Iron oxide-based catalyst, preparation thereof and application in dehydrogenation process

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention provides catalyst based on iron oxide and lanthanide compound wherein at least part of iron oxide is prepared via a method including thermal decomposition of iron halide and which contains lanthanide in amount corresponding to 0.07 to 0.15 mole per mole iron oxide found in catalyst (calculated as Fe2O3). A catalyst is also described wherein part of iron oxide contains residual halide. Preparation of catalyst involves providing a mixture containing sufficient amounts of at least iron oxide and lanthanide compound followed by calcination of the mixture. Alkylaromatic compound dehydrogenation process is further described involving contact of raw feed containing alkylaromatic compound with above-described catalyst as well as polymer or copolymer production process involving production of alkenylaromatic compound as described above and subsequent polymerization thereof or copolymerization with a monomer.

EFFECT: enabled production of alkenylaromatic compounds with improved characteristics owing de decreased formation of by-products.

18 cl, 2 ex

 

The scope of the invention

The present invention relates to a catalyst based on iron oxide and method of producing the catalyst. The present invention relates also to a method for dehydrogenation of alkylaromatic compounds comprising contacting the feedstock containing alkylaromatic compound with the catalyst of this invention.

Background of the invention

Catalysts based on iron oxide used in the dehydrogenation of alkylaromatic compounds with formation of the corresponding alkanolamines connection as the main target of the product.

However, when using catalysts based on iron oxide in the dehydrogenation of alkylaromatic compounds has several adverse reactions which reduce the yield alkanolamine compounds and, therefore, adversely affect the economy of the process. One of these adverse reactions is the formation of coke on the catalyst (nauglerozhivaniya catalyst), which reduces its service life. Other adverse reactions include education alkylaromatics, mutilations and deaccelerating aromatic compounds. For example, in the dehydrogenation of ethylbenzene base product is styrene, and undesirable side products are coke, penlac is tilen, toluene and benzene.

From the point of view of the applicability and use of alkanolamine compounds, often at least partially remove alkylaromatics connection from the products of dehydrogenation. Such removal typically requires a separate step of the way, usually consisting of hydrogenation to alkanolamides connection with the use of the catalyst for selective hydrogenation.

In patents US-A-5190906 and ER AND-1027928 revealed that the source of iron oxide for use in the catalysts based on iron oxide may be a process involving thermal decomposition of an iron halide. In fact, such catalysts based on iron oxide obtained by thermal decomposition of an iron halide, contain residual halide of iron.

For example, used in industry for the dehydrogenation of alkylaromatic compounds dehydrogenation catalysts based on iron oxide obtained by thermal decomposition of an iron halide, optionally contain small amounts of lanthanide, for example of 0.066 mol per mole of iron oxide based on Fe2O3.

When using such industrial catalysts for the dehydrogenation of alkylaromatic compounds as a by-product is formed alkylaromatics connection. It is very the most important to reduce the selectivity for by-product - alkylaromatics connection. As used in the description of the selectivity for a particular connection shall mean the portion of alkylaromatic compounds, turned into a particular connection.

The invention

When using a catalyst based on iron oxide obtained by thermal decomposition of an iron halide and containing such halide, selectivity for alkylaromatics connection is reduced if the catalyst, as disclosed below, contains a certain amount of lanthanide.

This conclusion is not obvious, such as the presence of lanthanide in catalysts based on iron oxide obtained by other methods, does not lead to a measurable decrease in the selectivity alkylaromatics connection. Documents specified above prior art is silent on the specific impact of lanthanide on selectivity for alkylaromatics compounds, which, apparently, depends on the source of iron oxide and/or the presence of a halide.

Accordingly, the present invention provides a catalyst based on iron oxide and compounds lanthanide, in which at least part of the iron oxide obtained by the process comprising thermal decomposition of an iron halide, and which contains lanthanide in the amount of from 0.07 to 0.15 mol per mo is ü iron oxide, present in the catalyst based on Fe2O3.

The present invention also provides a catalyst based on iron oxide and compounds lanthanide, in which at least part of the iron oxide contains residual halide and which contains lanthanide in the amount of from 0.07 to 0.15 mole per mole of iron oxide present in the catalyst based on Fe2O3. In this embodiment, the content of residual halide, calculated as the ratio of the mass of the halogen to the weight of this part of the iron oxide is, in particular, in the range from 10 to 3000 ppm by weight, preferably from 50 to 2000 ppm

The present invention also provides a method of producing a catalyst containing iron oxide and lanthanide in the amount of from 0.07 to 0.15 mole per mole of iron oxide present in the catalyst based on Fe2O3that includes obtaining a mixture containing the iron oxide and the connection lanthanide, and calcination of the mixture, where at least part of the iron oxide obtained by the process comprising thermal decomposition of an iron halide.

The present invention also provides a method of producing a catalyst containing iron oxide and lanthanide in the amount of from 0.07 to 0.15 mole per mole of iron oxide present in the catalyst based on Fe2O3that includes getting MESI, containing iron oxide and a compound of lanthanide, and calcination of the mixture, where at least part of the iron oxide contains residual halide, and the amount, calculated as the ratio of the mass of the halogen to the weight of this part of the iron oxide is, in particular, in the range from 10 to 3000 ppm by weight, preferably from 50 to 2000 ppm

The present invention also provides a method for the dehydrogenation of alkylaromatic compounds, which comprises contacting the feedstock containing alkylaromatic compound, with a catalyst according to the present invention.

The present invention provides a method of applying alkanolamine compounds for polymers or copolymers comprising the polymerization alkanolamides connection with the formation of a polymer or copolymer containing Monomeric fragments obtained from alkanolamides connection, where alkanolamine compound obtained in the method of dehydrogenation of alkylaromatic compounds of the present invention.

Detailed description of the invention

As used in the description, unless otherwise specified, the amount of metal components in the catalyst and the original mixes, different from the components of iron, expressed as the ratio of the number of moles of metal to the total number of moles of iron oxide present is it in the catalyst, based on Fe2O3.

The catalysts of the present invention is based on the iron oxide obtained by thermal decomposition of an iron halide, optionally in an oxidizing atmosphere, where iron(II) is oxidized to iron(III). The halide may be chloride and/or bromide. Typically, the halide of iron is an iron dichloride, in particular trichloride iron. Thermal decomposition may include spray calcination, where the solution of a halide of iron is sprayed from a nozzle into a heated reaction chamber direct heating, as described in patent US-A-5911967, which put the link in this description. Alternative methods of thermal decomposition using a halide of iron in the form of gas or solids. Typically, a solution of iron halide is a so-called waste pickle liquor. The iron oxide obtained by thermal decomposition of an iron halide, can be further processed to reduce the content of iron halide or may not be treated before its use in this invention. Appropriate processing methods disclosed in patents US-A-5401485 and US A-5597547 who put links in the description.

Used in this invention, the iron oxide obtained by thermal decomposition of an iron halide, typically may contain staticguard, the amount of which is calculated as the ratio of the mass of the halogen by weight of iron oxide, in amounts of less than 3000 ppm, preferably less than 2000 ppm and in particular less than 1500 ppm, As a rule, it is preferable that the content of residual halide was low. On the other hand, in the practice of this invention are often residual halide, calculated as the ratio of the mass of the halogen by weight of iron oxide is more than 10 ppm, more preferably 50 ppm

The preferred catalyst may be obtained by combining yellow iron oxide with iron oxide obtained by thermal decomposition of an iron halide. The person skilled in the art knows that the yellow iron oxide is a hydrate of oxide of iron, often described as α-FeOOH or Fe2O3·H2O. Yellow iron oxide can be suitably used in an amount up to 50 wt.%, calculated as the ratio of the mass of Fe2O3to the total mass of iron oxide, based on the Fe2O3present in the catalyst. Preferably, the yellow iron oxide is used in amounts of 1 wt.%, in particular from 5 to 30 wt.%, on the same basis, for example 8.8 wt.%, at least 10, 15, 17 or 20 wt.%.

The iron oxide obtained by thermal decomposition of an iron halide, can be combined with minor amounts of other ACS is Dov iron or compounds, providing iron oxide, but this generally is not preferred. Examples of other iron oxides are black and red iron oxides. An example of the red iron oxide is the so-called red iron oxide Penniman (Penniman), i.e. iron oxide obtained by the method of Penniman, as, for example, described in patent US-A-1368748. Examples of compounds providing iron oxide include goethite, hematite, magnetite, maghemite, lepidocrocite and mixtures thereof.

In General, it is preferable that the content of iron oxide obtained by thermal decomposition of an iron halide present in the catalyst, calculated as the ratio of Fe2O3relative to the weight of the iron oxide based on Fe2O3that was at least 50 wt.%, in particular, at least 70 wt.% and up to 100 wt.%.

Lanthanid is usually lanthanid with atomic number between 57 and 66 (inclusive). Preferably, lanthanid represents lanthanum or, in particular, cerium. Lanthanid usually used in amounts of at least 0.08 mol, in particular at least 0.1 mole, per mole iron oxide. Lanthanid usually used in a total quantity of not more than 0.15 mol, preferably not more than 0.14 mole per mole of iron oxide, as it leads to an overall improvement in selectivity for the target alkenylamine the practical connection. For example, lanthanide can be used in the amount of 0.09 mol, or 0,113 mol, or 0,116 mol, or 0.12 mol, or 0,122 mol, or 0,123 mol, or 0,126 mol, or 0.15 mole per mole of iron oxide.

Typically, the catalyst may contain one or more compounds of molybdenum, tungsten, vanadium, copper and/or chromium as an additional component. Compounds of these metals can increase dehydrating activity of the catalyst. In preferred embodiments it is possible to use tungsten or, in particular, molybdenum. The total number of one or more of molybdenum, tungsten, vanadium, copper and chromium may typically be at least about 0.001 mol, preferably at least 0,005 mol per mole of iron oxide. Usually the total amount is not more than 0.1 mol, preferably not more than 0.05 mol, in particular not more than 0.02 mole per mole of iron oxide. For example, tungsten can be used in a number 0,0075 mol, or 0,0135 mol, or 0,0275 mol per mole of iron oxide; molybdenum can be used in quantity to 0.011 mol, or 0.018 mol, or 0.019 mol per mole of iron oxide; chromium can be used in a number 0,0085 mol or 0.035 mole per mole of iron oxide; vanadium can be used in an amount of 0.01 mol or 0,043 mol, or 0.045 mol, or 0.046 mol, or 0,047 mol per mole of iron oxide, and copper can be used in a number 0,006 mol or of 0.081 mol on the ol oxide iron.

Usually, as an additional component in the catalyst may contain one or more compounds of an alkali metal. Compounds of these metals tend to reduce the deposition of coke on the catalyst during the dehydrogenation and thus can increase the service life of the catalyst. In addition, they are able to increase the selectivity for the target alkanolamides connection. In preferred embodiments, the alkali metal is cesium or rubidium, or, in particular potassium. Alkali metals can usually be applied in a total amount of at least 0.2 mole, preferably at least 0.25 mol and in particular at least 0.3 mol, more preferably at least 0.45 mol and most preferably at least 0.55 mole per mole of iron oxide and, as a rule, not more than 5 mol, usually not more than 1 mole per mole of iron oxide. For example, alkali metals can be applied in the total number of 0,525 mol, 0,534 mol, or 0,575 mol, or of 0.615 mol, or 0,623 mol, or 0,629 mol, or 0,643 mol, or 0.85 mole per mole of iron oxide.

Typically, the catalyst may be present as an additional component of one or more compounds of the alkaline earth metal. Compounds of these metals can increase the selectivity for the target alkanolamides with whom the Association and to decrease the rate of decrease of catalytic activity. In preferred embodiments of the alkaline earth metal is magnesium, or, in particular, calcium. The amount of alkaline earth metal may be at least 0.01 mol, usually at least 0.02 mol, in particular at least 0.03 mole per mole of iron oxide. Usually the total amount is not more than 1 mol, usually not more than 0.2 mol, in particular not more than 0.13 mol, preferably not more than 0.1 mol per mole of iron oxide. For example, the total amount of alkaline earth metal may be 0,025 mol, or 0,026 mol, or 0,075 mol, or 0,076 mol, or 0,078 mol, or 0,079 mol, or was 0.138 mol, 0.14 mol per mole of iron oxide.

For the invention is not essential, what kind of connection lanthanide, molybdenum, tungsten, chromium, copper, vanadium, alkali or alkaline earth metal is used. Accordingly, these metal compounds may be independently selected from hydroxides, bicarbonates, carbonates, carboxylates, such as formate, acetates, oxalates and citrates; nitrates; oxides; molybdates; wolframates; chromates and Vanadate. Oxygen-containing compounds of the type molybdates, wolframates, chromates and Vanadate can be used in the form of an acid or a suitable salt, such as salt, potassium, calcium, magnesium, or any ammonium salt. Typically, the carboxylates are derived carbó the OIC acid number of carbon atoms up to 10, inclusive, preferably from 1 to 6 carbon atoms inclusive. Generally speaking, after annealing the metal compounds are usually present in the catalysts in the form of the corresponding metal oxides and therefore it is preferable to use metal compounds were suitable precursors of oxides of metals.

The ways through which can be obtained catalysts are not essential for the invention. Typically, the catalyst can be produced by obtaining from a mixture of oxide (oxide) iron and any additional components, such as those listed above, any metal compounds, in sufficient quantities by calcination of the mixture. The required number can be calculated based on the composition of the obtained catalyst. Examples of methods can be found in patents US-A-5689023, US A-5171914, US A-5190906, US B1-6191065 and EP-A-1027928 who put links in the description.

Before calcination, the mixture can be molded in any suitable form, such as tablets, spheres, pellets, saddles, shamrocks, chetyrehlistnik, rings, stars, hollow and solid cylinders. Adding a suitable amount of water, for example up to 30 wt.%, usually from 2 to 20 wt.%, based on the weight of the mixture may facilitate the molding process. If water is added, it can at least partially be removed before annealing. Suitable IU the odes molding include granulation, extrusion, pressing, spraying and spray drying. If desired, spray drying can continue roasting.

Additive for molding or additive for the extrusion can be used, for example, saturated or unsaturated fatty acid such as palmitic, stearic or oleic acid) or its salt, acid, polysaccharide derivative or its salt, or graphite, starch or cellulose. You can use any salt of a fatty acid or acid derivative of the polysaccharide, for example ammonium salt or salt of any metal above. The fatty acid may contain from 6 to 30 carbon atoms inclusive, preferably from 10 to 25 carbon atoms, inclusive. When using a fatty acid or acid derivative of the polysaccharide, it can be combined with a salt of the metal used in the manufacture of a catalyst, to obtain salts of fatty acids, or acid, the derivative of a polysaccharide. A suitable amount of additives for molding or extrusion is, for example, up to 1 wt.%, in particular from 0.001 to 0.5 wt.% based on the weight of the moldable mixture.

The annealing includes heating the mixture, usually in an inert or oxidizing atmosphere, such as nitrogen, helium or oxygen-containing gas, such as air, oxygen enriched air or mixtures of oxygen with inert gas. T is mperature calcination is usually at least 600°C, preferably at least 700°C. it Was found that during annealing at higher temperature, the catalyst shows, mainly, increased selectivity in relation to education alkanolamides connection. In the practical application of this invention, the temperature of calcination will be respectively not more than 1200°S, preferably not more than 1100°C. for Example, the annealing can be performed at 725°or 767°or 845°or 860°or 921°or 925°or 950°C. Typically, the duration of annealing is from 5 minutes to 12 hours, usually from 10 minutes to 6 hours, for example, for 15 minutes or 1.5 hours or 3 hours, or 5 hours.

The structure of the catalyst surface, usually on the basis of pore volume, average pore diameter and surface area, you can choose within a wide range. The person skilled in the art knows that it is possible to influence the structure of the surface by selecting the temperature and duration of annealing, as well as through the use of additives for the extrusion process.

Accordingly, the pore volume is at least 0.01 ml/g, preferably at least 0.05 ml/g, Respectively, the pore volume is less than 0.5, preferably less than 0.2, in particular, not more than 0.18 ml/g, in particular not more than 0.16 ml/g, for Example, pore volume which can be amount of 0.118 ml/g, or 0,122 ml/g, or 0,143 ml/year, Respectively, the average diameter of pores is at least 500 Åin particular at least 1000 Å. Accordingly, the average diameter of the pores is not more than 5000 Åin particular, less than 3000 Å. In the preferred embodiment of the invention, the average diameter of pores is in the range from 1200 to 2800 Å. For example, the average diameter of the pores may be 1360 Åor 2080 Åor 2670 Å. As used in the description, the values of the volumes of pores and average pore diameters measured by the method of mercury intrusion according to ASTM D4282-92 to absolute pressure 6000 psia (4,2×107PA using Micromeretics Autopore 9420: contact angle 130°, mercury with a surface tension 0,473 N/m). As used in the description, the average diameter of pores is defined as the diameter of pores, which achieved 50% of the total mercury intrusion.

The surface area of the catalyst is respectively in the range of from 0.01 to 20 m2/g, more preferably from 0.1 to 10 m2/g, for example 2,6 m2/d, or 3.4 m2/g or 4.9 m2/g, or 5 m2/, As used in the description, under the surface refers to the surface area determined by the BET method (Brunauer, Emmett and teller), as described in the Journal of the American Chemical Society, 60 (1938), pp. 309-316.

The crushing strength of the catalyst, respectively, at the extremely the very least, 10 N/mm, preferably, if it is in the range from 20 to 100 N/mm, for example, about 55 or 60 N/mm

The method of obtaining alkanolamine compounds according to the invention (hereinafter called "the way dehydrogenation) includes contacting the mixture containing alkylaromatic compound, with a catalyst of the present invention. Often the way dehydrogenation is a gas-phase process in which gaseous source mixture containing the reactants in contact with a solid catalyst. The catalyst, respectively, in the form of a fluidized bed of catalyst particles, or more suitably, in the form of a compacted layer. The method can be implemented as a periodic way. However, it is preferable to carry out the method of dehydrogenation as continuous. The person skilled in the art it will be obvious that additional dehydrogenation product is hydrogen and, therefore, dehydration is not the oxidative process. Examples of methods of carrying out the method of dehydrogenation can be found in patents US-A-5689023, US A-5171914, US A-5190906, US B1-6191065 and EP A-1027928 who put links in the description.

Usually, alkylaromatic compound is an alkyl substituted benzene, although it is possible to use other aromatic compounds, for example alkyl substituted naphthalene, anthracene or pyrid is N. Alkyl substituent may contain any number of carbon atoms of two or more, for example up to 6, inclusive. Suitable alkyl substituents are propyl (-CH2-CH2-CH3), 2-propyl (i.e. 1-methylethyl-CH(-CH3)2), butyl (-CH2-CH2-CH2-CH3), 2-methylpropyl (-CH2-CH(CH3)2) and hexyl (-CH2-CH2-CH2-CH2-CH2-CH3), in particular ethyl (-CH2-CH3). Examples of suitable alkylaromatic compounds are butylbenzoyl, hexylbenzoyl, (2-methylpropyl " benzene, (1-methylethyl)benzene (i.e. cumene), 1-ethyl-2-methylbenzol, 1,4-diethylbenzene, in particular ethylbenzene.

It is advantageous to use water as an additional component of the original mixture, preferably in the form of steam. The presence of water will reduce the rate of coke deposition on the catalyst during the method of dehydrogenation. Usually the molar ratio of water and alkylaromatic compounds in the mixture is from 1 to 50, more preferably from 3 to 30, such as 5 or 10.

The method of dehydrogenation is usually carried out at a temperature in the range from 500 to 700°C, preferably from 550 to 650°With, for example 600°or 630°C. In one embodiment of the method of dehydrogenation isothermal hold. In other embodiments, the method of dehydrogenation Prov the field, and o adiabatically where these temperatures are the temperatures at the inlet of the reactor, and during the dehydrogenation temperature can be reduced typically by up to 150°S, more preferably 10 to 120°C. the Absolute pressure is usually in the range from 10 to 300 kPa, more preferably from 20 to 200 kPa, 50 kPa and 120 kPa.

Optionally, you can use one, two or more reactors, for example three or four. The reactors can be connected in series or in parallel. They can work individually and independently from each other, and each reactor can operate either in the same or in different conditions.

When carrying out the method of dehydrogenation as a gas-phase method using a reactor with a thickened layer average velocity of the fluid (LHSV) may preferably be in the range from 0.01 to 10 l/(l.h), more preferably in the range from 0.1 to 2 l/(l.h). As used here, the term "LHSV" refers to average hourly feed rate of the liquid, which is the volumetric rate of liquid flow of hydrocarbons, measured under normal conditions (i.e., 0° and 1 bar abs)divided by the volume of the catalyst layer or the total amount of catalyst, if there are two or more layers of catalyst.

In preferred embodiments of the invention conditions the way digid the investments chosen so that to the conversion of alkylaromatic compounds was in the range of from 30 to 80 mol.%, more preferably in the range from 35 to 75 mol.%, for example, 40 mol.% or 67 mol.%.

Alkenylamine connection you can select from the products of the method of dehydrogenation by any known means. For example, a method of dehydrogenation may include fractional distillation or reactive distillation. If desired, the method of dehydrogenation may include stage hydrogenation, in which at least part of the product is subjected to hydrogenation, whereby at least part alkylaromatic compounds, if present, becomes alkenylamine connection. Part of the product is subjected to hydrogenation, may be part of a product enriched alkylaromatics connection. Examples of such hydrogenation is known in this field. For example, the present invention can be easily applied methods known from patent US-A-5504268, US A-5156816 and US A-4822936 who put links in the description.

An advantage of the present invention is the fact that the number alkylaromatics compounds present in the dehydrogenation product, if any, less the amount obtained without the use of an invention that makes it less necessary to use phase hydrogenation, or stage of hiderow the deposits can be realized with a smaller amount of catalyst in relation to the initial mixture, or in more mild conditions. Another advantage of this invention is that the way to an improved dehydrogenation activity for a given selectivity or improved selectivity for a given activity, in particular when applied alkali metal with a relatively large number, for example at least 0.45 mol, in particular at least 0.55 mole per mole of iron oxide, preferably in combination with a large number of lanthanide, for example at least 0.07 mol, in particular at least 0.1 mol per mole of iron oxide. Such catalysts also tend to provide improved stability when working in the way dehydrogenation, at low molar ratio of water to alkylaromatic compound, for example less than 10, in particular not more than 7.

Alkanolamine compound obtained by the method of dehydrogenation of the present invention, can be used as a monomer for polymerization and copolymerization. For example, the styrene can be used in the production of polystyrene, styrene/diene rubbers, etc. Improved catalytic activity obtained with this invention, provides a more attractive method of obtaining alkanolamides connection and simultaneously leads to more Pref is Ekaterina method, including getting alkanolamides connection, and the subsequent use of the obtained alkanolamine compounds in the production of polymers and copolymers containing Monomeric units alkanolamine compounds. Information on applicable polymerization catalysts, polymerization processes and methods of processing of polymers and the use of the obtained polymers can be found in "Encyclopedia of Polymer Science and Engineering" 2nd Edition, Ed. N. F. Marks et al., New York, vol. 16, pp. 1-246), including references in this source, which is entered into the description by reference.

The invention is illustrated in the following non-limiting examples.

Example 1

The paste is prepared by mixing the following ingredients: iron oxide obtained by thermal decomposition of iron halide (regenerated iron oxide hoogovens and becomes, type RIO-250), yellow iron oxide (Bayer, type 920Z), cerium carbonate, potassium carbonate, molybdenum trioxide, calcium carbonate and water (about 10 wt.% in relation to the weight of the dry mixture). The pasta is made by extrusion in cylinders with a diameter of 3 mm and a length of 6 mm Tablets are dried in air at 170°C for 15 h and then calcined in air at 825°C for 1 h, After annealing the composition of the catalyst was as follows: of 0.615 mol of potassium, 0.12 mol of cerium, 0,0175 mol of molybdenum and 0.025 mole of calcium per mole of iron oxide based on F 2O3. The number of yellow iron oxide, in the form of Fe2O3that is 8.8% relative to the total amount (number of moles) of iron oxide in the form of Fe2O3contained in the catalyst.

To obtain styrene from ethylbenzene in isothermal testing conditions in the reactor of continuous operation were used, three samples of the catalyst. The samples were tested in three separate experiments. Each experience has complied with the following conditions: the absolute pressure of 76 kPa, the molar ratio of steam to ethylbenzene, equal to 10 LHSV 0.65 l/LC each experience a steady state was reached after 400 h and the temperature was chosen so that each experience was achieved 70% molar conversion of ethylbenzene. In three experiments, the temperature was 584,4, 582,6 and 584,6°i.e. on average 583,9°C. the Selectivity for styrene averaged 94,4 mol.%.

To obtain styrene from ethylbenzene in three separate experiments were used, three samples of the catalyst, as described in the previous paragraph, with the difference that the molar ratio of steam to ethylbenzene was equal to 5 instead of 10 and the absolute pressure was reduced from 76 to 40 kPa. In three experiments, the temperature was 596,8, 597,4 and 596,8°i.e. on average, 597,0°C. the Selectivity to styrene was on average of 96.2 mol.%.

Example 2

The first experiment was established and carried out similarly to example is 1. In the experiments varied the following quantities of components:

- potassium: 0,515, of 0.565 and of 0.615 mol/mol Fe2O3,

- calcium: 0.025, 0.050 and 0,075 mol/mol Fe2O3,

- cerium: 0,050, 0.085 and 0,120 mol/mol Fe2O3,

- molybdenum: 0,005, 0,0175 and being 0.030 mol/mol Fe2O3,

- copper: 0, 0.050 and 0.100 mol/mol Fe2O3,

- chrome: 0, 0.050 and 0.100 mol/mol Fe2O3,

yellow iron oxide: 0, 10 and 20 wt.% in relation to the total number of iron oxide; and

- temperature annealing: 725, 825 and 925°C.

It was studied the influence of these parameters on receipt of styrene from ethylbenzene.

It was shown that increasing the amount of cerium leads to a significant decrease in the selectivity for phenylacetylene.

This result was confirmed by a second series of experiments, which differed from the first by the fact that molybdenum is present in a fixed amount of 0,0175 mol/mol Fe2O3and copper and chromium were missing.

For comparison, we conducted a similar test experiments with red iron oxide Penniman instead of the iron oxide obtained by thermal decomposition of an iron halide. In this series used the following quantities of components:

- calcium: 0,025, of 0.075 and 0.125 mol/mol Fe2O3,

- cerium: 0,050, of 0.075 and 0.100 mol/mol Fe2O3and

- molybdenum: 0,010, 0,030 and 0,050 mol/mol Fe2O3.

the Amount of potassium was 0,550 mol/mol Fe 2O3and copper and chromium were absent; the temperature of annealing was 825°C. it Was found that increasing the amount of cerium does not lead to a noticeable decrease in the selectivity for phenylacetylene.

1. The catalyst based on iron oxide and compounds lanthanide, in which at least part of the iron oxide obtained by the process comprising thermal decomposition of an iron halide, and which contains lanthanide in the amount of from 0.07 to 0.15 mole per mole of iron oxide present in the catalyst based on Fe2About3.

2. The catalyst according to claim 1, in which the iron oxide obtained by the process comprising thermal decomposition of an iron halide, contains a halide in an amount of from 10 to 3000 ppm by weight, in particular from 50 to 2000 ppm by mass.

3. The catalyst based on iron oxide and compounds lanthanide, in which at least part of the iron oxide contains residual halide and containing lanthanide in the amount of from 0.07 to 0.15 mole per mole of iron oxide present in the catalyst based on Fe2About3.

4. The catalyst according to claim 3, in which the content of residual halide is in the range from 10 to 3000 ppm by weight, in particular from 50 to 2000 ppm by weight, calculated as the ratio of the mass of the halogen by weight parts iron oxide containing residual halide.

5. The catalyst is about any one of claims 1 to 4, where lanthanide is cerium.

6. Catalyst according to any one of claims 1 to 4, based, in addition, the connection of an alkali metal, in particular potassium, where the catalyst contains an alkali metal in a total amount of at least 0.45 mol per mole of iron oxide present in the catalyst based on Fe2About3in particular, in amounts of from 0.55 to 5 mol per mole of iron oxide present in the catalyst based on Fe2About3.

7. Catalyst according to any one of claims 1 to 4, which has a pore diameter of more 5000 Å.

8. Catalyst according to any one of claims 1 to 4, based, in addition, the compound of alkaline-earth metal, particularly calcium and/or magnesium, preferably calcium, where the catalyst contains an alkali-earth metal in a total amount from 0.01 to 0.2 mol per mole of iron oxide present in the catalyst based on Fe2About3in particular, in amounts of from 0.02 to 0.13 mol per mole of iron oxide present in the catalyst based on Fe2O3.

9. Catalyst according to any one of claims 1 to 4, based, in addition, the compound of molybdenum, tungsten, vanadium, copper and/or chromium, in particular, the compound of molybdenum and/or tungsten, which contains molybdenum, tungsten, vanadium, copper and/or chromium in a total amount of from 0.001 to 0.1 mol per mole of iron oxide present in kata is isatori, based on Fe2About3in particular, in amounts of 0.005 to 0.05 mol per mole of iron oxide present in the catalyst based on Fe2About3.

10. Catalyst according to any one of claims 1 to 4, which has a pore diameter of less than 3000, in particular in the range from 1200 to 2800 Å.

11. Catalyst according to any one of claims 1 to 4, based, moreover, on a yellow iron oxide.

12. The catalyst according to claim 11, in which yellow iron oxide contains up to 50 wt.%, in particular, in the range from 1 to 30 wt.%, calculated as the mass ratio of Fe2About3to the total mass of iron oxide based on Fe2O3present in the catalyst.

13. The method of producing catalyst according to any one of claims 1 to 12, comprising obtaining a mixture containing a sufficient amount of at least iron oxide and compounds lanthanide, and calcining the mixture.

14. The method according to item 13, in which the temperature of calcination is in the range from 600 to 1200°With, in particular, in the range from 700 to 1100°C.

15. The method of dehydrogenation of alkylaromatic compounds comprising contacting the mixture containing alkylaromatic compound, with a catalyst according to any one of claims 1 to 12.

16. The method according to clause 15, which is carried out in the presence of water at a molar ratio of water to the alkylaromatic compound is less than 10.

17. Method n is 15 or 16, in which alkylaromatic compound is ethylbenzene.

18. A method of obtaining a polymer or copolymer containing the following stages:

a) obtaining alkanolamides connection method according to any one of p-17,

b) polymerization of the specified alkanolamides connection together with an additional monomer, if necessary, with the formation of the polymer or copolymer.



 

Same patents:

FIELD: polymers, chemical technology.

SUBSTANCE: invention describes a method for preparing frothing polystyrene by polymerization of styrene for two stages. At the first stage forpolymerization is carried out in the presence of antipyrene, a chain growth regulator, benzoyl peroxide as a polymerization initiating agent. At the second stage the suspension polymerization is carried out in aqueous medium in the presence of polyvinyl alcohol as a stabilizing agent, chain growth regulator, tert.-butylperbenzoate as initiating agent and frothing agent. The forpolymerization stage is carried out in the presence of water and dicumyl peroxide as antipyrene synergist is added additionally, and O,O-tert.-myl-O-(2-hexyl)-monoperoxycarbonate is used a additional initiating agent in the following ratio of components relatively to styrene mass, %: benzoyl peroxide : O,O-tert.-myl-O-(2-hexyl)-monoperoxycarbonate : tert.-butylperbenzoate = (0.24-0.25):(0.04-0.06):(0.04-0.10), respectively. Method provides intensification of the styrene polymerization process, improvement of granulometric composition of preparing polystyrene and reducing specific energy consumptions in manufacturing frothing polymer granules.

EFFECT: improved preparing method.

3 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention describes a method for preparing styrene polymers by emulsion polymerization reaction in the presence of emulsifying agent and cobalt-organic initiating agent with tridentate ligands alkyl-{2-[(2-aminoethyl)imino]pent-3-ene-4-olate}(1,2-ethanediamine)cobalt (III) halides. As an initiating agent methods involves using a mixture consisting of initiating agent with alkyl ligand of normal structure and initiating agent with alkyl ligand of branched structure wherein their the sum concentration is 0.05-0.2 mas. p. per 100 p. p. of monomer and their ratio is from 2:1 to 9:1. The process is carried out at temperature 10-80°C and pH 4-10. Invention provides reducing the inductive period and possibility for using monomers with industrial treatment degree, i. e. stabilizing agent-containing monomers.

EFFECT: improved method for preparing.

5 cl, 1 tbl, 9 ex

FIELD: organometallic polymerization catalysts.

SUBSTANCE: invention relates to alkylcobalt(III) complexes with tridentate Schiff's bases wherein alkyl ligand contains functional group, notably hydroxyl, carboxyl, or amino group, in accordance with general formula:

(I),

in which W represents two-moiety unsaturated hydrocarbon bridge group expressed by formula =C(H)=C(CH3)- (propene-1,2-diyl) or o-C6H4 (o-phenylene); X is OH, NH2 or COONa; Y monovalent anion: Cl-, Br-, NO3- or ClO4-; and Z polymethylene bridge group (CH2)n, wherein n=3-11 when X = OH or NH2 and n=2-11 when X = COONa. The complex are used as initiators of emulsion polymerization and copolymerization of diene and vinyl monomers to produce reactive bifunctional oligomers and polymers with terminal functions, which oligomers and polymers are suitable for further conjugation with corresponding reagents.

EFFECT: extended choice of specific polymerization catalysts.

3 tbl, 30 ex

The invention relates to new compounds, such as poly(monoperoxyphthalate) the overall structure AND

< / BR>
where R, R1and n are defined in the summary of the invention, such as 1,1,1-Tris(tert-butylperoxycyclohexyl)ethane, intermediate compounds for their production, and methods for their production and use

The invention relates to the chemistry of polymers, namely, to obtain self-extinguishing expandable polystyrene, which is widely used as heat and sound insulation material in construction, including public buildings, as well as for making furniture, packing and so on

The invention relates to the production of film-forming oligomers of styrene, which can be used to prepare coatings

The invention relates to plastics industry, in particular the production of self-extinguishing polystyrene, which is widely used for the manufacture of heat-insulating plates in the construction and soft packaging

The invention relates to technology of polymers, in particular to methods for polystyrene latex, and can be used in the production of those for various applications (production of foam, water-based paints, coated paper, etc.)

A method of obtaining polystyrene latex by the emulsion polymerization of styrene with the introduction of the emulsifier and monomer during the process [1] However, this method does not allow to obtain a concentrated latex, sustainable synthesis

The invention relates to plastics industry, namely to obtain polystyrene polymerization of polystyrene suspension

FIELD: petrochemical process catalysts.

SUBSTANCE: reaction gas is passed in reaction zone through at least one fixed catalyst bed wherein reaction gas is subjected to dehydrogenation to produce molecular hydrogen and at least one dehydrogenated hydrocarbon. Reaction gas, before and/or after entering reaction zone, is supplemented by at least one molecular oxygen-containing gas, which partially oxidizes molecular hydrogen contained in reaction gas to form water steam. Gas product containing molecular hydrogen, water steam, at least one dehydrogenated hydrocarbon, and at least one hydrocarbon to be dehydrogenated is withdrawn from reaction zone, and divided into two parts, one of which is recycled into reaction zone.

EFFECT: simplified process and increased propylene formation selectivity.

12 cl, 2 dwg, 3 tbl, 4 ex

FIELD: petrochemical processes.

SUBSTANCE: invention concerns reactor with fluidized bed of fine catalyst, which reactor contains upright cylindrical body, sectioning grids with their free area increasing along the height of reactor, connecting pipes for supplying feedstock and evacuating contact gas, and receiving and withdrawing recycled catalyst, and cyclones with dust-removing risers. More specifically, upper grid has free area larger than 60 and lesser than 90% of the body section, ends of connecting pipes receiving recycled catalyst and ends of dust-removing risers are disposed above upper grid and below fluidized bed.

EFFECT: increased output of reactor, improved performance of dehydrogenation (increased yield of olefins and reduced consumption of catalyst), and improved environmental condition.

1 dwg

FIELD: petrochemical processes.

SUBSTANCE: feed stream is passed with admixed oxygen and diluent through catalyst bed at 400-500°C and constant flow rate 50 mL/min, said catalyst being catalytic system for heterogeneous reactions and representing geometrically structured system including microfibers of high-silica fibrous carrier, which is characterized by presence in IR absorption band of hydroxyl groups with wave number ν=3620-3650 cm-1 and half-width 65-75 cm-1. The carrier has specific surface as measured according to BET method from heat desorption of argon SAr=0.5-30 m2/g, surface area as measured by alkali titration method SNa=5-150 m2/g at ratio SNa/SAr=5-50, and at least one active element, whose principal portion is composed in the form of charged either metallic, or bimetallic clusters characterized in UV-vis diffuse reflection spectrum by specific bands in the region 34000-42000 cm-1 and ratio of integral intensity of band attributed to charged either metallic, or bimetallic clusters to integral intensity of band belonging to, respectively, either metallic, or bimetallic particles is not less than 1.0.

EFFECT: increased choice of oxidative dehydrogenation catalysts.

4 cl, 5 ex

FIELD: petrochemical processes.

SUBSTANCE: branched olefins are obtained via dehydrogenation of isoparaffin composition containing 0.5% or less quaternary aliphatic carbon atoms in presence of suitable catalyst. Isoparaffin composition is prepared via hydrocracking and hydroisomerization of paraffin wax and contains paraffins with 7 to 18 carbon atoms, these paraffins or at least a part of them are branched with average number of branches between 0.5 and 2.5 per paraffin molecule, the branches including methyl and optionally ethyl ones. Original paraffin wax is prepared using Fischer-Tropsch reaction. Resulting branched olefins are characterized by content of quaternary aliphatic structures 0.5% or less. Branched aromatic hydrocarbon and compositions of branched olefins, branched aromatic hydrocarbon, and branched alkylarenesulfonates are also disclosed.

EFFECT: improved quality characteristics of target products.

10 cl, 19 ex

FIELD: petrochemical processes.

SUBSTANCE: branched olefins are obtained via catalytic dehydration of isoparaffin composition including 0.5% or less of quaternary aliphatic carbon atoms. This isoparaffin composition comprises paraffins with number of carbons within a range of 7 to 35, said paraffins or at least a part thereof being branched with average number of branches from 0.7 to 2.5 and said branches including methyl and optionally ethyl branches. Indicated isoparaffin composition with is obtained via hydrocracking and hydroisomerization of wax. Thus obtained branched olefins contain 0.5% or less of quaternary aliphatic carbon atoms.

EFFECT: upgraded quality characteristics of desired products.

8 cl, 4 tbl, 11 ex

FIELD: industrial organic synthesis.

SUBSTANCE: ethylbenzene blend obtained through blending fresh ethylbenzene and recycled ethylbenzene with styrene content not above 0.1 wt % is subjected to catalytic dehydrogenation in presence of water steam at feed-to-steam weight ratio 1:2, temperature 600°C, ethylbenzene blend supply space velocity 0.5-1.0 h-1, and reactor pressure maintained within a range of 45 to 80 kPa absolute. Multistep rectification gives rectified styrene with concentration of desired product at least 99.8% and phenylacetylene impurity level not higher than 0.01 wt %. Recycled ethylbenzene is blended with fresh ethylbenzene and resulting ethylbenzene blend containing no more than 0.1 wt % styrene is supplied to dehydrogenation unit.

EFFECT: increased ethylbenzene-to-styrene conversion, improved process selectivity, and reduced level of phenylacetylene in commercial product.

5 tbl

FIELD: petrochemical industry; methods of production of styrene.

SUBSTANCE: the invention is pertaining to the field of petrochemical industry, in particular, to the method of production of styrene. The invention provides for dehydrogenation of the ethylbenzene charge gained after mixing of the fresh ethylbenzene with the recycled ethylbenzene on the ferrioxide catalytic agent at presence of the steam at the mass ratio of the raw to the steam of no less than 1:2, at the temperature of 580-640°С and the volumetric speed of feeding of the ethylbenzene charge of 0.23-0.45 m3/h. The hydrocarbon condensate (the product of the dehydrogenation) containing styrene, the unreacted ethylbenzene, the by-products including the phenyl acetylene impurity before the stage of the rectification is hydrogenated using the palladium-containing catalytic agents at the temperature of 20-30°С, the volumetric speed of 4.5-5.0 m3/h-1 and at the volumetric ratio of the hydrogen : raw - 35-45. The technical result of the invention is the increased purity of the produced styrene without reduction of productivity of the whole process of the marketable styrene.

EFFECT: the invention ensures the increased purity of the produced styrene without reduction of productivity of the whole process of the marketable styrene.

1 tbl, 8 ex

FIELD: organic chemistry, chemical technology, catalysts.

SUBSTANCE: invention describes a catalyst for dehydrogenation of (C2-C5)-hydrocarbons that comprises aluminum, chrome oxides, compound of modifying metal, alkaline and/or alkaline-earth metal. Catalyst comprises additionally silicon and/or boron compounds and as a modifying agent the proposed catalyst comprises at least one compound chosen from the following group: zirconium, titanium, iron, gallium, cobalt, molybdenum, manganese, tin. The catalyst is formed in the process of thermal treatment of aluminum compound of the formula Al2O3. n H2O wherein n = 0.3-1.5 and in common with compounds of abovementioned elements and shows the following composition, wt.-% (as measure for oxide): chrome oxide as measured for Cr2O3, 12-23; compound of a modifying metal from the group: Zr, Ti, Ga, Co, Sn, Mo and Mn, 0.1-1.5; silicon and/or boron compound, 0.1-10.0; alkaline and/or alkaline-earth metal compound, 0.5-3.5, and aluminum oxide, the balance. Catalyst shows the specific surface value 50-150 m2/g, the pore volume value 0.15-0.4 cm3/g and particles size 40-200 mcm. Also, invention describes a method for preparing this catalyst. Invention provides preparing the catalyst showing the enhanced strength and catalytic activity.

EFFECT: improved and valuable properties of catalyst.

12 cl, 2 tbl

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention provides catalytic composition for dehydration of alkylaromatic hydrocarbons optionally combined with ethane comprising: carrier consisting of alumina in δ phase or in θ phase, or in mixed δ+θ or θ+α, or δ+θ+α phase, modified with silicon oxide and having surface area less than 150 m2/g as measured by BET method; 0.1-35% gallium in the form of Ca2O3; 0.01-5% manganese in the form of Mn2O3; 0-100 ppm platinum; and 0.05-4% alkali or alkali-earth metal oxide, all percentages being based on the total weight of composition. Other variants of composition are also covered by invention. Methods of preparing such catalytic composition (options) envisage use of alumina-based carrier in the form of particles corresponding to group A of the Geldart Classification. Process of dehydration of alkylaromatic hydrocarbons optionally combined with ethane comprises: (i) dehydration of hydrocarbon stream optionally mixed with inert gas in fluidized-bed reactor in presence of catalytic composition consisted of alumina-supported and silica-modified gallium and manganese at temperature within a range of 400 to 700°C, total pressure within a range of 0.1 to 3 atmospheres, and gas hourly space velocity from 50 to 10000 h-1; and (ii) regeneration and heating of catalyst caused by catalytic oxidation of fuel in fluidized-bed reactor at temperature above 400°C.

EFFECT: increased activity of catalytic composition and prolonged lifetime thereof.

22 cl, 2 tbl, 16 ex

FIELD: petroleum chemistry, organic chemistry, chemical technology.

SUBSTANCE: method involves contacting the parent raw flow in the flow-type reactor with oxygen-free gas flow at increased temperature with a catalyst comprising a precious metal of VII group of the periodic system of elements. The industrial isomerization platinum-containing catalyst SI-1 or industrial hydrogenation catalyst "palladium on active aluminum oxide in sulfured form" is used as a catalyst. Contact of the parent raw with catalyst is carried out by its feeding in inert gas flow, for example, nitrogen at the volume rate 1-2 h-1 at temperature 320-370°C in the presence of the additive representing a solution of hydroquinone or p-benzoquinone in isopropyl alcohol and taken in the concentration 0.01-0.5 mole/l wherein the additive is fed to the parent raw flow in the amount 5-30 vol.%. Invention provides carrying out the highly selective isomerization and cyclization of light petroleum fractions in on industrial Pt- and/or Pd-containing catalysts with the high yield of the end products no containing aromatic compounds and not requiring the presence of hydrogen or hydrogen-containing gas for its realization and regeneration of the catalyst.

EFFECT: improved method for isomerization.

4 cl, 2 tbl, 2 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to production of alkylaryl hydroperoxides useful as starting material in production of propylene oxide and alkenylaryl. Process of invention comprises following stages: oxidation of alkylaryl compound to form reaction product containing alkylaryl hydroperoxide; contacting at least part of reaction product with basic aqueous solution; separation of hydrocarbon phase containing alkylaryl hydroperoxide from aqueous phase; containing at least part of above hydrocarbon phase with aqueous solution containing waste water, said aqueous solution containing less than 0.2% alkali metal and/or salt (determined as ratio of metal component to total amount of solution); and separation of hydrocarbon phase from aqueous phase. By bringing at least part of above hydrocarbon phase containing alkylaryl hydroperoxide into interaction with propylene and catalyst, alkylaryl hydroxide and propylene oxide are obtained. At least part of propylene oxide is then separated from alkylaryl hydroxide. Dehydration of at least part of alkylaryl hydroxide results in formation of alkenylaryl.

EFFECT: reduced amount of contaminating by-products in alkylaryl hydroperoxide preparation stage.

8 cl, 4 ex

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