloride salt of rare earth element or elements in a solvent, representing either water, alcohol, or a mixture thereof; (b) adding a nitrogen-containing base to cause the formation of sludge, and (C) collecting, drying and calcining the precipitate to obtain a composition MOCl.

In a third related aspect of the present invention proposed an additional composition, which can be used as a catalyst in the above way. The composition has the formula MCl3where M represents at least one rare earth element of the 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, there is also at least one rare earth element, in addition to cerium. The way to obtain this composition includes the following stages: (a) obtaining a solution of the chloride salt of rare earth element or elements in a solvent, representing l is Bo water, alcohol, or a mixture thereof; (b) adding a nitrogen-containing base to cause the formation of sludge, (C) collecting, drying and calcination of the precipitate and (d) contacting the calcined precipitate with a source of chlorine.

As indicated, a key distinguishing feature of the method of the present invention is to recyclization ethylene from the product stream back to the reactor for the first stage. After drying in accordance with methods known in this field, the hydrogen chloride formed in the product flow, preferably, also recyclist back for use in the first stage. Carbon monoxide is present in the product stream can also recycleability back to the first stage of the method.

Unlike known methods, the high selectivity of education Ministry of amelioration can be achieved by the method according to the present invention from a raw material containing ethylene, through the use of the catalysts described herein character. Typically, the selectivity of education Ministry of amelioration and in this way above 50 percent in terms of converted With2. With2refers to the ethylene raw material supplied to the reactor system as the sole hydrocarbon source or in combination with ethane. The selectivity of education Ministry of amelioration and preferably above 60 percent, calculated on converted With2. More PR is doctitle, the selectivity of education Ministry of amelioration and above 65 percent in terms of converted With2and very preferably, the selectivity of education Ministry of amelioration and above 70 percent in terms of converted C2. One reason for the higher selectively education Ministry of amelioration due to the fact that at typical process temperatures used in this method (which is usually lower than that described in comparative known methods for obtaining including infrastructure) catalysts described herein can significantly reduce the levels of unwanted higher chlorinated compounds, such as tri-, Tetra-, Penta - and hexachloropropane connection.

An additional advantage of this method is that you can use ethane to ethylene as a hydrocarbon source. In the reactor, preferably, a significant amount of ethane is subjected to oxidative dehydrogenation to ethylene. Catalyst and method of the present invention allow recycleability part or all of the quantity of ethylene from the product stream back into the stream of reactants. Any unreacted ethane present in the product flow, primarily recycleability back to the first stage of the method. Other light gases, such as combustion products, optionally, may be contained in recyclebank thread. When used with the locally supplied stream of ethane way preferably, carried out with such a balance of ethylene to the total number of moles per minute (i.e. stream) of ethylene in the product stream was essentially equal to the total number of moles per minute of ethylene entering the reactor. In fact, ethylene, apparently, continuously recyclized without depletion, while ethane is substantially consumed in the reactor. The preferred method of carrying out the invention, therefore, is such that the stream recycling would be the only source of ethylene in the first stage, and Ethan has provided a new source With2-hydrocarbon in the process.

The preferred sources of chlorine and oxygen are gases. The most preferred source of oxygen is gaseous oxygen. Desirable sources of chlorine are hydrogen chloride, chlorine, chlorinated hydrocarbons containing labile glory, and mixtures thereof. Preferred sources of chlorine, which are chlorinated hydrocarbons containing labile glory include carbon tetrachloride, 1,2-dichloroethane, ethylchloride and mixtures thereof. Most preferably, the flow of reactants continuously attended at least some amount of gaseous chlorine (Cl2). It was found in this respect that when Cl2use in the flow of the reactants as a source of chlorine, on the I of any given set of conditions, the quantity of combustion products (CO xcan be reduced compared with the case where Cl2do not use. In the alternative case assumes that if another source of chlorine, for example hydrogen chloride (including hydrogen chloride, separated from the product stream and recyclebank), used as the sole source of chlorine under normal operations, then Cl2should be given to the catalyst as in the beginning, and the suspension of the process before the conversion process is fully online, real-time, with the additional finding that after treatment (or pretreatment) Cl2the tendency of the catalyst to form these combustion products can be greatly reduced compared with a case in which Cl2was not used for processing or conditioning of the catalyst.

In light of the above here, experts in this field is capable of changing conditions in the reactor, so that conditions were sufficient to obtain the product stream comprising vinyl chloride, ethylene and hydrogen chloride. Conditions that usually vary by professionals in this area include: molar ratio of reactants in the feed raw materials; temperature; pressure and time of contact of the reactants with the catalyst. The reactor preferably stand between temperature above 350°With more prepact the tion, above 375°and a temperature less than 500°more preferably, less than 450°C. Typically, the reactor is maintained at a pressure between ambient pressure and pressure of 3.5 megapascals (MPa) (500 pounds per square inch (psi, excess.)). Operation under pressure can significantly adapt it for carrying out processing operations in the course of the stream, because the higher pressure provides the driving force for the movement of material in an installation for the separation or through this installation. The pressure in the process, preferably, is between ambient pressure and pressure of 2.1 MPa (300 psi) and, most preferably, between ambient pressure and pressure of 1.1 MPa (150 psi). The process can be carried out either by way of fixed bed or fluidized bed, although the way fluidized bed is preferred.

Another aspect relates to a catalyst used in the method according to this invention. Although the above method main point is the catalyst described herein, the catalyst has an additional use, for example, as a catalyst precursor, as a regenerated absorbent, as a substrate for catalyst and catalyst for other methods. As Illustra the AI, oxychloride rare earth elements can be used as a regenerated bases by exposure to HCl, with the result that they are converted into the corresponding chlorides of rare-earth metals, releasing water. The impact on the chlorides of rare earth elements water converts them back into oxychloride rare earth elements with the release of HCl. It should be noted that the particles and granules oxychloride rare earth elements do not undergo large changes in shape or size when chlorination. On the contrary, pure oxides of rare earth elements can undergo large changes during the chlorination, which cause severe destruction of the obtained particles. Chlorides of rare earth elements can also interact with methanol, forming methyl chloride. Therefore, the catalyst can be used in catalytic processes to obtain methyl chloride, not containing HCl.

The catalyst can also be used for the dehydrogenation of ethane, since the contacting of the stream of ethane, oxygen, and chlorine source, such as HCl, with catalyst yields a stream comprising predominantly ethylene and HCl. In addition, the contacting of the catalyst with a stream containing one or more products selected from ethylchloride, 1,2-dichloroethane and 1,1,2-trichloroethane is, leads to the dehydrochlorination of these products obtaining HCl and the corresponding unsaturated hydrocarbon or chloropetalum. In addition, when the salts of copper are in contact with a catalyst (either by their presence in solution in the deposition process, or the introduction of copper-containing solutions in the calcinated catalyst), processing of HCl catalyst provides a catalyst which can be used for oxychlorination process of ethylene to 1,2-dichloroethane. The catalysts are especially desirable due to their ability to operate at higher temperatures without increased formation of COx.

As described above, the catalyst according to this invention includes at least one rare earth material. Rare earth elements are a group of 17 elements, including scandium (number 21), yttrium (number 39) and the lanthanides (serial numbers 57-71) [James C. Hedrick, U.S. Geological Survey - Minerals Information -1997, "Rare-Earth Metals"]. The catalyst may be represented either in the form of a porous, granular material, or it can be deposited on a suitable carrier. The preferred rare earth materials are products on the basis of lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium. The most preferred rare earth substance is for use in the above method of obtaining the Ministry of amelioration and based on those rare-earth elements, which is usually treated as a monovalent substances. It turns out that the catalytic efficiency of substances with multiple valences is less desirable than substances that have the same valence. For example, it is known that cerium is a catalyst for the oxidation-reduction, with the ability to achieve stable oxidation States as a 3+and 4+. This is one reason why, if the rare earth material is based on tserii, the catalyst of the present invention further includes at least one rare earth element in addition to cerium. If one of rare earth elements used in the catalyst is a cerium, preferably, the cerium is presented in a molar ratio that is less than the total number of other rare earth elements present in the catalyst. More preferably, however, when cerium is essentially not present in the catalyst. The expression "essentially does not contain cerium" means any cerium is present in amount of less than 33 atomic percent rare earth components, preferably less than 20 atomic percent and, most preferably, less than 10 atomic percent.

Rare earth material for the catalyst of the present invention, more predpochtite is) based on lanthanum, neodymium, praseodymium, or a mixture thereof. Most preferably, when at least one of rare earth metals used in the catalyst is lanthanum. In addition to containing the ethylene raw material for the method of obtaining the Ministry of amelioration of the present invention the catalyst essentially does not contain iron and copper. Usually, the presence of materials that ways to oxidation-restoration (redox system), is undesirable for the catalyst. For the catalyst preferably also so that it essentially does not contain other transition metals that have more than one stable oxidation state. For example, manganese is another transition metal, the presence of which, preferably, is excluded from the composition of the catalyst. 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 greater than 10, more preferably greater than 15, and most preferably more than 50.

As indicated above, the catalyst may be deposited on an inert carrier. Preferred inert carriers include alumina, silica gel, silica-alumina, silica-magnesia, bauxite, magnesium oxide, silicon carbide, titanium oxide, zirconium oxide, silication and combinations thereof. However, in the preferred implementation, the media is not a zeolite. When an inert carrier material rare earth component of the catalyst is usually from 3 mass percent (mass. percent) to 85 mass. percent of the total weight of catalyst and carrier. The catalyst can be applied to the carrier using methods already known in this field.

It can also be useful to include other elements in the catalyst in the form of porous, granular material, and on the media. For example, the preferred elemental additives include alkaline earth metals, boron, phosphorus, sulfur, silicon, germanium, titanium, zirconium, hafnium, aluminum, and combinations thereof. These elements may be present to modify the catalytic efficiency of the composition or improve the mechanical properties (e.g., abrasion resistance) of the material.

Before mixing atlantabased raw source of oxygen and a source of chlorine in the reactor for the method of obtaining the Ministry of amelioration of the present invention, preferably, the catalytic composition consisted of salt, at least one rare earth metal, provided that the catalyst essentially does not contain iron and copper, and the next time the proviso that when using the cerium, the catalyst further includes, at the very measures which, another rare earth element in addition to cerium. Salt, at least one rare earth element, 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 the next time the proviso that when using the cerium, the catalyst additionally contains at least one rare earth element in addition to 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 and lutetium, or mixtures thereof, with the proviso that when cerium is present, there is also at least one rare earth element in addition to cerium. Most preferably, the salt is a porous, granular material of lanthanum oxychloride (LaOCl). As stated, this material is beneficial does not undergo large changes (e.g., destruction) by chlorination in suti in this way and provides additional useful property of water solubility in the context of the way after use (LaOCl first is wagoners Workum), so, if the spent catalyst must be removed from the reactor with a fluidized bed, fixed bed or other equipment or vessels of the way, this can be done without hydroprogne or conventional intensive force mechanical means simple leaching of waste under consideration catalyst from the reactor water.

Usually, when salt is oxychloride rare earth element (MOCl), it has a BET surface area 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/, Typically the BET surface area is less than 200 m2/, For the data above measurements adsorption isotherm of nitrogen measured at 77 K, and the surface area calculated from the isotherm data using the method of BET (Brunauer, S., Emett, P.H. and Teller, E., J. Am. Chem. Soc., 60, 309 (1938)). In addition, it is noted that phase MOCl have a picture of the characteristic powder diffraction x-ray (XRD), which differ from the phases MCl3.

You can also, as shown in several earlier examples, apply a mixture of rare earth elements ("M") in the composition MOCl. For example, M may be a mixture of at least two rare earth elements selected from lanthanum, cerium, neodymium, prasadi is a, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium. Similarly, it is also possible to use mixtures of different compositions MOCl, where M is different for each song MOCl in the mixture.

After mixing atlantabased raw source of oxygen and a source of chlorine in the reactor the catalyst is formed in situ from a salt of at least one rare earth element. Although this characterization is not meant to limit the composition or method of the present invention in any way, it is believed that the in situ formed catalyst comprises 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, provided that when using the cerium, the catalyst additionally contains at least one rare earth element in addition to cerium. Usually, when salt is a chloride rare earth element (MCl3), he has a BET surface area of at least 5 m2/g, preferably at least 10 m2/g, more preferably at least 15 m2/g, even more preferably at least 20 m2/g, and most preferably, ENISA least 30 m2/year

The oxychloination usually referred to as oxidative addition of two atoms of chlorine to ethylene from HCl or other recovered chlorine source. Catalysts capable of this chemical transformation, were classified as modified catalysts Deacon [Olah, G.A., Molnar, A., Hydrocarbon Chemistry, John Wiley and Sons (New York, 1995), pg 226]. Chemistry Deacon refers to the Deacon reaction, the oxidation of HCl with obtaining elemental chlorine and water.

Without limiting the present invention, as stated below, in contrast to oxychloination, the preferred method and the catalyst described above as using oxidehydrogenation when converting athenagorase and atlantabased threads in the Ministry of amelioration and with high selectivity. Oxidehydrogenation is the conversion of hydrocarbon (using a source of oxygen and chlorine in a chlorinated hydrocarbon, where the carbon keep either their initial valence, or have them restored valence (e.g., sp3-carbon preserve sp3or turn into sp2and sp2-carbon persist or become sp). This differs from the generally accepted definition of the oxychlorination process by which ethylene is converted to 1,2-dichloroethane with increasing valency of carbon (i.e. sp2-carbon of Pribram who are in sp 3-carbon).

In the light described here, the experts in this field can, without doubt, to develop alternative methods of obtaining compositions of the present invention. However, at present considered the preferred method of obtaining a composition comprising oxychloride rare earth metal (MOCl), which includes the following stages: (a) obtaining a solution of the chloride salt of rare earth element or elements in a solvent comprising either water, alcohol or mixtures thereof, (b) adding a nitrogen-containing base to induce the formation of deposits and (C) collecting, drying and calcining the precipitate to form material MOCl. Usually 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 can also be represented in the form of a mixture of nitrogen-containing base to other bases that do not contain nitrogen. Preferably, nitrogen-containing base is of tetraalkylammonium hydroxide. The solvent phase (a), preferably is water. Drying catalytically useful compositions can be accomplished by any method, including spray drying, drying in scavenged drying Cabinet and other known methods. For preferred at the present time the I method of operation of fluidized bed is preferred catalyst, dried spray.

The method at present considered to be preferred to obtain a catalyst composition comprising a chloride rare earth metal (MCl3), includes the following stages: (a) obtaining a solution of the chloride salt of rare earth element or elements in a solvent comprising either water, an alcohol or a mixture thereof; (b) adding a nitrogen-containing base to induce sediment; (C) collecting, drying and calcination of the precipitate and (d) contacting 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 a solution of nitrogen-containing base, drying it, adding it to the reactor, heated to 400°in the reactor for carrying out calcination and then contacting the calcined precipitate with a source of chlorine with the formation of the composition of the catalyst in situ in the reactor.

EXAMPLES

The invention will be further illustrated in the following examples, which are intended solely for illustrative purposes.

Example 1

To demonstrate receipt of vinyl chloride from a stream comprising ethylene, get porous, refractory composition comprising lanthanum. The solution LaCl3in water obtained by dissolving one part of commercially available hydrated chloride Lunt is on (obtained from J.T. Baker Chemical Company) in 8 parts of deionized water. Add dropwise with stirring ammonium hydroxide (obtained from Fisher Scientific, certified ACS specification) to neutral pH (universal indicator paper) causes the formation of gel. The mixture is centrifuged and the solution decanted from the solid part. Add approximately 150 ml of deionized water and gel vigorously stirred for dispersion of the solid part. The resulting solution is centrifuged and the solution decanted. This phase of the washing cycle is repeated two more times. Collected, washed gel is dried for two hours at 120°and then calcined at 550°C for four hours in air. The resulting solid is ground and sieved, while receiving particles suitable for the next test. This procedure gives a solid, corresponding powder x-ray diffraction LaOCl.

Particles placed in a clean Nickel (alloy 200) reactor. The reactor is configured such that in the reactor it was possible to submit ethylene, ethane, HCl, oxygen and inert gas (a mixture of No and Ar). The function of argon is an internal standard for the analysis of raw material and exhaust gas chromatography. The time of contacting the stream with a catalyst calculated as the volume of catalyst divided by the flow rate at standard conditions is the third. The ratio of the raw material components is given in molar relationship. In the reaction system immediately served athenagorase flow when the stoichiometric ratio of ethane, HCl and oxygen. It provides a balanced stoichiometry to obtain the Ministry of amelioration of ethylene.

In table 1, below, presents the results of testing of the reactor with the use of this composition.

Column 1 of table 1 shows the high selectivity of the formation of vinyl chloride, when the catalytic system is introduced ethylene under oxidation conditions in the presence of HCl. The composition comprises helium to simulate reactor operating with air as the gas-oxidant.

Column 2 of table 1 shows the high selectivity of the formation of vinyl chloride, when the catalytic system is introduced ethylene under oxidation conditions in the presence of HCl. The composition is now enriched fuel in order to avoid the restrictions caused by flammable and does not contain helium.

Column 3 of table 1 shows the high selectivity of the formation of vinyl chloride and ethylene, when the catalytic system is introduced ethane under oxidation conditions in the presence of HCl. Composition simulates the reactor, operating with air as the gas-oxidant. Ethylene raw materials are not available. The ethylene present in the reactor is the product of partial oxidation of ethane.

To Lanka 4 table 1 shows the results when served as ethane and ethylene. The reactor operates in such a way as to ensure that the number of ethylene entering the reactor and the effluent from the reactor, were equal. When the operation in this way the ethylene demonstrates the visibility of 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 of ethylene leaving the reactor are equal. The ratio of ethylene to argon integrated chromatographic peak is identical for raw materials for the reactor and the product stream. So by recycling the ethylene plays in the reactor device.

Table 1
Molar ratio of the raw components
With2H423,703
C2H60012
HCl2212,5
O21111
Inert gases6,804 0
T (degrees C)401400401419
The time of contacting the stream with a catalyst (C)12,35,021,812,4
Turning About2(percentage)47,353,7of 54.893,9
Selectivity (%)
With2H4--44,7-
C2H4Cl210,714,00,112,8
MBX76,678,134,568,5

Example 2

To further demonstrate the usefulness of the composition ethylene is subjected to the oxidative conversion of the vinyl chloride using different sources of chlorine. The solution LaCl3in water obtained by dissolving one part of commercially available hydrated lanthanum chloride (from the firm Avocado Research Chemicals Ltd.) 6.6 parts of deionized water. Quick add with stirring 6 M ammonium hydroxide in water (diluted, certified ACS reagent from Fisher Scientific company) causes the formation of gel. The mixture is filtered to collect the solids. SOBR the config gel dried at 120° With before calcination at 550°C for four hours in air. The resulting solid is ground and sieved. The sieved particles are placed in pure Nickel reactor (alloy 200). The reactor is configured such that the ethylene, HCl, oxygen, 1,2-dichloroethane, carbon tetrachloride and helium can enter into the reactor. The time of contacting the stream with a catalyst calculated as the volume of catalyst divided by the flow rate at standard temperature and pressure. Speed flows are molar relationship. The composition is heated to 400°and is treated with a mixture of 1:1:3 HCl:O2:Not within 2 hours before the operation.

The resulting composition is exposed to to obtain a vinyl chloride-ethylene injection, the source of chlorine and oxygen at 400°C. the following table shows the data obtained between 82 and 163 hours flow, in which use different sources of chlorine. Chlorine is served in the form of HCl, carbon tetrachloride and 1,2-dichloroethane. Ministry of amelioration and means vinyl chloride. The time of contacting the stream with a catalyst calculated as the volume of catalyst divided by the flow rate at standard temperature and pressure. The reactors operate with the outlet of the reactor at ambient pressure. As ethylene and 1,2-dichloroethane, called With2connections.

Table 2
Molar ratio of the raw components
With2H42,02,02,02,0
C2H60,00,00,00,0
CCl40,50,50,00,0
With2H4Cl20,00,01,80,0
HCl0,00,00,01,9
O21,01,01,01,0
Not+Ar8,99,08,96,7
T°)400399401400
The time of contacting the stream with a catalyst (C)8,04,08,6a 4.9
Fractional conversion (%)
With2H440,427,018,720,1
With2H60,00,00,00,0
CCl4 94,878,40,00,0
With2H4Cl20,00,098,30,0
HCl0,00,00,044,7
O268,842,055,2of 37.8
Selectivity per mole transformed With2
Including infrastructureto 59.6of 56.486,078,5
With2H4Cl214,830,70,02,2
With2H5Cl0,60,40,21,6

These data show that under oxidative obtaining vinyl chloride can be used various sources of chlorine. When using all of the sources, carbon tetrachloride, 1,2-dichloroethane and HCl, the vinyl chloride is formed as the dominant product.

Example 3

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

Table 3 summarizes the data where the raw materials of the reactor is adjusted so that the flow of ethylene (mole/min)included in the reactor, and the flow of ethylene leaving the reactor were essentially equal. Raw materials of the reactor similarly adjusted so that the flow of HCl, incoming and outgoing from the reactor, were essentially equal. The conversion of oxygen is set slightly smaller than the complete transformation that allows you to monitor the activity of the catalyst. When carrying out operations specified components used raw materials are ethane, oxygen and chlorine. The impression that as ethylene and gaseous HCl is not formed and not spent. The time of contacting the stream with a catalyst calculated as the volume of catalyst divided by the flow rate at standard temperature and pressure. The next example illustrates the use of chlorine gas as a source of chlorine upon receipt of vinyl chloride.

Table 3
Molar ratio of the raw components
With2H42,1
With2H64,5
Cl20,5
HCl2,4
O21,0
Not+Ar7,4
T°)400
The time of contacting the stream with a catalyst (C)9,4
Fractional conversion (%)
With2H41,8
With2H627,3
Cl299,8
HClof-1.4
O296,4
Selectivity (%)
Including infrastructure79,0
C2H4Cl27,2
C2H5Cl1,7
COx5,1
With2H40,5

For all examples here including infrastructure means vinyl chloride, C2H4Cl2is only 1,2-dichloroethane. COxis a combination of co and CO2.

Example 4

The composition of the catalyst obtained in example 1 was used to show the effect of temperature on catalytic efficiency. The results are shown in table 4.

Table 4
The effect of temperature on the composition of lanthanum
Molar ratio of the raw components
With2H41,91,91,9
With2H60,00,00,0
Cl20,00,00,0
HCl1,91,91,5
O21,01,01,0
Not+Ar6,66,67,1
T°)349399450
The time of contacting the stream with a catalyst (C)a 4.9the 9.79,6
Fractional conversion (%)
With2H48,2/td> 33,035,2
With2H60,00,00,0
Cl2
HCl7,536,046,5
O28,849,257,1
Selectivity (%)
Including infrastructure67,787,479,8
C2H4Cl22,50,20,8
C2H5Cl28,11,30,4
COx1,60,98,9

The data show that the ability of the composition to form the vinyl chloride slightly changes when the temperature changes. Lower temperatures reduce speed, but the selectivity is changed only slightly.

Examples 5 to 12

Examples 5 to 12 illustrate the generation of multiple compositions of rare earth elements, and each contains only one rare earth material. Data illustrating the effectiveness of the decree is different compositions, are given in table 5.

Example 5

The solution LaCl3in water obtained by dissolving one part of commercially available hydrated lanthanum chloride (from the company Aldrich Chemical Company) in 6,67 parts of deionized water. Quick add with stirring 6M ammonium hydroxide in water (diluted, certified ACS reagent, obtained from Fisher Scientific company) causes the formation of gel. The mixture is centrifuged to collect the solid. The solution is decanted from the gel and unload. The gel is again suspended in 6,66 parts of 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 resulting solid is ground and sieved. The sieved particles are placed in pure Nickel reactor (alloy 200). The reactor is configured such that the ethylene, ethane, HCl, oxygen and inert gas (a mixture of helium and argon), it was possible to introduce into the reactor. Powder x-ray diffraction shows that the material is LaOCl. The measured BET surface area is 42,06 m2/year Specific data efficiency for this example are shown below in table 5.

Example 6

The solution NdCl3in water obtained by dissolving one part of commercially available hydrated neodymium chloride (Alfa Aesar) in 6,67 h the posts in deionized water. Quick add with stirring 6 M ammonium hydroxide in water (diluted, certified ACS reagent, obtained from Fisher Scientific company) causes the formation of gel. The mixture is filtered to collect the solids. The collected gel dried at 120°before calcination in air at 550°C for four hours. The resulting solid is ground and sieved. The sieved particles are placed in pure Nickel reactor (alloy 200). The reactor is configured such that the ethylene, ethane, HCl, oxygen and inert gas (a mixture of helium and argon), it was possible to introduce into the reactor. Powder x-ray diffraction shows that the material is NdOCl. The measured BET surface area is 22,71 m2/year Specific data efficiency for this example are shown below in table 5.

Example 7

The solution PrCl3in water obtained by dissolving one part of commercially available hydrated praseodymium chloride (Alfa Aesar) in 6,67 parts of deionized water. Quick add with stirring 6 M ammonium hydroxide in water (diluted, certified ACS reagent, obtained from Fisher Scientific company) causes the formation of gel. The mixture is filtered to collect the solids. The collected gel dried at 120°before calcination in air at 550°C for four hours. Formed the solid substance is milled and sieved. The sieved particles are placed in pure Nickel reactor (alloy 200). The reactor is configured such that the ethylene, ethane, HCl, oxygen and inert gas (a mixture of helium and argon), it was possible to introduce into the reactor. Powder x-ray diffraction shows that the material is PrOCl. The measured BET surface area is 21,37 m2/year Specific data efficiency for this example are shown below in table 5.

Example 8

The solution SmCl3in water obtained by dissolving one part of commercially available hydrated samarium chloride (Alfa Aesar) in 6,67 parts of deionized water. Quick add with stirring 6 M ammonium hydroxide in water (diluted, certified ACS reagent, obtained from Fisher Scientific company) causes the formation of gel. The mixture is filtered to collect the solids. The collected gel dried at 120°before calcination at 550°C for four hours. The resulting solid is ground and sieved. The sieved particles are placed in pure Nickel reactor (alloy 200). The reactor is configured such that the ethylene, ethane, HCl, oxygen and inert gas (a mixture of helium and argon), it was possible to introduce into the reactor. Powder x-ray diffraction shows that the material is SmOCl.

The measured BET surface area is 30,09 m2/, Con the specific data efficiency for this example are given below, in table 5.

Example 9

A solution of HoCl3in water obtained by dissolving one part of commercially available hydrated holmium chloride (Alfa Aesar) in 6,67 parts of deionized water. Quick add with stirring 6 M ammonium hydroxide in water (diluted, certified ACS reagent, obtained from Fisher Scientific company) causes the formation of gel. The mixture is filtered to collect the solids. The collected gel dried at 120°before calcination at 500°C for four hours. The resulting solid is ground and sieved. The sieved particles are placed in pure Nickel reactor (alloy 200). The reactor is configured such that the ethylene, ethane, HCl, oxygen and inert gas (a mixture of helium and argon), it was possible to introduce into the reactor. The measured BET surface area is 20,92 m2/year Specific data efficiency for this example are shown below in table 5.

Example 10

The solution ErCl3in water obtained by dissolving one part of commercially available hydrated erbium chloride (Alfa Aesar) in 6,67 parts of deionized water. Quick add with stirring 6 M ammonium hydroxide in water (diluted, certified ACS reagent, obtained from Fisher Scientific company) causes the formation of gel. The mixture is filtered to collect the solids. The collected gel is dried at 20° With before calcination at 500°C for four hours. The resulting solid is ground and sieved. The sieved particles are placed in pure Nickel reactor (alloy 200). The reactor is configured such that the ethylene, ethane, HCl, oxygen and inert gas (a mixture of helium and argon), it was possible to introduce into the reactor. The measured surface area BET is 19,80 m2/year Specific data efficiency for this example are shown below in table 5.

Example 11

The solution YbCl3in water obtained by dissolving one part of commercially available hydrated ytterbium chloride (Alfa Aesar) in 6,67 parts of deionized water. Quick add with stirring 6 M ammonium hydroxide in water (diluted, certified ACS reagent, obtained from Fisher Scientific company) causes the formation of gel. The mixture is filtered to collect the solids. The collected gel dried at 120°before calcination at 500°C for four hours. The resulting solid is ground and sieved. The sieved particles are placed in pure Nickel reactor (alloy 200). The reactor is configured such that the ethylene, ethane, HCl, oxygen and inert gas (a mixture of helium and argon), it was possible to introduce into the reactor. The measured surface area BET is 2,23 m2/year Specific data efficiency for a given p is the iMER below in table 5.

Example 12

The solution YCl3in water obtained by dissolving one part of commercially available hydrated yttrium chloride (Alfa Aesar) in 6,67 parts of deionized water. Quick add with stirring 6 M ammonium hydroxide in water (diluted, certified ACS reagent, obtained from Fisher Scientific company) causes the formation of gel. The mixture is filtered to collect the solids. The collected gel dried at 120°before calcination at 550°C for four hours. The resulting solid is ground and sieved. The sieved particles are placed in pure Nickel reactor (alloy 200). The reactor is configured such that the ethylene, ethane, HCl, oxygen and inert gas (a mixture of helium and argon), it was possible to introduce into the reactor. The measured BET surface area is 29,72 m2/year Specific data efficiency for this example are shown below in table 5.

Table 5
Composition of oxychlorides rare earth elements used to obtain vinyl chloride
Example56789101112
Molar ratio of the components is s raw materials
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°)399403401400400400400399
The time of contacting the stream with a catalyst (C)8,721,311,417,617,722,823,121,3
Fractional conversion (%)
C2H423,713,222,814,7a 12.715,43,313,8
HCl47,624,9of 40.920,815,9/td> 22,45,019,8
O258,8to 59.455,053,448,148,8of 21.247,8
Selectivity (%)
Including infrastructure75,374,474,261,033,344,06,135,0
C2H4Cl211,32,96,12,914,5of 17.58,818,8
With2H5Cl3,56,94,410,616,812,837,016,5
COx4,811,8the 9.722,4to 33.823,126,427,5

The data show the usefulness of solids containing rare-earth elements compositions for turning atlantageorgia flows in the vinyl chloride.

Examples 13 to 17

Examples 13 to 17 illustrate the generation of multiple compositions of rare-earth metals, and each contains a mixture of rare earth materials. Data illustrating the effectiveness of this is x data are given in table 6.

Example 13

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

Example 14

The solution LaCl3and SmCl3in water obtained by dissolving one part of commercially available hydrated lanthanum chloride (from the firm Spectrum Quality Products) and 0.67 parts commercial access the CSO hydrated samarium chloride (Alfa Aesar) in 13,33 parts of deionized water. Quick add with stirring 6 M ammonium hydroxide in water (diluted, certified ACS reagent, obtained from Fisher Scientific company) causes the formation of gel. Measured final pH value is 8,96. The mixture is centrifuged to collect the solid. The solution is decanted from the gel and unload. The collected gel dried at 80°before calcination at 550°C for four hours. The resulting solid is ground and sieved. The sieved particles are placed in pure Nickel reactor (alloy 200). The reactor is configured such that the ethylene, ethane, HCl, oxygen and inert gas (a mixture of helium and argon), it was possible to introduce into the reactor. The measured BET surface area is 21,01 m2/year Specific data efficiency for this example are shown below in table 6.

Example 15

The solution LaCl3and YCl3in water obtained by dissolving one part of commercially available hydrated lanthanum chloride (from the firm Spectrum Quality Products) and 0.52 part of commercially available hydrated yttrium chloride (Alfa Aesar) in 13,33 parts of deionized water. Quick add with stirring 6 M ammonium hydroxide in water (diluted, certified ACS reagent, obtained from Fisher Scientific company) causes the formation of gel. Measured final pH value is 8,96. A mixture of centres is pirouet to collect solids. The solution is decanted from the gel and unload. The collected gel dried at 80°before calcination at 550°C for four hours. The resulting solid is ground and sieved. The sieved particles are placed in pure Nickel reactor (alloy 200). The reactor is configured such that the ethylene, ethane, HCl, oxygen and inert gas (a mixture of helium and argon), it was possible to introduce into the reactor. The measured BET surface area is 20,98 m2/year Specific data efficiency for this example are shown below in table 6.

Example 16

The solution LaCl3and HoCl3in water obtained by dissolving one part of commercially available hydrated lanthanum chloride (from the firm 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 6 M ammonium hydroxide in water (diluted, certified ACS reagent, obtained from Fisher Scientific company) causes the formation of gel. Measured final pH value is 8,64. The mixture is centrifuged to collect the solid. The solution is decanted from the gel and unload. The collected gel dried at 80°before calcination at 550°C for four hours. The resulting solid is ground and sieved. The sieved particles are placed in a number of the initial Nickel reactor (alloy 200). The reactor is configured such that the ethylene, ethane, HCl, oxygen and inert gas (a mixture of helium and argon), it was possible to introduce into the reactor. The measured BET surface area is 19,68 m2/year Specific data efficiency for this example are shown below in table 6.

Example 17

The solution LaCl3and HoCl3in water obtained by dissolving one part of commercially available hydrated lanthanum chloride (from the firm Spectrum Quality Products) and 0.75 part of commercially available hydrated ytterbium chloride (Alfa Aesar) in 13,33 parts of deionized water. Quick add with stirring 6 M ammonium hydroxide in water (diluted, certified ACS reagent, obtained from Fisher Scientific company) causes the formation of gel. Measured final pH value is 9,10. The mixture is centrifuged to collect the solid. The solution is decanted from the gel and unload. The collected gel dried at 80°before calcination at 550°C for four hours. The resulting solid is ground and sieved. The sieved particles are placed in pure Nickel reactor (alloy 200). The reactor is configured such that the ethylene, ethane, HCl, oxygen and inert gas (a mixture of helium and argon), it was possible to introduce into the reactor. The measured BET surface area is 20,98 m2/year Specific data efficiency on the I this example below in table 6.

Table 6
The effectiveness of compositions containing two rare earth material
Example1314151617
The molar ratio of the raw components
C2H43,73,63,63,63,6
HCl2,02,02,02,02,0
O21,01,01,01,01,0
Not+Ar0,20,20,20,20,2
T°)401401400399400
The time of contacting the stream with a catalyst (C)3,715,713,716,920,6
Fractional conversion (%)
With2H416,811,312,512,49,2
HCl36,013,1 11,915,9
About245,9to 47.252,247,138,7
Selectivity (%)
Including infrastructure75,851,051,428,911,1
C2H4Cl2the 9.77,512,414,520,6
With2H5Cl4,111,88,9of 17.023,8
COx6,927,525,838,943,8

The data further show the usefulness of the bulk compositions of rare earth elements containing a mixture of rare earth materials, for turning atlantageorgia flows in the vinyl chloride.

Examples 18 to 25

Examples 18 to 25 are compositions containing rare earth materials with other additives present.

Example 18

The solution LaCl3in water obtained by dissolving one part of commercially available hydrated lanthanum chloride (from the company Aldrich Chemical Company) in 6,67 parts of deionized water. To 0.35 part of commercially obtained powder CeO2(Rhone-Poulenc) add 0,48 part of the hydroxide of ammo the Oia (Fisher Scientific). Containing lanthanum and cerium mixture is added together with stirring to form a gel. The resulting mixture containing the gel, filtered and the collected solid calicivirus in air at 550°C for 4 hours. The resulting solid is ground and sieved. The sieved particles are placed in pure Nickel reactor (alloy 200). The reactor is configured such that the ethylene, ethane, HCl, oxygen and inert gas (a mixture of helium and argon), it was possible to introduce into the reactor. Specific data efficiency for this example are shown below in table 7.

Example 19

Lanthanum-containing composition obtained by the method of example 5, ground using a mortar and pestle with the formation of fine powder. One part of the milled powder is mixed with 0,43 part of the powder BaCl2and then pulverized using a mortar and pestle with the formation of the close of the mixture. Containing lanthanum and barium mixture is pressed with the formation of lumps. Lumps calicivirus at 800°C in air for 4 hours. The resulting material is placed in a clean Nickel reactor (alloy 200). The reactor is configured such that the ethylene, ethane, HCl, oxygen and inert gas (a mixture of helium and argon), it was possible to introduce into the reactor. Specific data efficiency for this example are shown below in table 7.

Example 20

The dried silicon dioxide Grace Davison Grade 57 dried at 120°C for 2 hours. A saturated solution of LaCl3in water obtained using commercially available hydrated lanthanum chloride. The dried silica impregnated to the point of initial wetting solution LaCl3. Impregnated with the silica enable 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 clean Nickel reactor (alloy 200). The reactor is configured such that the ethylene, ethane, HCl, oxygen and inert gas (a mixture of helium and argon), it was possible to introduce into the reactor. Specific data efficiency for this example are shown below in table 7.

Example 21

The solution LaCl3in water obtained by dissolving one part of commercially available hydrated lanthanum chloride (from the firm Spectrum Quality Products) to 6.67 parts of deionized water. Quick add with stirring 6 M ammonium hydroxide in water (diluted, certified ACS reagent, obtained from Fisher Scientific company) causes the formation of gel. The mixture is centrifuged to collect the solid. The solution is decanted from the gel and unload. The gel is again suspended 12.5 parts of acetone (Fisher Scientific), centrifuged and the liquid decanted and you ruhut. Stage washing with acetone repeat 4 more times with the use of 8.3 parts of acetone. The gel is again suspended 12.5 parts of acetone and add to 1.15 parts hexamethyldisilazane (from the company Aldrich Chemical Company) and the solution 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 resulting solid is ground and sieved. The sieved particles are placed in pure Nickel reactor (alloy 200). The reactor is configured such that the ethylene, ethane, HCl, oxygen and inert gas (a mixture of helium and argon), it was possible to introduce into the reactor. The measured BET surface area is 58,82 m2/year Specific data efficiency for this example are shown below in table 7.

Example 22

The solution LaCl3in water obtained by dissolving one part of commercially available hydrated lanthanum chloride (Alfa Aesar) and 0.043 parts of a commercially available HfCl4(from company Acros Organics) in 10 parts of deionized water. Quick add with stirring 6 M ammonium hydroxide in water (diluted, certified ACS reagent, obtained from Fisher Scientific company) causes the formation of gel. The mixture is centrifuged to collect the solid. RAS is a thief decanted from the gel and unload. The collected gel dried at 80°before calcination at 550°C for 4 hours. Specific data efficiency for this example are shown below in table 7.

Example 23

The solution LaCl3in water obtained by dissolving one part of commercially available hydrated lanthanum chloride (Alfa Aesar) and 0,086 parts of a commercially available HfCl4(from company Acros Organics) in 10 parts of deionized water. Quick add with stirring 6 M ammonium hydroxide in water (diluted, certified ACS reagent, obtained from Fisher Scientific company) causes the formation of gel. The mixture is centrifuged to collect the solid. The solution is decanted from the gel and unload. The collected gel dried at 80°before calcination at 550°C for 4 hours. Specific data efficiency for this example are shown below in table 7.

Example 24

The solution LaCl3in water obtained by dissolving one part of commercially available hydrated lanthanum chloride (Alfa Aesar) and 0.043 parts of a commercially available ZrOCl2(from company Acros Organics) in 10 parts of deionized water. Quick add with stirring 6 M ammonium hydroxide in water (diluted, certified ACS reagent, obtained from Fisher Scientific company) causes the formation of gel. The mixture is centrifuged to collect the solid. The solution decant the shape from the gel and unload. The gel is again suspended in 6,67 parts of deionized water and then centrifuged. The solution is decanted and discharged. The collected gel calicivirus at 550°C for 4 hours. Specific data efficiency for this example are shown below in table 7.

Example 25

The solution LaCl3in water obtained by dissolving commercially available hydrated lanthanum chloride in deionized water to obtain 2,16 M solution. Commercially obtained zirconium oxide (obtained from Enhelhard) 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 calicivirus in air at 550°C for 4 hours. The resulting solid is ground and sieved. The sieved particles are placed in pure Nickel reactor (alloy 200). The reactor is configured such that the ethylene, ethane, HCl, oxygen and inert gas (a mixture of helium and argon), it was possible to introduce into the reactor. Specific data efficiency for this example are shown below in table 7.

Table 7
Composition of rare earth elements with additional components
Example181920 2122232425
Molar ratio of the raw components
C2H43,73,63,73,73,73,73,63,7
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 time of contacting the stream with a catalyst (C)4,820,36,73,67,97,812,816,7
Fractional conversion (%)
With2H418,211,714,124,618,516,5 18,715,2
HCl34,622,124,457,1of 40.938,235,221,1
About255,633,248,052,050,347,450,9of 56.4
Selectivity (%)
Including infrastructure64,554,653,656,076,471,873,255,1
C2H4Cl211,515,210,0of 31.49,6a 12.75,27,3
With2H5Cl5,010,07,42,94,0a 4.9a 4.912,4
COx10,818,626,66,07,68,813,624,1

The data show the receipt of vinyl chloride from Atlanterra flows using catalysts based on lanthanum, which contain other elements or supported on a carrier.

Examples 26 through 31

In examples 26 to mokhzani some modifications, possible to change the useful compositions of rare earth elements.

Example 26

The solution LaCl3in water obtained by dissolving one part of commercially available hydrated lanthanum chloride (from the firm Spectrum Quality Products) in 10 parts of deionized water. Quick add with stirring 6 M ammonium hydroxide in water (diluted, certified ACS reagent, obtained from Fisher Scientific company) causes the formation of gel. The mixture is centrifuged to collect the solid. The solution is decanted from the gel and unload. Get a saturated solution of 0.61 parts of chloride of benzyltriethylammonium (from the company Aldrich Chemical Company) in deionized water. The solution is added to the gel and mix. The collected gel calicivirus at 550°C for 4 hours. Specific data efficiency for this example are shown below in table 8. This example illustrates the use of added ammonium salts for modifying obtain compositions of rare earth elements.

Example 27

The solution LaCl3in water obtained by dissolving one part of commercially available hydrated lanthanum chloride (from the firm Spectrum Quality Products) in 10 parts of deionized water. Quick add with stirring 6 M ammonium hydroxide in water (diluted, certified ACS reagent, obtained from Fisher Scientific company) calls the AET the gel formation. The mixture is centrifuged to collect the solid. One part of glacial acetic acid is added to the gel and the gel is again dissolved. Adding a solution of 26 parts of acetone causes the formation of sludge. The solution is decanted and the solid calicivirus at 550°C for 4 hours. Specific data efficiency for this example are shown below in table 8. This example illustrates the production of useful compositions of lanthanum decomposition of the adducts of carboxylic acids and chlorine containing compounds of rare earth elements.

Example 28

The solution LaCl3in water obtained by dissolving one part of commercially available hydrated lanthanum chloride (from the firm Spectrum Quality Products) in 10 parts of deionized water. Quick add with stirring 6 M ammonium hydroxide in water (diluted, certified ACS reagent, obtained from Fisher Scientific company), causes the formation of a gel. The mixture is centrifuged to collect the solid. The collected gel again suspended at 3.33 parts of deionized water. Then add 0,0311 parts reagent phosphoric acid (Fisher Scientific company) does not cause visible changes in suspended gel. The mixture is again centrifuged and the solution decanted from the phosphorus-containing gel. The collected gel calicivirus at 550°C for 4 hours. Calcined firmly the substance has a surface area BET 33,05 m 2/year Specific data efficiency for this example are shown below in table 8. This example illustrates a composition of rare earth element containing phosphorus as phosphate.

Example 29

The solution LaCl3in water obtained by dissolving one part of commercially available hydrated lanthanum chloride (from the company Acros Organics) 6.6 parts of deionized water. The solution is obtained by mixing 0.95 parts of a commercially available DABCO, or 1,4-diazabicyclo[2.2.2]octane (from the firm Pharmaceuticals INC), 2.6 parts of deionized water. Rapid mixing with the mixing of the two solutions results in the formation of gel. The mixture is centrifuged to collect the solid. The collected gel again suspended in 6,67 parts of deionized water. The mixture is again centrifuged and the solution decanted from the gel. The collected gel calicivirus for 4 hours at 550°C. the Calcined solid material has a surface area BET 38,77 m2/year Specific data efficiency for this example are shown below in table 8. This example illustrates the suitability of the alkylamine in obtaining useful compositions of rare-earth element.

Example 30

The solution LaCl3in water obtained by dissolving one part of commercially available hydrated lanthanum chloride (from the company Acros Organics) in 10 parts of deionizer the Anna water. To this solution is rapidly added with stirring 2.9 parts of a commercially available hydroxide of Tetramethylammonium (purchased by Aldrich Chemical Company), thereby causing the gel formation. The mixture is centrifuged and the solution decanted. The collected gel again suspended in 6,67 parts of deionized water. The mixture is again centrifuged and the solution decanted from the gel. The collected gel calicivirus for 4 hours at 550°C. the Calcined solid material has a surface area BET 80,35 m2/year Specific data efficiency for this example are shown below in table 8. This example illustrates the suitability of the hydroxide of alkylamine for the formation of a useful composition of rare earth element.

Example 31

The solution LaCl3in water obtained by dissolving one part of commercially available hydrated lanthanum chloride (from the firm Avocado Research Chemicals Ltd.) in 6,67 parts of deionized water. To this solution is rapidly added with stirring and 1.63 parts of a commercially available 5 n NaOH (Fisher Scientific)), thereby causing the gel formation. The mixture is centrifuged and the solution decanted. The collected gel calicivirus for 4 hours at 550°C. the Calcined solid material has a surface area BET 16,23 m2/year Specific data efficiency for this example are shown below in table 8. This example is showing the suitability not containing nitrogen bases for the formation of catalytically interesting materials. Although it is possible that functional data tested materials with inferior materials obtained with the use of the nitrogenous bases.

Table 8
Additional ways to obtain a lanthanum-containing composition
Example262728293031
Molar ratio of the raw components
C2H43,63,73,63,73,73,7
HCl2,02,02,02,02,02,0
O21,01,01,01,01,01,0
Not+Ar0,20,20,20,20,20,2
T°)401400400399400401
The time of contacting the stream with a catalyst (C)8,620,8the 4.78,76,220,0
Fractional conversion (%)
With2H418,88,7the 15.617,421,09,3
HCl35,87,720,041,548,422,3
About253,032,648,850,656,817,9
Selectivity (%)
Including infrastructure73,426,072,1of 76.877,6of 17.5
C2H4Cl28,711,97,17,37,846,2
With2H5Cl3,522,75,64,22,925,6
COx9,838,6a 12.77,66,39,1

Example 32

To further demonstrate the suitability of the composition of 1,2-dichloroethane dehydrochlorination to obtain vinyl chloride using the composition as a catalyst. The solution LaCl3receive by dissolving one part of commercially available hydrated lanthanum chloride (from the Irma Avocado Research Chemicals Ltd.) in 6,67 parts of deionized water. Quick add by stirring 6 M ammonium hydroxide in water (diluted, certified ACS reagent, obtained from Fisher Scientific company) causes the formation of gel. The mixture is centrifuged to collect the solid. The collected gel dried at 120°before calcination in air at 550°C for four hours. The resulting solid is ground and sieved. The sieved particles are placed in pure Nickel reactor (alloy 200). The reactor is configured such that 1,2-dichloroethane and helium can enter into the reactor. The time of contacting the stream with a catalyst calculated as the volume of catalyst divided by the flow rate. Flow rate is given in molar relationship. The composition is heated to 400°and treated With 1:1:3 mixture of HCl:O2:Not within 2 hours before surgery. Reactor system operates with the supply of raw materials containing ethane and ethylene, to obtain a vinyl chloride for 134 hours at a temperature of 400°C. At this time, the composition of the raw material change that it contained Not only and 1,2-dichloroethane in the ratio of 5:1 at a temperature of 400°C. the flow Rate is adjusted to get the time of contact with the catalyst of 16.0 seconds. Analysis of the product shows more than of 99.98 percent conversion of 1,2-dichloroethane with a molar selectivity of the formation of vinyl chloride larger h is m 99,11%. After 4.6 hours on stream the experiment. Analysis of the product stream at a specified time shows that the transformation of 1,2-dichloroethane is 99,29% with a molar selectivity of conversion to vinyl chloride is higher than 99,45%.

Other embodiment of the invention will be obvious to experts in this field as a result of discussion of this specification or practice of the invention described here. Note that the description and examples should be considered only as illustrative, and the true scope and essence of the invention is defined by the following claims.

1. The method of producing vinyl chloride from ethylene by oxidehydrogenation, including:

(a) combining chemicals, including ethylene, a source of oxygen and a source of chlorine in the reactor containing the catalyst at a temperature of 350-500°and pressures from atmospheric up to 3.5 MPa, i.e. under conditions sufficient to obtain the product stream comprising vinyl chloride and ethylene;

moreover, the catalyst includes one or more rare-earth materials, provided that the atomic ratio of rare earth metal and the redox metal (iron and copper) in the catalyst is more than 10, and the next time the proviso that when cerium is present, the additional catalyst is about includes, at least one rare earth element other than cerium, and

(b) the management recycling of ethylene from the product stream back to use on stage (a).

2. The method according to claim 1, where the catalyst is a composition of the formula MOCl or MCl3where M represents a rare earth element or a mixture of rare earth elements selected from lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium.

3. The method of claim 2 where the catalyst is a composition of the formula MOCl.

4. The method according to claim 3, where the composition of the catalyst has a BET surface area ranging from 12 to 200 m2/year

5. The method according to claim 4, where the composition of the catalyst has a BET surface area of 30 to 200 m2/year

6. The method according to any of claim 2 to 5, where the composition of the catalyst was prepared by a process comprising the following stages:

(a) obtaining a solution of the chloride salt of rare earth element or elements in a solvent, representing either water, alcohol, or a mixture thereof;

(b) adding a nitrogen-containing base to cause the formation of sludge, and

(c) collecting, drying and calcining the precipitate to form a composition MOCl.

7. The method of claim 2 where the catalyst is a composition of the formula MCl2.

8. The method according to claim 7, where the composition of the catalyst forms the crystals MCl 3has a BET surface area of 5 to 200 m2/year

9. The method of claim 8, where the composition of the catalyst has a BET surface area of 30 to 200 m2/year

10. The method according to any of claims 7 to 9, where the catalyst was prepared by a process comprising the following stages:

(a) obtaining a solution of the chloride salt of rare earth element or elements in a solvent, representing either water, alcohol, or a mixture thereof;

(b) adding a nitrogen-containing base to cause the formation of sludge;

(c) collecting, drying and procline sediment, and

(d) contacting the calcined precipitate with a source of chlorine.

11. The method according to any one of claims 1 to 10, where the source of chlorine is gaseous and represents at least one of the following: hydrogen chloride, chlorine, chlorinated hydrocarbons, containing movable chlorine, and mixtures thereof.

12. The method according to any one of claims 1 to 11, where the ethane is also mixed with ethylene, a source of oxygen and a source of chlorine in the reactor.

13. The method according to item 12, where the total number of moles per minute of ethylene entering the reactor, essentially equal to the total number of moles per minute of ethylene leaving the reactor in the product flow, and, further, where essentially all ethylene leaving the reactor, recyclist.

14. The method according to item 12 or 13, where the ethane present in the product flow, also recyclist back for use with the adiya's () method.

15. The method according to any one of claims 1 to 14, where at stage (b) hydrogen chloride from the product stream also recyclist back for use in stage (a) of the method.

16. The method according to any one of claims 1 to 15, where the product stream contains carbon monoxide, and carbon monoxide recyclist of the flow of product back for use in stage (a) of the method.

17. The method according to any one of claims 1 to 16, where the cerium present in the catalyst present in an amount of less than 33 at.% relatively rare earth components.

18. The method according to any one of claims 1 to 17, where the component of the catalyst, which is a rare earth material, based on lanthanum, neodymium, praseodymium or mixtures of one or more specified elements.

19. The method according to p, where a component of the catalyst, which is a rare earth material, based on lanthanum.

20. The method according to any one of claims 1 to 19, where the catalyst is a porous, granular catalyst.

21. The method according to any one of claims 1 to 20, where the catalyst further includes elements selected from alkaline earth metals, boron, phosphorus, titanium, zirconium, hafnium and combinations thereof.

22. The method according to claim 20, where the catalyst loaded into the reactor in the form of granular salt MOCl, where M represents a rare earth element or a mixture of rare earth elements selected from lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, who adaline, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium.

23. The method according to item 22, where the catalyst loaded into the reactor is a bulk catalyst LaOCl.

24. The catalytic composition formula MOCl to obtain vinyl chloride, 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 and lutetium, with the proviso that when cerium is present, there is also at least one rare earth element other than cerium, the catalyst is characterized as having a BET surface area ranging from 12 to 200 m2/g, and where the atomic ratio of rare earth metal and the redox metal (iron and copper) in the catalyst is more than 10.

25. The composition according to paragraph 24, where M represents a mixture of at least two rare earth elements from lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium.

26. Composition according to any one of p and 25, where the composition is deposited on an inert carrier.

27. Composition according to any one of p-26, where the composition is a porous, granular material.

28. Composition according to any one of p-27, where the surface area BET is oppozitsii is from 30 to 200 m 2/year

29. Composition according to any one of PP-28, where the catalyst composition includes LaOCl.

30. Composition according to any one of PP-29 obtained by the process comprising the following stages:

(a) obtaining a solution of the chloride salt of rare earth element or elements in a solvent, representing either water, alcohol, or a mixture thereof;

(b) adding a nitrogen-containing base to cause the formation of sludge, and

(c) collecting, drying and calcination of the precipitate with the formation of the composition MOCl.

31. The catalytic composition of the formula MCl3to obtain vinyl chloride, 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 and lutetium, with the proviso that when cerium is present, then there is at least one rare earth element other than cerium, the catalyst is characterized as having a BET surface area of 5 to 200 m2/g, and where the atomic ratio of rare earth metal and the redox metal (iron and copper) in the catalyst is more than 10.

32. The composition according to p, where M represents a mixture of at least two rare earth elements from lanthanum, cerium, neodymium, praseodymium, dis is roziya, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium.

33. Composition according to any one of p-32, where the BET surface area of the composition is from 30 to 200 m2/year

34. Composition according to any one of p-33, where the catalyst includes LaCl3.

35. Composition according to any one of p-34, where the composition produced by the method comprising the following stages:

(a) obtaining a solution of the chloride salt of rare earth element or elements in a solvent, representing either water, alcohol, or a mixture thereof;

(b) adding a nitrogen-containing base to cause the formation of sludge;

(c) collecting, drying and calcination of the precipitate and

(d) contacting the calcined precipitate with a source of chlorine.

36. The composition according to p, where the source of chlorine is gaseous and is selected from HCl, Cl2and mixtures thereof.

37. Way catalytic dehydrochlorination raw materials containing one or more components selected from ethylchloride, 1,2-dichloroethane and 1,1,2-trichloroethane, using the composition 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 and lutetium, with the proviso that when cerium is present, is also present, m is Nisha least one rare earth element other than cerium, the catalyst is characterized as having a BET surface area ranging from 12 to 200 m2/g, and where the atomic ratio of rare earth metal and the redox metal (iron and copper) in the catalyst is more than 10.

38. The method according to clause 37, where in the formula describing the composition, M is a mixture of at least two rare earth elements from lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium.

39. The method according to any of p-38, where the composition is deposited on an inert carrier.

40. The method according to any of p-39, where the composition is a porous, granular material.

41. The method according to any of p-40, where the BET surface area of the composition is from 30 to 200 m2/year

42. The method according to any of PP-41, where the catalyst composition includes LaOCl.

43. The method according to any of PP-42, where the composition obtained by the process comprising the following stages:

(a) obtaining a solution of the chloride salt of rare earth element or elements in a solvent, representing either water, alcohol, or a mixture thereof;

(b) adding a nitrogen-containing base to cause the formation of sludge, and

(c) collecting, drying and calcination of the precipitate OBR is reattaching the composition MOCl.

44. Way catalytic dehydrochlorination raw materials containing one or more components selected from ethylchloride, 1,2-dichloroethane and 1,1,2-trichloroethane using the catalytic composition of the formula MCl3where M represents at least one rare earth element selected from lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium, with the proviso that when cerium is present, then there is at least one rare earth element other than cerium, the catalyst is characterized as having a BET surface area of 5 to 200 m2/g, and where the atomic ratio of rare earth metal and the redox metal (iron and copper) in the catalyst is more than 10.

45. The method according to item 44, where in the formula describing the composition, M is a mixture of at least two rare earth elements from lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium.

46. The method according to any of paragraphs 44 and 45, where the BET surface area of the composition is from 30 to 200 m2/year

47. The method according to any of paragraphs 44-46, where the catalyst includes LaCl3.

48. The method according to any of paragraphs 44-47, which composition produces the t way, includes the following stages:

(a) obtaining a solution of the chloride salt of rare earth element or elements in a solvent, representing either water, alcohol, or a mixture thereof;

(b) adding a nitrogen-containing base to cause the formation of sludge;

(c) collecting, drying and calcination of the precipitate, and

(d) contacting the calcined precipitate with a source of chlorine.

49. The method according to p, where the source of chlorine is gaseous and is selected from HCl, Cl2and mixtures thereof.

50. The method according to claim 1, where the used catalyst differs in that it is water soluble after a period of use in the method.

51. The method of producing vinyl chloride from ethylene by oxidehydrogenation, including:

combining reactants comprising ethylene, a source of oxygen and a source of chlorine in the reactor containing the catalyst at a temperature of 350-500°and pressures from atmospheric up to 3.5 MPa, i.e. under conditions sufficient to obtain the product stream comprising vinyl chloride and ethylene;

moreover, the catalyst includes one or more rare-earth materials, provided that the atomic ratio of rare earth metal and the redox metal (iron and copper) in the catalyst is more than 10, and the next time the proviso that when cerium is present, it can produce the p further includes, at least one rare earth element other than cerium.

52. The method according to 51, where the catalyst is a composition of the formula MOCl or MCl3where M represents a rare earth element or a mixture of rare earth elements selected from lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium.

53. The method according to paragraph 52, where the catalyst is a composition of the formula MOCl.

54. The method according to item 53, where the composition of the catalyst has a BET surface area ranging from 12 to 200 m2/year

55. The method according to any of PP and 53, in which the catalytic composition was prepared by a process comprising the following stages:

(a) obtaining a solution of the chloride salt of rare earth element or elements in a solvent, representing either water, alcohol, or a mixture thereof;

(b) adding a nitrogen-containing base to cause the formation of sludge, and

(c) collecting, drying and calcining the precipitate to form the composition MOCl.

56. The method according to paragraph 52, where the catalyst is a composition of the formula MCl3.

57. The method according to p, where the composition of the catalyst of the formula MCl3has a BET surface area of 5 to 200 m2/year

58. The method according to any of PP and 57, where the catalyst was prepared by a process comprising the following stages:

(a) aluchemie solution of the chloride salt of rare earth element or elements in a solvent, representing either water, alcohol, or a mixture thereof;

(b) adding a nitrogen-containing base to cause the formation of sludge;

(c) collecting, drying and calcination of the precipitate, and

(d) contacting the calcined precipitate with a source of chlorine.

59. The method according to any of PP-58, where the source of chlorine is a gas and represents at least one of the following gases: hydrogen chloride, chlorine, chlorinated hydrocarbons, containing movable chlorine, and mixtures thereof.

60. The method according to any of PP-59, where the ethane is mixed with ethylene, a source of oxygen and a source of chlorine in the reactor.

61. The method according to any of PP-60, where the component of the catalyst, which is a rare earth material, based on lanthanum, tserii, neodymium, praseodymium, dysprosium, Samaria, ytterbia, gadolinium, arbie, yttria, holmium, terbia, europium, tulie, de Lutece, or their mixtures.



 

Same patents:

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: 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

FIELD: chemistry of organochlorine compounds, chemical technology.

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

EFFECT: improved method preparing.

2 cl, 15 ex

FIELD: industrial organic synthesis.

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

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

4 cl, 1 tbl, 8 ex

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

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

EFFECT: method with high conversion ratio and selectivity.

3 cl, 2 ex

FIELD: organic synthesis catalysts.

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

EFFECT: reduced expenses on starting materials.

2 cl, 3 ex

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

The invention relates to a method of processing organochlorine waste by method of hydrogenolysis
The invention relates to a method for vinylidenechloride aqueous-alkaline dehydrochlorination 1,1,2-trichloroethane in the presence of a catalyst and an alcohol additive
The invention relates to a method for vinylidenechloride aqueous-alkaline dehydrochlorination 1,1,2-trichloroethane by the action of aqueous NaOH in the presence of a catalyst
The invention relates to a method for Pentafluoroethane containing 1-chloro-Pentafluoroethane less than 0.02 percent by weight

The invention relates to a method for separation of the products of pyrolysis of dichloroethane in the production of vinyl chloride

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

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