Method periodic regeneration with hydrogen deactivated solid catalyst alkylation
(57) Abstract:The invention relates to the regeneration of the solid catalyst, which comprises the reaction product of a metal halide selected from the group comprising aluminum, zircaloy, tin, tantalum, titanium, gallium, antimony, phosphorus, iron, boron and their mixture, and bound surface hydroxyl groups of the refractory inorganic oxide and metal with zero valency selected from the group comprising platinum, palladium, Nickel, ruthenium, rhodium, osmium, iridium, and their mixture. Method for periodic regeneration of the catalyst is partially deactivated when the liquid-phase alkylation of C2-6-alkene C4-6-alkanol is the output of the catalyst of liquid-phase hydrocarbons and processing of the resulting catalyst with hydrogen at 6.9 - 13790 kPa and 10-300oC for 1 to 20 hours Method is effective in restoring the lost activity and through many cycles of regeneration. 5 C.p. f-crystals. Even in the era of antiknock additives, such as tetraethyl lead, used as a component of motor fuel alkylates is widespread and is important. In subsequent years, alkylates, should become a more important component of motor fuel is estaet, since the composition of gasoline varies in response to concern about the environment and in accordance with the legislation in some parts of the world. These government regulations most relevant to the increasing importance of alkylates relate to the lead and Bhutan. Antiknock additive of lead compounds is the most easy way to increase the octane number of gasoline, but due to continuing concern about the impact of the discharge lead you gradually removed lead from gasoline, which is already made in the USA more than 90%. Bhutan is another effective auxiliary agent that increases the octane number, but has a tendency to evaporate from gasoline, especially in warm weather, contributing to smog formation. Under current U.S. rules he has almost completely removed from gasoline.The term "alkylate" usually refers to a complex mixture resulting from the alkylation of olefins present or formed in the flow of the feed olefins, C2-C6intermediate products, primarily formed from alkanes, mainly branched alkanes, predominantly alkanolamine, to a complex mixture of products labelled as alkylate contained mainly trimethylpentane, as they are violachannel components that significantly improve the quality of motor fuels, in addition, the chemistry of alkylation as a result of several major chemical reactions characteristic ion of carbon, which plays a Central role in the process of alkylation. Thus, the transfer chains (intermolecular hydrogen transfer and offset alkyl), oligomerization and disproportionation are to be placed in the alkylate as by-products substance with 5 to 12 carbon atoms plus the carbon atoms from a feed material containing only4olefins and alkanes.The alkylation of olefins typically catalyze strong acids. Although this alkylation was in the focus of intensive and continuous research over several decades, the requirements for optimal selectivity at high conversion had limited commercial catalyst selection for all practical purposes sulfuric acid and liquid hydrogen fluoride. Despite the fact that a process based on each of these acids, have achieved commercial approval, enerali HF. A brief but useful overview of how alkylation using HF as a catalyst represented by B. R. Shah in "Handbook of Petroleum Refining Processes" R. A. Meyers, editor, McGraw-Hill Book Company, 1986, cc.1-3 1-28.In an overly simplified description of the process of alkylation catalyzed by HF, as follows. Submitted olefin and isobutane (HC) streams are combined and mixed with HF in a reaction zone alkylation. Stemming from the reactor stream is divided into the desired alkylate, acid and other light gases, which are mostly unreacted isobutane. HF or immediately return to the reactor, or before that regenerate in whole or in part. Unreacted CYCLOBUTANE again fed into the reactor, and the alkylate is then used for making motor fuel.Currently in the United States show interest in HF (hydrofluoric acid) in the sense of its impact on the environment. Hydrofluoric acid is classified as high-risk substance (Acutely Hazardous Material), and in southern California the appropriate Department (Board of South Coust Air Quality Management District) requires recently stop using for HF alkylation prior to 1 January 1998. Believe that this reduction should be universal tendenziell of alkylates. It is crucial to have as an effective catalyst is a solid acid, which will help develop the process with a fixed bed of the catalyst (a necessary alternative in the oil industry).One of the permitted solid alkylation catalysts C2-C6of olefins, alkanes containing 4 to 6 carbon (hereinafter, a process designated as a motor fuel alkylation) is the reaction product between one or more metal halides, active catalysts reaction Friedel -, and a refractory inorganic oxide containing dispersed metal, with activity in hydrogenations of olefins. Such catalyst is well known in practice, as illustrated by examples in the description of U.S. patent A-2999074, and include, for example, the reaction product of aluminum chloride and aluminum oxide containing platinum with zero valency. Typically, these catalysts are deactivated when using when decontamination is measured by the percent conversion of the olefin, and this requires a means of repeated regeneration of these catalysts, that is, to restore their activity, to use their catalyt is minimally destructive to the process of alkylation of motor fuel. However note that most requires that the catalyst has not acted conditions or agents that are extraneous to the process of alkylation. In addition, it is necessary to minimize the regeneration time relative to the time of alkylation. Indeed, if the full cycle is the amount of time during which the catalyst used in the alkylation (cycle time alkylation), and the time during which the catalyst regenerate (the time of the regeneration cycle), it is necessary that the latter was as short as possible. Of course, the ideal time of the regeneration cycle is zero, but this corresponds to the case when the catalyst is not deactivated, which, unfortunately, contrary to practice.Found a simple and yet effective way of regeneration of the deactivated catalyst satisfying all the above criteria. More detail is found that after removal of the deactivated catalyst liquid hydrocarbon treatment catalyst with hydrogen at approximately the same pressure as the pressure used in the alkylation, and at a sufficiently low temperature provides almost complete regeneration, often improving the quality of productgeneral and requires suitable from a commercial point of view time.The patent US-A--4098833 relates to the regeneration of the catalyst (metal halide and acid of Bronsted containing fluorine), where as the alkylation catalyst, you can use the deactivated catalyst using hydrogen and selected hydrogenation component on a noble metal. The catalyst of the known patent is different from the catalyst used in the present invention, in many respects, including the fact that the first catalyst without carrier liquid and always includes a fluorine-containing acid of Bronsted.Muller and others in the U.S. patent US-A-3318820 describes the regeneration of the isomerization catalyst consisting essentially of the reaction product of an aluminum halide and hydroxyl groups of the solid adsorbent containing surface hydroxyl acids such as aluminum oxide and silicon dioxide by treatment with hydrogen, followed by treatment with gaseous HCl. Component of the hydrogenation noble metal is not mentioned, and an essential part of the regeneration process is the following after treatment with hydrogen treatment of HCl.The aim of the present invention is to restore the activity of the solid catalyst (metal halide), reacted the number of metal active in hydrogenation, where such catalysts are deactivated, when using it as a catalyst of liquid-phase alkylation of motor fuel. One option includes the handling of catalyst, released almost completely from the liquid phase, with hydrogen at a temperature of 10 - 300oC and a partial pressure of hydrogen 6,9 - 13790,0 kPa. In a more specific embodiment, the refractory inorganic oxide is alumina. In another specific embodiment, the metal halide is aluminum chloride. In another more specific embodiment, the metal halide is aluminum chloride, the refractory inorganic oxide is alumina, and metal, with activity in the hydrogenation, is paid. In another embodiment, the catalyst is treated with hydrogen in the previously mentioned temperature and pressure and in the presence of liquid isobutane and donor chloride.Although the group of catalysts which can be described as the reaction products of Friedel-crafts active metal halide and surface hydroxyl groups of the inorganic oxide, and which additionally contain metal with zero valency, with activity in the hydrogenation of demonstrates is the quality components of motor fuel, such catalysts are rapidly deactivated. Therefore, there is a need to develop methods of regeneration of the catalyst, preferably using a relatively simple procedure, inexpensive and effective in terms of recovery of catalytic activity with repeated regeneration. This description discloses such a way that practically frees the catalyst from the reaction mixture of liquid-phase reactions with subsequent treatment of the catalyst with hydrogen at a temperature of at least 10oC to a temperature of about 300oC and a partial pressure of hydrogen of at least 6.9 kPa to 13790,0 kPa. Treatment of the catalyst with hydrogen can be produced either by using catalysts, practically free from liquid or in the presence of liquid isobutane and donor chloride.As used in this invention catalysts are well known in practice (see US-A-2999074 and US-A-3318820), there is no need long to describe here, the following description will be sufficient for understanding the present invention. Refractory inorganic oxides suitable for use in this invention have a surface area of at least about 35 m2/g, preferably bol materials having a greater surface area, although there are also some exceptions. Suitable refractory inorganic oxides include aluminum oxide, titanium dioxide, zirconium dioxide, chromium oxide, silicon dioxide, boron oxide, aluminum silicate, aluminum phosphate, and combinations thereof. Particularly preferred among them is aluminum oxide. Any phase of aluminum oxide can be used as long as it has a surface area of at least 35 m2/g and has a hydroxyl group, with regard to practical application, it excludes alpha-alumina, although the various phases are not necessarily equivalent in effectiveness as catalysts for the alkylation of motor fuel.It is necessary that the refractory inorganic oxide had a surface hydroxyl groups which are not adsorb water, and preferably hydroxyl (OH) group oxygens which are connected with metal inorganic acidic. These latter hydroxyl group is sometimes referred to as chemically bound to the hydroxyl. Because the presence of adsorbed water usually does harm to obtaining catalysts of the present invention, refractory inorganic oxides first process is ur, which specifically and preferably remove physically adsorbed water without chemical changes other hydroxyl groups. For example, the temperature is from 350 to 700oC is usually sufficient to aluminum oxide.Usually metal with zero valence and activity in hydrogenation processes applied on the refractory metal oxide to the reaction of the surface hydroxyl groups with a halide of the metal. Although it is proved that this procedure is convenient and effective, it is not the only sequence of operations that can be applied to obtain an effective catalyst. Found that a particularly effective metals are Nickel and noble metals: platinum, palladium, ruthenium, rhodium, osmium and iridium, although among the noble metals, the most preferred are palladium and platinum. The desired metal can be mixed with the refractory inorganic oxide by any suitable method such as impregnation, co deposition, immersion, etc. Such methods are well known and need no description. The metal content can be varied from about 0.01 to about 1.0 percent by weight of the noble metal from the final weight of the catalyst and from primer the t under controlled conditions to remove physically adsorbed water, but in a fairly mild conditions so as not to remove the chemically bound hydroxyl groups.After application of the metal and annealing the surface hydroxyl groups of the refractory inorganic oxide react with the metal halides, with activity in the Friedel-Crafts. Metals that can be used include aluminum, zirconium, tin, tantalum, titanium, gallium, antimony, phosphorus and boron. Suitable halides include fluorides, chlorides and bromides. Representatives of such metal halides include aluminum chloride, aluminum bromide, iron chloride (III) bromide iron (III), zirconium chloride, zirconium bromide, boron TRIFLUORIDE, titanium tetrachloride, gallium chloride, tin tetrachloride, fluoride, antimony, tantalum chloride, tantalum fluoride, chloride, phosphorus, fluoride, phosphorus, etc. Among these metal halides are preferred halides of aluminum, especially aluminum chloride. With the exception of boron TRIFLUORIDE, the preferred halides are chlorides.The reaction of halides of metals of the present invention with surface hydroxyl groups of the refractory inorganic oxide is easy to implement, for example, by sublimation or distillation of the metal halide role of galgenwaard on 1 mol of adsorbed metal halide. The reaction temperature depends upon such variables as the reactivity of the halides of the metals and their sublimation temperature or boiling point, when the metal halide reacts in the gas phase, as well as from the nature of the refractory inorganic oxide. For example, using aluminum chloride and aluminum oxide as specific examples, it is easy to carry out the reaction in the temperature range from 190 to 600oC.It was found that the following method is very effective in restoring the lost activity of such catalysts is effective over many regeneration cycles. First, it is necessary to remove virtually all of the liquid reaction mixture from the catalyst that you simply make, providing a draining all of the liquid phase of the catalyst. After removal of the liquid phase, the catalyst is treated with hydrogen at a partial pressure of from about 6.9 to 13790 kPa (1-2000 pounds/inch (0.07 - 140,6 kg/cm2). The temperature at which the catalyst is treated with hydrogen, range from 10 to 300oC. the regeneration time has an inverse dependence on temperature. Therefore, if you want less regeneration time, are preferred at higher temperatures, for this piccottini is the period of time from 1 to 20 hours However, other factors are favorable low temperature regeneration. The most desirable is the regeneration in terms of conducting the alkylation to reduce the cost of heating and cooling and to ensure simplicity and ease of regeneration to be performed. Indeed, it is preferable to carry out the regeneration in the temperature range from about 10 to 2000oC, for which the regeneration time of about 6 hours is enough for maximum recovery.The following examples illustrate the invention.The basic procedure. Typical alkylation conditions include a temperature of 10oC, the reaction pressure 3200 kPa (450 lbs/inch=31,64 kg/cm2), LHSV (volume rate of fluid per hour) of butene-2 0.2 h-1when molar ratio isobutane/butene 100, 75, 45, or 20. The alkylation is carried out in the presence of 2000 million shares chloride (such as butyl chloride) and hydrogen, the amount of which is 0.25 mol the number of butene.Regeneration of the catalyst with hydrogen is as follows. At the end of the cycle alkylation (i.e., when the catalyst is significantly deactivated) introduces a stream of isobutane with a bulk velocity ILHSV and remove the original product isobutane/olef hydrogen together with 10-1000 million-1chloride, such as butyl chloride, and increase the pressure in the system to 3200 kPa (450 lb/in2= 31,64 kg/cm2). The temperature was raised to 200oC and maintain at this level for 4 h, after which the reactor is cooled to 10oC for about 2 h, and then fill and washed by a stream of isobutane for another 1-2 hours, the Whole procedure lasts about 10 o'clockExample 1. Regeneration of pure hydrogen.Prepare a catalyst containing 0.25 wt.% platinum 1.6 mm (1/16") the catalyst is gamma-alumina, which sublimated aluminum chloride in an amount corresponding to 0.75 wt.% Al. The aluminium content is not precisely measured, it is better to define it based on the content of chloride. Then the catalyst is treated with donor chloride, in such a way that it initially contains chloride in the amount of 3-7 wt.%, while suitable donors chloride are alkylchloride or hydrogen chloride. The catalyst used in the alkylation of motor fuel in the installed above conditions and regenerate, as described above, after 10 cycles of alkylation. Between cycles 2 and 10 do not see a noticeable loss of activity, all cycles carried out at the ratio of isobutane/butene 45. For all cycles medium the/P> Control is carried out using the same catalyst, deletion of platinum. Regeneration does not see; the catalyst after treatment with hydrogen remains deactivated in the same degree, significant recovery is not happening.Similar experiments carried out using gallium chloride, CaCl3instead of aluminium chloride. Although experiments on regeneration is not very long, the deactivated catalyst is fully regenerate under the above conditions. The resulting alkylate yields the value of RON 90,5.In another experiment replace platinum palladium (0.5 wt.%) in the catalyst containing aluminum chloride, aluminum oxide. Regeneration is successful, and the average value RON of the products of alkylation is about 88,5.Example 2. Regeneration isobutane, butyl chloride and hydrogen.As the regeneration carried out in a stream of isobutane, hydrogen, witnessing the loss of catalysts chloride with subsequent deactivation of the catalyst, it is desirable to carry out the regeneration in the presence of organic chloride such as butyl chloride. When such a regeneration at the end of the cycle alkylation enter isobutene containing 1000 million shares chloride is EMA that the feed mixture away. After 2 washing jet of fluid pressure to increase 4238 kPa (600 lb2= 42,19 kg/cm2), raise the temperature to about 135oC and maintain it at this level for 12 o'clockAfter cooling the catalytic mixture to 10oC stop the flow of the mixture in the reactor and remove regenerating gas. Usually the procedure takes 16 to 18 o'clockThe catalyst is aluminium chloride on the catalyst is gamma-alumina containing 0.25 wt.% platinum, easily regenerate in the above-mentioned conditions, obtaining the product of alkylation with secondary RON 90,5. When the butyl chloride is missing in the flow of regeneration gas, the catalyst is first very quickly deactivated, then it cannot be regenerated to a satisfactory degree. This indicates the desirability, if not necessity of the presence of butyl chloride in a stream of regeneration gas, where there are isobutane, as representative of the hydrocarbons, and hydrogen. Separate experiments show that platinum can be replaced or 0.5 wt.% palladium or Nickel, which provide the catalysts regenerated in the same conditions as above. For the last two catalysts derived alkylate has an average value of about RON 88,5.It is shown that the catalysts obtained by sublimation 1) of zirconium tetrachloride, ZrCl4on aluminum oxide containing 0.25 wt.% platinum, 2) of titanium tetrachloride, TiCl4on gamma-alumina containing 0.25 wt.% plate, and 3) aluminium chloride on spherical aluminosilicate (75 to 90 wt.% silicon dioxide) having 0.25 wt.% platinum, also can be regenerated through several cycles of alkylation. In all cases the resulting alkylates give the average value of RON 88-89.The catalysts obtained from the three-phase boron-modified alumina with or without 0.25 wt.% platinum. The catalyst without platinum cannot be regenerated, while the catalyst with platinum is recovered after many cycles alkylation using any procedure or procedure of example 1. In all cases alkylates obtained have an average value of about RON 91,5. 1. How periodic the UB>6-alkene C4- C6-alkanol, and the catalyst comprises the reaction product of the metal halide, including fluoride, chloride or bromide of a metal selected from the group comprising aluminum, zirconium, tin, tantalum, titanium, gallium, antimony, phosphorus, iron, boron and their mixture, and bound surface hydroxyl groups of the refractory inorganic oxide and metals with zero valency selected from the group comprising platinum, palladium, Nickel, ruthenium, rhodium, osmium, iridium, and their mixture, characterized in that that is basically all liquid phase hydrocarbons is removed from the catalyst and the resulting catalyst is treated with hydrogen at a partial pressure of 6.9 - 13790,0 kPa and at a temperature of 10 - 300oC for 1 to 20 h, followed by separation of the regenerated catalyst.2. The method according to p. 1, characterized in that use a metal halide selected from the group comprising aluminum, zirconium, titanium, gallium, boron and their mixture.3. The method according to p. 1, characterized in that use metal with zero valency selected from the group comprising platinum, palladium and a mixture thereof.4. The method according to PP.1, 2 or 3, characterized in that the catalyst is treated with hydrogen at 10 - 200oC.6. The method according to PP.1 to 4, characterized in that the treatment with hydrogen is carried out in the presence of liquid isobutane and donor chloride.
FIELD: chemical industry; production of a catalyst carrier material and the catalyst.
SUBSTANCE: the invention is dealt with the field of chemical industry. The method of production of a catalyst carrier material includes the following stages: (a) treatment of the utilized catalyst of titanium dioxide-on-silicon dioxide to clear from coke; (Ь) washing of the catalyst cleared from the coke by a flushing fluid chosen from a water solution of an inorganic acid, a water solution of an ammonium salt and their combinations; (c) drying and calcination of the catalyst washed out and cleared from the coke with production of the catalyst carrier material. The technical effect - the material produced this way is fit for use as the carrying agent material for titanium dioxide in a heterogeneous catalyst for epoxidation of olefines in alkylene oxide.
EFFECT: the invention ensures production of the material fit for use as the carrying agent material for titanium dioxide in a heterogeneous catalyst for epoxidation of olefines in alkylene oxide.
12 cl, 4 ex, 1 tbl
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention describes a method for preparing oxirane in reactor comprising a liquid reaction medium. Method involves carrying out reaction between olefin and peroxide compound in liquid reaction medium in the presence of a solid catalyst and a solvent. Solid catalyst comprises zeolite as an active component and it is used in form of particles wherein at least part of particles present in reactor in the fluidized state. Invention provides increasing rate of the process that results to the enhanced output.
EFFECT: improved preparing method.
FIELD: petrochemical industry; methods of reactivation of the alumina catalyzer of dehydration of methylphenylcarbinol (MPhC).
SUBSTANCE: the invention is pertaining to the field of petrochemical industry, in particular , to the method of reactivation of the catalyzer of the vapor-phase dehydration of methylphenylcarbinol. The offered method of the reactivation of the catalyzer of dehydration of methylphenylcarbinol is realized with the help of the carbon-containing compounds and coke burning-off by the air oxygen in the flow of the water steam and the subsequent wash by the acid water solution capable to give back hydrogen in the form of the proton. The volumetric ratio of the acid solution to the catalyzer at the wash is kept equal to 1÷10:1. In the process of the catalyzer wash the water solution of the acid having the temperature of 5-90°C is used. The technical result of the invention is reduction of the water consumption at realization of the reactivation of the alumina catalyzer of dehydration of methylphenylcarbinol.
EFFECT: the invention ensures reduction of the water consumption at realization of the reactivation of the alumina catalyzer of dehydration of methylphenylcarbinol.
9 ex, 1 tbl
FIELD: chemical industry; environmental protection technologies and methods of utilization of the waste mercury-containing catalyzer.
SUBSTANCE: the invention is pertaining to the field of environmental protection technologies, in particular, to the processes of utilization of the waste mercury-containing catalyzer for the process of hydrochlorination of the ethine. The invention presents the method of utilization of the mercury-containing catalyzer by its heating in the medium of the reducing gas, in the capacity of which use the residual gas of the high-temperature homogeneous pyrolysis of hydrocarbons. The heating is conducted at the temperature of 400-700°C within 4-7 hours. The technical result of the invention is the complete extraction (99.99 %) of mercury from the waste catalyzer, that transforms the mercury into the non-toxic substance.
EFFECT: the invention ensures the complete extraction of mercury from the waste catalyzer, that transforms the mercury into the non-toxic substance.
5 tbl, 6 ex, 1 dwg
SUBSTANCE: invention relates to field of oil processing, in particular CO oxidation catalysts, used as additive to cracking catalyst for oxidising oxygen into carbon dioxide in process of cracking catalyst regeneration. Claimed catalyst for CO oxidation in process of cracking catalyst regeneration contains manganese compounds, aluminium oxide and natural bentonite clay, with the following component content, wt %: manganese in terms of MnO2 6-20, bentonite clay - 24-44, Al2O3 - the remaining part, and has microspherical form of particles with average size 70 mc, wear resistance 92-97%, bulk density 0.7-0.8 g/cm3. Described is method of preparing catalyst for CO oxidation in process of cracking catalyst regeneration, which includes mixing manganese (IV) hydroxide, obtained by precipitation of manganese nitrate from water solution with ammonium, with composition, which consists of aluminium hydroxide and bentonite clay, preliminarily processed with concentrated nitric acid (12.78 mole/l), composition drying and burning, which is carried out step by step: at temperature 500°C during 4-6 hours, and then at temperature 950-970°C during 4 hours.
EFFECT: increase of catalyst activity and wear-resistance.
2 cl, 1 tbl, 12 ex
FIELD: technological processes.
SUBSTANCE: invention relates to sorption equipment and may be used to restore protective properties of chemical adsorbents-catalysts and filtering-absorbing canisters equipped with them that have expired shelf life. A method is described to regenerate a carbon-based sorbent-catalyst that lost activity during storage, including treatment with a chemical reagent containing ammonia, and further thermal treatment, where a reagent is an ammonium-air mixture with ammonia concentration (40±5) vol.%, which for (15±1)s is passed through a layer of a chemical adsorbent-catalyst arranged in an equipped filtering-absorbing canister, at the temperature of (22±3)°C and flow of (30±1.5) dm3/min with subsequent soaking for (5-6) min and thermal treatment for (5-6) min, by air heated up to (150±5)°C and flow of (200±20) dm3/min. (40±5) vol.%, which for (15±1)s is passed through a layer of a chemical adsorbent-catalyst arranged in an equipped filtering-absorbing canister, at the temperature of (22±3)°C and flow of (30±1.5) dm3/min with subsequent soaking for (5-6) min and thermal treatment for (5-6) min, by air heated up to (150±5)°C and flow of (200±20) dm3/min.
EFFECT: restoration of protective properties of a chemical adsorbent-catalyst in composition of filtering-absorbing canisters with expired shelf life without their disassembly.