The method of producing botanophobia of the olefins in the fischer-tropsch synthesis
(57) Abstract:Usage: petrochemistry. Essence: contained in the fraction4hydrocarbons by Fischer-Tropsch synthesis the butenes is subjected to oligomerization stage oligomerization and from a mixture of oligomerization get debuted that at the stage clear rectification divided into di-n-butene and di-isobutene. In one form of execution of the method contained in the olefins in the Fischer-Tropsch synthesis ethylene will timeresult, and the mixture dimerization return to the stage 12 of the separation fraction WITH4. In another form of execution of way between the stage 12 of the separation fraction WITH4and the stage 13 selective hydrogenation include stage 5 of esterification, which is contained in the feed line 1 fraction4isobutan subjected to interaction with supplied through line 25 alcohol with getting the exhaust line 26 alkyl tert-butyl ether and only the remaining n-butene will oligomerized in stage 2 oligomerization, so that as the exhaust line 4 debathena formed exclusively di-n-butene, taken on the line 6. In addition, there may be a stage 27 isomerization, which neproreagirovavshimi in stage 2 of oligomerization of n-butene will isomerized to isobutene, CLASS="ptx2">The invention relates to a method of producing botanophobia of the olefins in the Fischer-Tropsch synthesis. Butanilicaine represent a valuable source of nutrients for obtaining alcohols. The preferred butanilicaine are isomeric octane, which are dimeric butenes and which, therefore, also referred to as debutta. High demand by debutta is di-n-butene. Therefore, the invention relates also to the way in which di-n-butene is separated from dibucaine. In addition, the invention relates to methods, the result of which receive, in addition to higher botanophobia, as dibucaine exclusively di-n-butene, the by-products are valuable alkyl tert-butyl ethers.Debuted is a mixture of isomers, which is formed along with the highest butanilicaine as a result of dimerization and/or co-dimerization of butenes, that is, n-butene and/or isobutene when oligomerization of butenes. Di-n-butene is called the product of the dimerization of n-butene to 1-butene and/or 2-butene. Essential components of di-n-butene are 3-methyl-2-hepten, 3,4-dimethyl-2-hexene and, to a lesser extent, n-octene. Di-isobutene represents sikuli, than debuted, which, for its part, is more extensive than di-n-butene.Debuted, di-n-butene and di-isobutene are the source materials for the production of isomeric nonanols by hydroformylation and hydrogenation of the resulting aldehyde with 9 carbon atoms. Esters of these nonanalog, in particular esters of phthalic acid, are plasticizers, which are produced in large numbers and used primarily for PVC. Nonanol of di-n-butene are less extensive than nonanol from dibucaine, which on its part is less extensive than nonanol of di-isobutene. Esters of nonanalog of di-n-butene due to its more linear patterns have technological advantages in comparison with esters of nonanalog based dibucaine and di-isobutene and are in great demand.The butenes for the dimerization can be obtained, for example, of the fraction4resulting from cracking with steam or catalytic cracking in a fluidized bed. The fraction is processed, usually by separating 1,3-butadiene selective leaching, for example, N-organic. Isobutene is realizowane high demand products. He is subjected to, for example, interaction with isobutane with obtaining high-octane isooctane or alkanols, such as methanol, to obtain tert-butyl ether, which, as an additive to motor gasoline improves its octane number. After the reaction of isobutene remain n-butene, n - and isobutane. However, the share of n-butene in the cleavage products of cracking with steam or catalytic cracking in a fluidized bed is relatively low. It is less than 10% by weight of the main target product ethylene. On cracking unit with water vapor with a capacity of 600,000 tons of ethylene per year receive only about 60,000 t of n-butene in the year. The number of n-butene (as well as isobutene), however, can be improved by dehydrogenation 15000 t n - and isobutane in the year that get along with n-butene. This, however, is not recommended, as the setup for the dehydrogenation require high capital investment and are unprofitable in the event of such minor performance.As already mentioned, isobutene is a high demand cracking product and therefore, as a rule, cannot be used for oligomerization. However, the number of n-butenes, neposredstvennom layer, not enough to produce a sufficient number of dibucaine for installation obtain nonanalog, the performance of which is so big that it can compete economically with existing large units receiving significant alcohols to obtain plasticizers, such as 2-ethylhexanol. This means that you need to collect obtained at different crackers n-butene and undergo oligomerization to cover the needs of large production units nonanalog in dibucaine. Alternatively, you can collect another undivided fraction4from different cracking units and process in place to n-butene. This is opposed, however, by the fact that the transport of liquefied gases is expensive, not least because of the required costly security measures.It is therefore desirable to provide butenes for oligomerization only one place without transportation over long distances in the quantities required to operate a large plant for producing nonanalog having, for example, the performance 200000-800000 t/year. It is also desirable to use the butenes, which are inevitably get in the way of the IU is also desirable to have a method of obtaining botanophobia, in which valuable di-n-butene can be separated from dibucaine. Further preferably, such a control method, in addition to higher botanophobia as dibucaine formed exclusively di-n-butene, and as desired by-products was simple alkyl tert-butyl ethers. It is also desirable to be able to regulate the proportion of these substances.The method according to the invention is illustrated by flowchart on the attached figures 1 and 2, which set out the following variants of the method with mandatory and optional stages of the method.The invention is a method of producing botanophobia of the olefins in the Fischer-Tropsch synthesis, which is contained in the feed line 1 fraction4olefins in the Fischer-Tropsch synthesis the butenes is subjected to oligomerization stage 2 oligomerization, and allocated on line 3 mixture of oligomerization receive exhaust line 4 debuted.This method with its various optional stages, which are explained in the following by means of figure 1, referred to as option A.Option B, which corresponds to figure 2, referred to as the way in which the first stage 5 of esterification with the 25 alkanols with getting the exhaust line 26 alkyl tert-butyl ether and oligomerized only the remaining n-butene with getting as dibucaine exclusively di-n-butene, exhaust line 6. In a particular form of implementation of option B has a stage 27 isomerization, which neproreagirovavshimi in stage 2 of oligomerization of n-butene will isomerized to isobutene, which returns to the step 5 of esterification.In particular, recent form run-option B has a high flexibility. Depending on the requirements of the market, you can get varying amounts of di-n-butene and alkyl tert-butyl ether.Fractions WITH4as an initial matter how
The original substance of the proposed method is supplied through line 1 to a fraction WITH4derived from the way the Fischer-Tropsch process, in which, as is known from synthesis gas (carbon monoxide and hydrogen) to produce hydrocarbons or oxygen-containing products. Synthesis gas can be obtained from a variety of energy sources, such as, for example, natural gas, fuel oil, residual oil, lignite and coal, in almost any quantity.Synthesis Fischer was originally developed for the production of gasoline, however, after the Second world war, interest was focused primarily on the development of ways to get rich alpha-olefin hydrocarbon fractions with low Chi is tion of the output of ethylene, and propylene, as these olefins are the main components of many important chemicals, such as, for example, polyethylene, polypropylene, polyvinyl chloride, ethylene oxide and propylene oxide.Obtaining mainly short-chained hydrocarbons with 2 to 6 carbon atoms, the predominant way seem olefins and, in particular, alpha-olefins, provides, for example, the method according to application EP 0 216 972. Its essential feature is the choice of a particular catalyst, namely, single-phase, kurbadstrasse and restored spinel without carrier formed from oxide compounds empirical formula FexCoy04in which x and y denote integers or decimal numbers, provided that the sum x + y = 3 and the ratio x/y is at least 7. The surface of the catalyst is at least about 0.1 to 5 m2/, as a promoter, the catalyst may contain a compound of the metal of group IA or IIA of the periodic system of elements.The catalyst is pyrophoric. Therefore inactivate using small amounts of oxygen in an inert gas to improve the handling. It can be used in the form of a suspension in an inert organic is or mixture of such substances, in quantities of from 10 to 50 g of dry catalyst at 500 g organic liquid. Before filing a synthesis gas catalyst condition, that is again activated by flushing with nitrogen and treatment with hydrogen at elevated temperature.The ratio of carbon monoxide and hydrogen in the synthesis gas may vary within wide limits and is preferably 1:1 to 2:1. The optimum temperature to achieve the desired short-chained alpha-olefins with 2 to 6 carbon atoms equals 230 to 270oWith, in particular 240-260oC. This temperature is critical, since at elevated temperatures to produce more methane, and low temperatures facilitate the formation of waxy products. The method is carried out, generally at a pressure in the range from 350 to 2200 kPa.In such circumstances and in the manner fixed bed catalyst preferably produce hydrocarbons with 2 to 6 carbon atoms, most of which represents olefins, preferably alpha-olefins. Fraction WITH4the standard way separated from hydrocarbon mixtures, mainly by fractional distillation at low temperature and/or high blood pressure.It must be emphasized that the quality is one more likely to apply any fraction4derived from plants operating according to the method of Fischer-Tropsch. In South Africa in optimized ways Fischer-Tropsch process on an industrial scale to produce more than 400,000 t of ethylene and 500,000 tons of propylene per year. The drawback of these methods is that inevitably produces about the same amount of higher hydrocarbons and, in particular, hydrocarbons with 4 carbon atoms, for which there is virtually no appropriate application, in addition to their use as additives to gasoline fuels. But even for fuel fraction WITH4probably not suitable because of its high proportion of olefins, which bowed to resinification, and because of its high vapor pressure, which is the environmental load. Thus the method according to the invention provides a useful application inevitably formed substances and improves the value creation method of Fischer-Tropsch.Option a
From supplied through line 7 energy on stage 8 synthesis gas to produce synthesis gas corresponding to its purpose, composition, line 9 serves on stage 10 of the Fischer-Tropsch synthesis, which produces, for example, by the method according to application EP 0 216 972, rich in olefins, a mixture of hydrocarbons with a large share of the given exhaust line 1 fraction WITH4for example , by liquefaction of gaseous components at a temperature of -30oWith and fractional distillation. The obtained fraction WITH4has, as a rule, the following composition:
1-Butene - 7010%
Isobutan - 105%
2-Butene - 105%
n/Isobutan - 123%
1,3-Butadiene - Tracks
You can increase the output of the exhaust line 1 fraction4by dimerization postupyushey on stage 12 of the separation of ethylene on stage 12A of dimerization. Suitable for this, for example, a method of obtaining a trading product dimersol described by the author Y. Chauvin and others in the source "Erdol, Erdgas, Kohle" 106, 7/8 (1990 ), pp. 309 FF. Working in the liquid phase with a catalyst of the type of Ziegler catalysts based on compounds of Nickel, which activate using ORGANOMETALLIC compounds. "Degenerated polymerization of dotimer proceeds under mild conditions at a temperature of about 20-80oC. Conversion cycle is 50-90%. A mixture of dimerization return to the stage 12 of the separation.Supplied through line 1 to a fraction WITH4contains traces of 1,3-butadiene. It is recommended to remove these dieny, as even a negligible amount of dienes can damage the catalyst for oligomerization. A suitable method is the selective hydrogenation of 1P. the source of "Erdol &Kohle, Erdgas, Petrochemie, 1986, page 73 and ate. In the liquid phase method are fully dissolved hydrogen in stoichiometric quantities. As selective hydrogenation catalysts are suitable, for example, Nickel and, in particular, palladium on a carrier, e.g. 0.3 weight. % palladium on active coal or preferably aluminum oxide. A small amount of carbon monoxide in the range h/mill. contributes to the selectivity of the hydrogenation of 1,3-butadiene to monoolefins and counteracts the formation of polymers, the so-called green oil, inactivating the catalyst. The method is carried out at room temperature or slightly elevated temperatures up to 60oC and at high pressure, suitable components up to 20 bar. The content of 1,3-butadiene in the feed line 1 fraction4thus reduced to values below 1 h/mil., which do not interfere with oligomerization.In addition, it is advisable before entering on the stage 2 oligomerization maximum freed from 1,3-butadiene fraction WITH4to apply for stage 14 cleaning, representing a molecular sieve, allowing removes other harmful oligomerization catalyst substance and povyshaetsya described by the author F. Nierlich, etc. in the patent EP 0 395 857. It is advisable to use a molecular sieve with a pore diameter of equal to 4-15 mainly 7-13 In some cases, for economic reasons, it is advisable to mixture dehydrogenation sequentially fed through molecular sieves with different pore sizes. The method can be carried out in the gas phase, liquid phase or gazogidrat phase. Pressure, respectively, as a rule, 1 to 200 bar. It is advisable to work at room temperature or elevated temperatures up to 200oC.Chemical properties of molecular sieves is less important than their physical characteristics, i.e., in particular the size of the pores. Consequently, it is possible to apply a variety of molecular sieves such as crystalline, natural aluminum silicates, for example silicates with a layered lattice, and synthetic molecular sieves, such as zeolite sieves with structure. The zeolites of type a, X and Y can be obtained as a commercial product companies Bayer AG, Dow chemical Co., Union Carbide Corporation, Laporte Industries Ltd. and Mobil oil Co. Suitable are also such synthetic molecular sieves, which along with aluminum and silicon contain other, introduced by casinoonline atakticheskie zeolites, in addition to aluminum and silicon in the lattice introduced by mixed precipitation more other atoms, such as boron or phosphorus.As already mentioned, the stage 13 selective hydrogenation stage 14 cleaning the molecular sieve are optional, pre-emptive measures for the method according to the invention. The sequence can in principle be any, but is indicated in Fig.1 the sequence.Supplied through line 1 fraction WITH4if necessary, pre-treated in the manner described, serves on stage 2 oligomerization, representing a significant portion of the proposed method. Oligomerization is the co-oligomerization of n-butene and isobutene carried out by a well-known manner, as described, for example, the author F. Nierlich source "Oligomerization for Better Gasoline", Hydrocarbon Processing, 1992, pp. 45 FF., or F. Nierlich, etc. in the above mentioned patent EP 0 395 857. As a rule, are in the liquid phase as a homogeneous catalyst is used, for example, a system consisting of octoate Nickel (II) chloride ethylaluminum and free fatty acid number (see patent DE 28 55 423), or preferably use one of the many known catalysts the Catalysts often additionally contain aluminum. So in the patent GDR 160 037 describes a receipt containing Nickel and aluminum catalyst deposition on silicon dioxide as a carrier. Other suitable catalysts are obtained by replacing the surface of the media positively charged particles, such as protons or sodium ions, Nickel ions. It is possible in the case of a variety of media, such as amorphous aluminum silicate (see R. Espinoza and others in the source, "Appl. Kat", 31, 1987, pages 259-266), crystalline aluminum silicate (see patent DE 20 29 624), zeolites ZSM (see patent NL 8 500 459), zeolites of type X (see patent DE 23 47 235), zeolites of type X and Y (see A. Barth, and others in the source "Z. Anorg. Allg. Chem." 521, 1985, pages 207-214) and mordenite (see application EP 0 233 302).Co-oligomerization expediently carried out depending on the catalyst at a temperature of 20-200oC and a pressure of 1-100 bar. The reaction time (or the time of contact) is usually 5-60 minutes the Parameters of the method, in particular the type of catalyst, temperature and time of contact, coordinate, so that the desired degree of oligomerization was achieved. In the case of nonanalog as the desired target product, we are primarily talking about the dimerization. Needless to say that this reaction cannot euxesta cycle. The optimum combination of parameters of the method can be determined without problems by conducting preliminary tests.From supplied through line 3 mixture of oligomerization on stage 15 of the separation fraction WITH4separate exhaust line 16 residual gas, which as a return gas line 17 to partially return to the stage 2 oligomerization and partially withdrawn from the loop line 18 as exhaust gas. The return part of the exhaust line 16 residual gas is required, because, as already mentioned, the conversion in stage 2 of oligomerization is incomplete. Exhaust line 18 exhaust gas to be output from the loop to take a small number (123%) n/isobutane, usually available at a fraction WITH the4. Of course, taken on lines 18 exhaust gas also contains butenes, mainly n-butene, preferably as oligomerized isobutan already in the faction WITH4in a small amount. Exhaust line 16 residual gas is separated into the exhaust line 17 back to the gas exhaust line 18 of the exhaust gas in such a ratio that the content of n - and isobutane in the exhaust line 16 residual gas has not increased too much. Stationary is leegomery on line 19 serves on stage 20 of the separation of oligomers, where they are separated by distillation in the exhaust line 4 debuted, taken along the line 21 tribute (or dodecen) and exhaust line 22 residue. Exhaust line 21 tribute is a desired by-product. It can be HYDROFORM-place products hydroformylation you can gidrirovanii and thus obtained tridecanol you can ethoxylate, resulting in gain valuable component of detergents. Exhaust line 4 debuted directly suitable as starting material for obtaining nonanalog, especially as it is relatively linear because of the high proportion of n-butene in the faction WITH4. If important special properties of nonanalog of di-n-butene, the exhaust line 4 debutin can be divided into stages 23 clear rectification on the exhaust line 6 di-n-butene and exhaust line 24 di-isobutene that as more branched molecules boil at lower temperatures. The latter can also be used to obtain alcohols to obtain plasticizers or, if necessary, after hydrogenation, as an additive to motor gasoline.Option B
Option B supplied from line 1 fraction4stage 5 earcanal with getting the exhaust line 26 alkyl tert-butyl ether. The reaction is practically selective, since both isomers of n-butene is much less reactive than isobutene. In stage 2 oligomerization will oligomerized exclusively n-butene, so as dibucaine formed exclusively di-n-butene, taken on the line 6.Suitable alkanols, supplied through line 25, is primarily alkanols with 1 to 6 carbon atoms, for example methanol, ethanol or Isobutanol. Their interaction with Isobutanol described, for example, the source of "Methyl-Tert-Butyl Ether", Ullmanns Encyclopedia of Industrial Chemistry, volume 16, page 543 FF. The reaction is carried out in the liquid phase or in gazogidrat phase at a temperature of 50-90oWhen the pressure is installed at the corresponding temperature. It is advisable to work with a small excess of alkanol, thereby increasing the selectivity of the conversion of isobutene and decreases its dimerization. As the catalyst used, for example, acidic bentonite or acidic ion exchanger with large pores. From a liquid mixture of esterification in the distillation exhaust line 26 alkyl tert-butyl ether and, if necessary, excess alkanol, which can be returned in the response.Department of isobutene by vzaimodei ether, in particular tert-butyl ester as increasing octane additive to motor gasoline.In the case of a special form of execution of option B has a stage 27 isomerization, in which part of n-butene turn to isobutene. Additional isobutene return to the step 5 of esterification. Thus it is possible to vary the proportion of di-n-butene and alkyl tert-butyl ether and its adjustment to the needs of the market.Isomerization of olefins is also called skeletal isomerization. Stage 27 isomerization expediently connected to stage 15 of the separation fraction WITH4. Exhaust line 16 residual gas containing up to about 70. % of n - and isobutane, and then divided into three partial flow, namely the exhaust line 17 back to the gas exhaust line 18 of the exhaust gas and the exhaust line 28 gas isomerization. Isomerization of n-butene to isobutene has been developed in the recent past. An overview of the different ways are listed by author F. Nierlich source "Recent Developments in Olefin Processing for Cleaner Gasoline", Oil Gas European Magazine, 1992 , 4, pp. 31 FF. A common feature of all methods is that n-butene is mixed with steam and passed through an acidic catalyst, such as acid will someresult to isobutene to achieve equilibrium, component depending on the temperature of 35-50% of isobutene and 65-50% n-butene. From supplied through line 29 isomerization mixture under pressure to separate the high-boiling components by flushing 30 circulating water. Not condensed in these conditions, the part supplied through line 29 isomerization mixture leaving the top of the column as an azeotrope consisting (mainly) of hydrocarbons with 4 carbon atoms and water, served on the separation stage 31 in the column. From the top of the column goes azeotrope consisting of low-boiling components and water, and in the lower part of the column receive hydrocarbons with 4 carbon atoms and a small amount of high-boiling components, which were not deposited at the stage 30 of the washing water-circulating and that the subsequent separation stage 32, also representing the column, as the cubic product is separated from the opening of the head part of the hydrocarbons with 4 carbon atoms, which is returned to the step 5 of esterification. 1. The method of producing botanophobia of olefins, obtained by synthesis according to the method of Fischer-Tropsch, characterized in that the olefins are divided into division stage allocation fraction4hydrocarbons obtained by synthesis according to methods which are square-debuted.2. The method according to p. 1, characterized in that contained in the olefins in the Fischer-Tropsch synthesis ethylene will dimerized and the mixture dimerization return to the stage of separation.3. The method according to any of the p. 1 or 2, characterized in that between the stages of separation and oligomerization provided by stage selective hydrogenation to remove 1,3-butadiene and/or molecular sieve as the cleansing stage.4. The method according to any of paragraphs. 1-3, characterized in that formed during the oligomerization of oligomers by distillation get debuted and tribute (dodecen).5. The method according to p. 4, characterized in that debuted share on stage, a clear rectification on di-n-butene and di-isobutene.6. The method according to any of paragraphs. 1-4, characterized in that between phase separation and phase selective hydrogenation provided the stage of esterification, which is contained in the feed fraction4hydrocarbon isobutane subjected to interaction with the supplied alcohol to obtain an alkyl tert-butyl ether and only the remaining n-butene will oligomerized at the stage of oligomerization, so as dibucaine formed exclusively di-n-butene.7. The method according to one of paragraphs. 1-6, otlichayushiesya, served on the stage of esterification.
FIELD: regeneration of heat and extraction of impurities.
SUBSTANCE: the invention is pertaining to the method of regeneration of heat and extraction of impurities from the area of the heat-producing reaction in the fluidized flow, conducted for conversion into light olefins of oxygenates present in the flow of the oxygenate (oxygen-containing) raw. raw. The offered method includes the new system of a two-stage quick chilling intended for extraction at the first stage of water from the outgoing from the reactor flow and regeneration of heat of this flow for the purpose, at least, of the partial evaporation of the raw flow due to indirect heat-exchange between the oxygenated raw and the flow of the upper product of the first stage or the flow of recirculation of the first stage. The flow of purification being withdrawn from the first stage, contains the large share of impurities and the high-boiling oxygenates. In the second stage besides conduct extraction of water from the products flow containing light olefins, and produce the flow of the purified water, which requires only the minimum evaporation of the water for production of the water flow of the high degree purification. The method allows to concentrate the impurities in a rather small flow and ensures the significant saving of power and money resources at production of a flow of the vaporous raw guided into the area of realization of the heat-exchange reaction in the fluidized flow.
EFFECT: the invention ensures concentration of the impurities in a rather small flow and the significant saving of power and money at production of the flow of the vaporous raw directed into the area of realization of the heat-exchange reaction in the fluidized flow.
19 cl, 3 tbl, 4 dwg, 5 ex
FIELD: petrochemical processes.
SUBSTANCE: narrow-range hydrocarbon stock is fed into reaction-distillation tower at a level located between lower and upper tower parts to perform isomerization and disproportionation of hydrocarbons. Reaction mixture is maintained in vapor-liquid equilibrium state to concentrate lighter reaction products in vapor phase and higher ones in liquid phase by means of controlling temperature profile and in-tower pressure. Higher olefins are withdrawn as bottom product and lighter olefins from the top of tower.
EFFECT: increased yield of desired product.
41 cl, 4 dwg, 5 ex
FIELD: petroleum chemistry.
SUBSTANCE: claimed method includes oligomerization of one or more alpha-olefins with ethylene in presence of metal-containing catalytic system, using one or more bisaryl pyrimidine-MXa complex and/or one or more [bisaryl pyrimidine-MYpLb+]q- complex. Process is carried out at ethylene pressure less than 2.5 MPa.
EFFECT: method for production of target product of increased yield.
10 cl, 1 tbl, 3 dwg, 17 ex
FIELD: industrial organic synthesis catalysts.
SUBSTANCE: catalyst contains following active components: Pd (0.001-1%), Bi (0.001-5%), at least of Ag, Cu, Zn, K, Na, Mg, Ca, Be, Sn, Pb, Cd, Sr, Ba, Ra, Mn, Zr, Mo, and Ge (0.001-10%), and at least one of rare-earth metals deposited on porous inorganic carrier (the balance.). Catalyst is capable of selectively and rapidly hydrogenating strongly unsaturated hydrocarbons such as alkynes. Catalyst is suitable for industrial cracking process and is characterized by favorable long regeneration period, long service time, and low cost.
EFFECT: improved performance characteristics of catalyst at low cost.
23 cl, 5 tbl, 22 ex