Process for the selective hydrogenation of highly unsaturated compounds in hydrocarbon streams

 

(57) Abstract:

Usage: petrochemistry. The inventive method for selective hydrogenation of diolefins and acetylene compounds rich in olefin aliphatic hydrocarbon stream consists of contacting the raw flow of 4.44-148,89oC, low partial pressure of hydrogen 0,007-4,922 kg/cm2and the total pressure 0-24,61 kg/cm2in distillation column containing a layer of catalytic hydrogenation, which is a component of a distillation structure, such as caused PdO, Packed in a tubular wire mesh. The flow of raw material is introduced into the lower part of the catalyst layer or below and in contact with hydrogen, introduced into the catalyst bed. The head wrap is withdrawn from the upper section of the column, condensed, separated and partially recycle the catalyst bed. CBM stream is selected and partially recycle. Allocate the target flow of the products of hydrogenation and light gases. The technical result - the absence of significant hydrogenation of monoolefins and the formation of oligomers. 2 C. and 43 C.p. f-crystals, 13 tab., 4 Il.

The scope of the invention

The invention relates to the selective hydrogenation of diolefins and acetylene compounds in Paonia in the structure, that serves as a catalyst and the structure of the distillation process for simultaneous reaction and separation of the reactants and products of reaction.

Close of the invention

Mixed flows refineries often contain a wide range of olefinic compounds. This is especially true for products of catalytic or thermal cracking. These unsaturated compounds include ethylene, acetylene, propylene, PROPADIENE, methylacetylene, butenes, butadiene, amylene, hexene, etc. Many of these compounds have value, especially as raw material for chemical products. Especially ethylene subject of regeneration. Also valuable are propylene and butenes. However, the olefins with more than one double bond and acetylene compounds (containing a triple bond) are used less and harm many chemical processes involving compounds with one double bond, such as polymerization processes. For the range under consideration hydrocarbon destruction of highly unsaturated compounds is an important process pre-treatment of raw materials, since these compounds has been found to harm the majority of the processing, storage and use of potochnyi C8blending components for gasoline and raw materials for simple ether.

Refinery fraction C5has value as a component of a mixture of gasoline or as a source of isoamylene for simple ester by reaction with lower alcohols. Tert-amylotrophic ether (tame) is rapidly gaining valuable to refiners in the recent Clean Air Act, which establishes some new restrictions on the composition of gasoline. Some of these requirements are to: 1) include a certain amount of oxygenates such as methyl tert-butyl ether (MTBE), tame or ethanol, 2) to reduce the amount of olefins in gasoline, 3) to reduce the vapor pressure (volatility).

Hydrocarbons, C5in raw materials for the installation tame contained in a single fraction of a light distillate, which contains all of the hydrocarbons from C5to C8and above. This mix is free to contain 150-200 components and, consequently, the identification and separation of the products difficult. Several minor components (diolefin) in raw materials will slowly react with oxygen during storage with the formation of tars and other undesirable materials. However, these material. Therefore, it is desirable to remove these components, regardless of whether you want to use the fraction of light distillate as a component of a mixed fuel or as raw material in the tame process.

The use of solid powdered catalyst in a distillation process in combination reactor distillation column described in U.S. patents NN 4 307 177, 4 307 254, 4 336 407, 4 504 687, 4 918 243 and 4 978 807 (etherification); 4 242 530 (dimerization); 4 982 022 (hydration); 4 447 668 (dissociation); 4 950 834 and 5 019 669 (aromatic alkylation). In addition, the U.S. patents NN 4 302 356 and 4 443 559 reveal the structure of the catalyst, which are useful as structures distillation process.

Hydrogenation is a reaction of hydrogen with multiple carbon-carbon bond to "saturation" of the connection. This reaction is well known and is usually performed when surfmaster pressures and moderate temperatures using an excess of hydrogen over a metal catalyst.

Among the metals, which are known to catalyze the hydrogenation reaction are platinum, rhenium, cobalt, molybdenum, Nickel, tungsten and palladium. Typically, a commercial form of the catalyst used caused the oxides of these metals. Oxide, sing. These metals also catalyze other reactions, especially dehydrogenation at elevated temperatures. In addition, they can promote the reaction of olefinic compounds with themselves or other olefins to form dimers or oligomers with increased residence time.

Selective hydrogenation of hydrocarbon compounds has been known for some time. Peterson and others in the Selective hydrogenation of pyrolysis gasoline", presented at the Petroleum Division of the American Chemical Society in September 1962, discussed the selective hydrogenation of C4and the highest diolefines. Boito and others in the "Latest catalyst hydrogenation", hydrocarbon Processing. March 1985, presented a General, not set right, the review of various applications of hydrogenation catalysts, including selective hydrogenation rich in propylene flow and other factions. Conventional liquid-phase methods of hydrogenation is carried out at the present time, require a high partial pressures of hydrogen, usually more than 14 kg/cm2and more often up to 28 kg/cm2and more. Liquid-phase hydrogenation of the partial pressure of hydrogen is essentially the pressure in the system.

U.S. patent N 2 717 202 (Bailey) expanding the physical alteration of the injected pump catalyst and undisclosed conditions of pressure. U.S. patent N 4 221 653 (Chervenak and others) reveals sapotaceae hydrogenation with the use of the fluidized bed at extremely high pressures. The description of the patent in the UK N 835 689 discloses sapotaceae hydrogenation in the jet layer at a high pressure of fractions of C2and C3to remove acetylenes.

U.S. patent No. 5 087 780 (Hanbrid) discloses a process hydroisomerization of butenes using as a catalyst of palladium oxide supported on alumina, in the structure used as a catalyst and as an element in the catalytic distillation reactor - distillation column. Hydrogenation of dienes also occurs at high partial pressure of hydrogen is greater than the absolute pressure 4,922 kg/cm2but not at an absolute pressure of about 0,703 kg/cm2.

The advantage of the present invention is that diolefine (diene) and acetylene compounds contained in the hydrocarbon stream in contact with the catalyst, into olefins or alkanes with very little, if any, the formation of oligomers or minor, if any, the saturation monoolefins.

Disclosure of the invention

The present invention includes ethylene, together with a stream of hydrogen at the effective partial pressure of hydrogen of at least 0.007 kg/cm2absolute to less than 4,922 kg/cm2absolute, preferably less than 3,515 kg/cm2the absolute, in a distillation column containing a hydrogenation catalyst, which is a component of a distillation structure, and selective hydrogenation of part of the highly unsaturated compounds. Within the specified partial pressure of hydrogen is not used more hydrogen than is necessary to maintain the catalyst (most likely for the recovery of metal oxide catalyst and maintaining it in the hydride state) and hydrogenation of highly unsaturated compounds, and excess hydrogen is usually produced. Preferably the partial pressure of hydrogen is in the range from 0,007 to 0,703 kg/cm2absolute, more preferably not more than 0,492 kg/cm2an absolute. Optimal results were obtained in the range of partial pressures of a 0.035-0,352 kg/cm2excess.

Hydrocarbon stream typically contains aliphatic C2-C9compounds that can be narrow fractions or enable interval of the carbon content. In the invention it was found that GI is hydrogen, required in liquid-phase processes, which are still of commercial operations for this type of thread, but gives the same or better result. Consequently, capital investment and operating costs for this hydrogenation is substantially lower than for the previous commercial processes.

Without limiting the scope of the invention is believed that the mechanism of the effectiveness of this method consists in the condensation part of the vapors in the reaction system, which absorb sufficient hydrogen in the condensed liquid to achieve the desired close contact between hydrogen and the highly unsaturated compounds in the presence of a catalyst, leading to their hydrogenation.

Highly unsaturated compounds may be present in very small quantities, such as a few parts per million, and to the prevailing quantities, for example greater than 90 wt.%. The present invention can be used to remove impurities or to make a marketable quantities vysokoperedelnyh compounds in the target monoolefinic or alkanes.

The rate of hydrogen must be adjusted at the specified partial pressure in such a way as to be sufficient for the shows hydrogenation of monoolefins, and that (pressure) is understood as "effective partial pressure of hydrogen in the terms used here.

As can be easily understood, the number of highly unsaturated compounds in the hydrocarbon stream is a factor in the reasons for the choice of the optimal partial pressure of hydrogen, since at least the stoichiometric amount of hydrogen must be available for reaction in the system. When highly unsaturated compounds are impurities which are present in quantities of parts per million, lower range of partial pressure of hydrogen is redundant, but it is necessary because of the lack of selective reagent. Also the nature of the reaction between gas and liquid and the obvious need to absorb the liquid hydrogen make hydrogen excess in the range of partial pressures of the preferred form of operation.

An additional feature of the method is that part of monoolefins located in the stream or obtained by selective hydrogenation of diolefins may be samaritana into more valuable products. Isomerization reach the same family of catalysts used in the hydrogenation. Usually the relative velocities of the reactions of various seinemaritime of monoolefins;

(3) hydrogenation of monoolefins.

In General, it was shown that in the stream containing diolefin, diolefine will gidrirovaniya before isomerization will occur. It was also found that very low total pressure can be used to obtain optimal results in some embodiments of the present hydrogenation, preferably in the range of 3,515-10,55 kg/cm2redundant with the same excellent result. Both high and low pressure in a wide range can be used with satisfactory results.

In Fig. 1 shows a simplified flow diagram of the first variant of the present invention.

In Fig. 2 shows a simplified flow diagram of a second variant of the present invention.

In Fig. 3 shows a simplified flow diagram of a third variant of the present invention.

In Fig. 4 shows a simplified flow diagram of a fourth variant of the present invention.

Detailed description and preferred options

Although hydrogenation reactions are described as reversible at elevated temperatures above about 482,22oC (see, for example, article Peterson, cited above), when the fact is the label of the way, when the catalyst element is distillation, the equilibrium is violated, directing the reaction to completion, the reaction has a high guiding power, because the reaction products are removed and can not contribute to the feedback (principle of Lechatelier). In this way, in which there is a reversible reaction, the removal of reaction products to increase the guiding force of the reaction is no advantage. Also the poor performance of the previous methods, vapor-phase hydrogenation did not assume the use of a reaction distillation type. Therefore, it was not expected that the catalytic distillation will be useful for irreversible hydrogenation.

I believe that in this reaction the catalytic distillation is useful, first, because the reaction is occurring concurrently with distillation, the initial reaction products and other flow components are removed from the reaction zone as quickly as possible, reducing the likelihood of adverse reactions. Secondly, because all the components are boiling, the reaction temperature is governed by the boiling point of the mixture at a pressure system. Heat of reaction are simply leading to higher boiling, but not to increase the temperature at a given delerue pressure in the system. Bandwidth throttling (time = hour space velocity liquid-1) gives further control of product distribution and largely control side reactions such as oligomerization. Another advantage that this reaction may be present in catalytic distillation, leaching is the effect that internal irrigation provides the catalyst, thereby reducing the accumulation of the polymer and the coke formation. Internal irrigation may vary in the range from 0.2 to 20 W/W (weight of liquid directly below the layer of Katalizator/mass of distillate) and give good results: for C3-C5streams usually in the range of 0.5 to 4 W/e

Absolutely amazing, but a low partial pressure of hydrogen used in the distillation system does not affect the hydrogenation, as might be expected from the data on high partial pressure of hydrogen used in liquid-phase systems, which is a worldwide standard. From the installed previously, I believe that the phenomenon of condensation, which is a constant factor in distillation, leads to the same or better availability of hydrogen, the high pressure in the liquid phase, i.e. hydrogen papastavrou hydrogenation of acetylene compounds and diolefins, contained in enriched propylene stream to clean the stream and producing large amounts of propylene. Enriched with propylene stream is fed into the reactor - distillation column in the reaction distillation zone containing caused Pallavicini catalyst in the form of a catalytic distillation structure. The hydrogen serves in an amount necessary to maintain the reaction and is believed to restore oxide and maintaining it in the hydride state. Previously believed that the hydride state is an active state, however, a very low number of available hydrogen, which give excellent results may indicate otherwise. In any case, the state of the catalyst is the subject of theory associated with the mechanism, and not an object of the present invention. Reactor - distillation column operates at such pressure that the reaction mixture boils in the catalyst bed. If necessary, the VAT stream containing any high-boiling material, may be allocated for complete separation.

IN C3version operating at the previously mentioned partial pressure of hydrogen, the present invention includes a process for the selective hydrogenation of diolefins and the ACI (I) the first stream, containing propylene, diolefin and acetylene compounds, and (II) a second stream containing hydrogen, the reactor - distillation column in the feed area;

(b) simultaneously in the reactor - distillation column

(i) contacting the first and second streams in a distillation reaction zone with a hydrogenation catalyst capable of acting as a distillation structure thereby providing reaction essentially all diolefins and acetylene compounds with hydrogen with the formation of propylene and other hydrogenated products in the reaction mixture, and

(ii) allocation of propylene contained in the first stream, and propylene formed in the reaction of diolefins and acetylene compounds from the reaction mixture by fractional distillation, and

(C) removal of propylene selected from stage (b) (ii), together with the propane and lighter compounds, including unreacted hydrogen from the reactor - distillation column in the form of head straps. Perhaps the method may include the removal of any C4and more high-boiling compounds from the reactor - distillation column in the form of the cubic product. Significant losses of propylene during the hydrogenation occurs.

In Varian is racchi light naphtha, containing a mixture of hydrocarbons, together with a stream of hydrogen in the reactor - distillation column containing a hydrogenation catalyst, which is a component of a distillation structure, and selective hydrogenation of diolefins light naphtha. At the same time lighter components, including unreacted hydrogen, distilled and separated in the form of head straps from the product of the partial hydrogenation of light naphtha. Additionally and simultaneously with the selective hydrogenation and distillation of the C5-monoolefins isomerized in more desirable raw material for production of tert-mileticova ether (tame) by reaction of isoolefine with methanol. Essentially all diolefine become monoolefinic with very little hydrogenation monoolefins.

In the next version with the use of a light naphtha feedstock is mainly stream C5and the product is light naphtha is to divert as CBM product. Head straps are directed to a condenser, which condenses all, able to condense, and the part used as irrigation from the top of the column. In various embodiments, may be used to reflux the number of 0.5-20:1.

In another embodiment, using light naphtha as SS5the hydrocarbons separated from C6and higher components in the lower section of the reactor - distillation column. C6and higher components to divert as blue stream, while C5translated by boiling in the upper part of the reactor - distillation column, which contains the catalytic distillation structure, selectively hydrogenating diolefine. Hydrogenated C5taken from the top of the column together with the excess hydrogen and sent to the condenser, which condenses all that can condense, and then separated from neskondensirovannyh components (mainly hydrogen), for example, in a drum separator with irrigation. Part of the liquid from the separator is returned to the reactor - distillation column as irrigation, and the remainder is to divert as a product that can be directly sent to the installation tame. If necessary, higher catalytic distillation structure, you can use the optional inert distillation structure with a side-wall C5product for separating excess hydrogen together with other light components, such as air, water, etc. that may cause problems in downstream ustanawiania of diolefines, contained in a light naphtha, and involves the following stages:

(a) feeding (1) a first stream containing light naphtha containing diolefin, and (2) a second stream containing hydrogen, the reactor - distillation column in the feed area;

(b) simultaneously in the reactor - distillation column

(i) contacting the first and second streams in a distillation reaction zone with a hydrogenation catalyst capable of acting as a distillation structure thereby providing reaction essentially all diolefines with hydrogen with the formation of pentanol and other hydrogenated products in the reaction mixture, and

(ii) the use of such pressure in the reactor - distillation column, which is a part of the mixture evaporates exothermic heat of reaction;

(C) removal of liquid from stage (b) (ii) of the reactor - distillation column as the cubic product; and

(g) venting vapors from stage (b) (ii) together with any unreacted hydrogen from the reactor - distillation column as head straps.

Diolefine contained in C5the fraction boiling higher than other compounds and, therefore, can concentrate in the area of the catalyst, while monore the teres, are the reactions:

(1) isoprene (2-methylbutadiene) with hydrogen, giving 2-methylbutan-1 and 2-methylbutan - 2;

(2) CIS - and TRANS-1,3-pentadiene (CIS - and TRANS-piperylene) with hydrogen, giving penten-1 and penten-2;

(3) 3-methylbutane-1 2-methylbutan-2 and 2-methylbutan-1;

(4) 2-methylbutane-1 2-methylbutan-2;

(5) 2-methylbutan-2 2-methylbutan-1;

(6) 1,3-butadiene to butene-1 and butene-2.

The first two reactions to remove unwanted components, while the third is useful for raw materials tame reactor. 3-Methylbutan-1 does not react with methanol in the presence of sulfoxylates catalyst with the formation of tame, whereas two 2-methylbutane react. The present invention is realized by the method in the column filled with the catalyst, which, as it contains a vapour phase and a little of the liquid phase as in any distillation. Reactor - distillation column operates at such pressure that the reaction mixture boils in the catalyst bed. This method operates at a pressure in the head of the reactor - distillation column 0-24,61 kg/cm2excess, preferably 17,58 and less, and the temperature within the distillation reaction zone of 4.44-148,89oC, preferably 43,33-132,22oC, and the required partial is I per hour, coming in the reaction distillation column, per unit weight of catalyst in the catalytic distillation structures may vary in a very wide range within other parameters, for example from 0.1 to 35.

The benefits of using reactor - distillation column in this way selective hydrogenation are in the best selectivity conversion diolefine in the olefin, the conservation of heat and the separation by distillation, which can remove some impurities from the feedstock prior to contacting with the catalyst and concentrating the desired components in the area of the catalyst.

"Foam" layer of the catalyst support preferably by regulating the speed of withdrawal of the cube and/or head straps, which improves the efficiency of the catalyst, thereby reducing the required height of the catalyst layer. According to estimates, the liquid boils and physical condition is really a foam with a higher density than the normal density in the filled distillation column, but less than the fluid without boiling vapors, as described in U.S. patent No. 5 XX1 441, which is included in the consideration. Essentially understand what type of foam called "Jidkova rising steam creates foam. In fact, the continuous phase is liquid, but not steam, as it usually exists during distillation. The result is an increased contact of the liquid with a catalytic material by distillation and improved selective hydrogenation.

The temperature in the reactor is determined by the boiling point of the liquid mixture present at any given pressure. The temperature in the lower parts of the columns will reflect the composition of the material in this part of the column will be higher than at the top; that is, at constant pressure the change in temperature indicates a change in the composition in the column. To change the temperature, change the pressure. Temperature control in the reaction zone, therefore, carried out by changing the pressure; when the pressure increases, the temperature in the system increases and Vice versa.

As described, the catalytic material used in the method of hydrogenation, is in a form that serves as a distillation attachment. Generally speaking, the catalytic material is a component of a distillation system, functioning as a catalyst and as a distillation attachment, that is, the nozzle distillation columns has Gehenna, as the catalyst remains as a separate item. You can use any suitable hydrogenation catalyst, such as metals of group VIII of the Periodic system of elements as a main catalytic component, alone or with promoters and modifiers, such as palladium/gold, palladium/silver, cobalt/zirconium, Nickel, preferably deposited on a carrier such as alumina, refractory brick, pumice, coal, silica, resin, etc.

The preferred catalytic material contains an oxide of palladium, preferably 0.1 to 5.0 mass. % applied to the appropriate media, such as alumina, carbon, or silicon oxide, for example 3,175 mm extrudates of alumina. In the preferred catalytic distillation structure particles of catalytic material is placed inside a porous plate or sieve, which contain the catalyst and provide a distillation of the surface in the form of a wire mesh structure, such as a tubular structure of wire mesh or any other similar structure.

The preferred structure of the catalyst for this hydrogenation reactions is a flexible, semi-rigid open mesh trotereau, in one of several options, recently developed in connection with this method.

The new structure of the catalyst developed for the hydrogenation described in U.S. patent No. 5 266 546, fully incorporated here into consideration. In short, the new structure of the catalyst is a catalytic distillation structure, which is a flexible, semi-rigid open mesh tubular material such as wire mesh of stainless steel, filled with particles of catalytic material, and the tubular material has two ends and a length from half to two diameters of tubular material, the first end sealed by the first axis with the formation of the first seam and a second end sealed by the second axis with the formation of the second seam, so that the plane of the first seam along the axis of the tubular material and the plane of the second seam along the axis of the tubular material divide each other in half angle of 15-90o.

U.S. patent No. 4 242 530 and U.S. patent No. 4 443 559 included here into consideration, reveal marked the catalyst in several pockets, a fabric tape or tubular design of wire mesh, which are secured in the reactor - distillation column using the open grid C.93, included in the reference, describes several other known suitable structures and reveals new design, suitable for this method.

Particles of catalytic material can be a powder, small irregular lumps or fragments, small beads, and so on, the shape of the particles of catalytic material in the structure is not crucial as there is sufficient surface area to ensure acceptable reaction rate. The particle size of the catalyst can be best determined for each catalytic material (as porosity or the available area of the inner surface will vary for different materials and of course to influence the activity of the catalytic material).

In the present method, the preferred hydrogenation catalyst structures for stuffing are those patterns that use more open structure permeable plates or wire mesh.

In Fig. 1 shows a simplified flow diagram in a preferred embodiment, for C5-hydrocarbons. Reactor - distillation column 10 contains the nozzle of a suitable hydrogenation catalyst as part of a distillation structure 12 out of 14. Light naphtha is served by line 1 into reactor - distillation column 10 below the nozzle of the catalyst. Gaseous hydrogen is served by line 2 in the lower part of the nozzle layer of catalyst or near it.

Preferably C5-raw material and hydrogen is fed into the reactor - distillation column separately or they can be mixed before serving. The mixed raw material is introduced below the layer of catalyst or in the lower part of the layer. Hydrogen itself is injected below the layer of catalyst and C5stream is preferably introduced below the layer. Although the hydrocarbon is preferably introduced below the layer, in order not to let the heavy impurities such as sulfur compounds, it can also be introduced to the middle one-third of the layer. The pressure is chosen such to keep dieny and other highly unsaturated compounds in the catalyst bed, while propylene and lighter connection is distilled over in the column head.

Heat contribute to the cube along the line 4 circulation through the evaporator 40 and back to the column through line 13. After start of the reaction heat of reaction, which is exothermic, causing more evaporation of the mixture in the layer. Pairs are selected from the top through line 3 and is directed to the condenser 20, where essentially all able condensive the soup faction, where the condensed material is collected and separated from neskondensirovannyh material, such as unreacted hydrogen. Part of the condensed material collected in the collection irrigating fraction is directed to the top of the reactor - distillation column 10 through line 6. Product distillation allocated on line 9, suitable as raw materials for reactor tame. Neskondensirovannyh material produced from the collection of irrigation fraction in line 7, to conserve hydrogen can be recycled to the reactor (not shown).

CBM product essentially does not contain diolefins, divert on line 8 and may direct the preparation of mixed gasoline as stable gasoline. The method is useful because the high heat of hydrogenation is absorbed by the evaporation of the liquids, so that the temperature control is achieved by regulating the pressure in the system. All excess hydrogen otparivat of the cubic product. In the case of C5-hydrocarbons digidrirovannye components less volatile and tend to remain in the reactor for a longer time contributing to a more complete reaction.

In Fig. 2 shows a second variant of the invention, in which light naphtha is fed to the column 10 above the IG. 1. Fig. 3 shows a third variant, in which the column has an extra ordinary distillation design 216 upstream of the catalytic distillation structure 12 to separate all4-hydrocarbons lighter material, hydrogen, and other higher boiling components from C5-hydrocarbons, which are taken as a side stream through line 209.

Example 1

In this example, the hydrocarbon stream is enriched with propylene, for example, C3the fraction of gas fractionation plant process for catalytic cracking or steam cracking. A typical analysis of such a flow is given in table II.

The catalyst is 0.3 mass. % PdO on the extrudates 3,175 mm Al2O3(aluminium oxide), a hydrogenation catalyst, supplied by United Catalysts Inc. indicated G68F. Typical physical and chemical properties of the catalyst provided by the manufacturer, are presented in table. I.

It is believed that the catalyst is a palladium hydride, which is formed during the operation.

The rate of hydrogen supplied to the reactor must be sufficient to maintain the catalyst in active form, as hydrogen is consumed at the catalyst on the hydrogenation. The speed at which to maintain the hydrogenation reactions and replenish the flow of hydrogen from the catalyst, but below the required for the hydrogenation of propylene, and to prevent zaklepywanie columns. Usually the molar ratio of hydrogen to acetylene compound in the raw material in a fixed bed will be about of 1.05 to 2.5, preferably of 1.4 to 2.0. The presence of a hydrogen feedstock, as described here, does not impact adversely on the physical operation of the catalytic distillation system (see tab. II).

Propylenediamine raw materials and the hydrogen can be fed into the reactor - distillation column separately or they can be mixed before serving. The mixed raw material is introduced below the layer of catalyst or in the lower part of the layer. Hydrogen itself is injected below the layer of catalyst and C3stream is preferably introduced below the layer. The hydrocarbon introduced into the layer, can lead to a deactivation of the catalyst by impurities. The selected pressure is such that holds dieny and acetylene in the catalyst bed, while allowing propylene and lighter components to Athanasia as the head of a shoulder strap. All unreacted hydrogen comes out on top together with C3-hydrocarbons.

As a pilot plant used laboratory column with a diameter of 2.54 cm and a height of 4,572 m Catalyst (240 g, 0.3 wt.%create a catalytic distillation structure, described in U.S. patent No. 5 266 546 included in the review. Catalytic distillation structure was loaded in the middle 3 m columns, and the upper and lower 0,763 m was filled with inert distillation packing. In the column was filed enriched in propylene raw material and heated to initiate the reaction. The pressure in the head of the column was maintained in the range 16,87-22,20 kg/cm2. In the pilot unit CBM product has not been selected and the equilibrium quantity of C4- and higher hydrocarbons of about 15 vol.% was present in the lower section of the column, which was indicated at a constant temperature of about 60oC. Constant temperature also indicated that there is no accumulation of heavier materials in the oligomerization. If there is any residual diene, the temperature in Cuba would rise due to the accumulation of heavy components. Therefore, there is a full selective removal of dienes and acetylenes. In industrial installations or installations larger scale CBM selection should be used to perform the separation of C4- and higher hydrocarbons from propylene. Table IV gives the results of the pilot experience.

Example 2

The catalyst is 0.34 wt.% PO on the fields 3-8 mimic the properties of the catalyst, presented by the manufacturer, are given in table. III.

It is believed that the catalyst is a palladium hydride, which is formed during the operation. The rate of hydrogen supplied to the reactor must be sufficient to maintain the catalyst in active form, as hydrogen is consumed at the catalyst on the hydrogenation.

"An effective amount of hydrogen" as that term is used here in relation to C5-hydrocarbons is at least 1.0 to 1.0, preferably of 2.0 to 1.0, for example, 10 moles of hydrogen per mole of diolefin.

Use shown in Fig. 4 steel column 310 with a diameter of 7.62 cm and a height of 9,144 m evaporator 340, the condenser 320 and irrigation system 330 and 306. The average height of the column 4,572 m fill catalytic distillation structure 312, containing 0.34 wt.% palladium on spherical 3,175 mm aluminium oxide, which is in the pockets of fiberglass tape, wrapped with wire mesh stainless steel. The column is rinsed with nitrogen at a pressure of up to 1,406 kg/cm2redundant. Light naphtha, pre-fractionated to remove the greater part of C6and higher material, serves first in the column on line 301 in the number 22,68 kg/( line 308 and begin circulation through the evaporator along the lines 304 and 313. The evaporator 340 is heated to achieve pairs of top of the column, as evidenced by the same temperature 54,44oC throughout the column. Hydrogen is introduced into the bottom of the column with the speed 0,227-0,283 m3/h on lines 302. The pressure in the column is then controlled to maintain the temperature of the cube about 160oC and the temperature of the catalyst layer is about 126,67oC. Therefore, the pressure in the column head support about 14,06 kg/cm2redundant. Head shoulder straps taken through line 303 and partially condense in the condenser 320 and the whole condensable material collected in the collection 330 irrigating faction and return to the top of the column as irrigation line 306. Neskondensirovannyh material released from the collector via line 307. Liquid CBM material is taken through line 308. The results are shown in table V, which compares the analysis of raw materials and cubic product.

Example 3

During the experiment of example 2, the pressure in the head of the column was adjusted to change the temperature of the catalyst layer. At lower temperatures the conversion diolefines was lower, but the main difference was that the temperature is much stronger effect on the isomerization of 3-methylbutane-1. Table VI compares the type field
This series of experiments demonstrates the unexpected removal of dienes from C4streams at extremely low partial pressures of hydrogen. It also shows that a lower total pressure is also acceptable. Experiments were performed in two techniques. In the first technique used conventional distillation - continuous steam phase. The second technique used is preferably a liquid phase type "IFS".

The reactor used in experiment 1, there was a column with a diameter of 7.62 cm, containing 6,096 m nozzles of the catalyst 0,028 m3the catalytic material (0.5% of Pd on 8-12 mesh aluminum oxide-E144SDU produced Calcicat, Catalyst and Performance Chemicals Division, Mallinckrodt, Inc.) and 1.4 m steel rings Poll diameter 15,875 mm above and 4.7 m steel rings Poll diameter 15,875 mm below the catalyst layer containing 0,028 m3the catalytic material (0.5% of Pd on 8-12 mesh aluminum oxide-E144SDU produced Calcicat, Catalyst and Performance Chemicals Division, Mallinckrodt, Inc. ) and 1.4 m steel rings Poll diameter 15,875 mm above and 7.62 m of wire demister and 15,240 m steel rings Poll diameter 15,875 mm below the catalyst bed. The catalyst was loaded in a tubular 2.54 cm wire sheath located diagonally on a wire demister and make sure that rolled in packages with a diameter of the pressure in the head 8,44 kg/cm2excessive and in the evaporator direct hydrocarbon feedstock at a rate of approximately 9,072 kg/h and the evaporator set at 10%, which is maintained for 15 minutes, during this time, the speed of the raw material is set to maintain 50-75% level in Cuba up until the temperature in the column head will not differ on 20oC from the temperature in the cube, and then increase the feed rate to 45 kg/h When the excess pressure reaches 0,070 kg/cm2serves hydrogen with speed 0,425 m3/H. the Cube is heated to a uniform temperature 71,11oC and include the average flow irrigation. Choose the pressure in the column head and spend the reaction distillation. Hydrocarbon, C4-raw materials improve, and the results of each are shown in tables VII and VIII.

The experiments conducted by the method GFS, remove all dieny, while conventional distillation leaves a few parts per million under the same conditions. The speed of the internal irrigation is understood as the ratio of the liquid immediately below the nozzle of the catalyst to distillate (W/W). The data show that the method GFS provides better removal of dienes.

Example 5

Streams of light naphtha fluid catalytic cracking

Use is manufactured by United Catalyst, Inc. Catalytic nozzle (9,144 m, 0,0425 m3the catalytic material prepared in the form of a distillation structure, as described in example 4 was loaded into a 7.62 cm column, using 1,524 m steel rings Poll 15,875 mm diameter and 3,048 m unfilled space above and 0,914 m wire demister and 15,240 m steel rings Poll diameter 15,875 mm below the catalyst bed. Distillation was collected gidroobladnannya C5from the top of the column and the heavier hydrocarbons from the cube. Raw materials, conditions and results for each of the three experiments are shown in tables IX-XI.

The results of the experiment 3 at 74 hours of operation at low partial hydrogen pressure and high flow rate were lower than expected. The increase in the partial pressure of hydrogen only to 0,309 kg/cm2abs. when working within a 272 h by conventional distillation method improves the removal of diene 10 times.

Example 6

C3streams

Used the method of example 4, however, the catalyst in experiment 1 was G68C, 0,3% palladium on 3-6 mesh aluminum oxide produced by United Catalyst, Inc. 6.086 m nozzles catalyst (0.028 m3the catalytic material is prepared in the form of distillation structures, as described in U.S. patent N 5.266.546 that t is relative to each other. Catalytic nozzle was loaded into 7.62 cm column containing 1,524 m steel rings Poll 15,875 mm diameter and 3,048 m unfilled space above and 0,914 m wire demister and 15,240 m steel rings Poll diameter 15,875 mm below the layer. The same structure and the column used in the experiment 2, but the catalyst was G68H (0.3% of Pd and 0.3% Ag aluminum oxide) from United Catalyst.

The distillation is carried out with a selection hydroblasting C5from the top of the column and the heavier components from the cube. Raw materials, conditions and results for each of the three experiments are shown in tables XII and XIII.

1. Process for the selective hydrogenation of highly unsaturated compounds, which consists in contacting the hydrocarbon stream containing highly unsaturated compounds, which include diolefin and/or acetylene, in the presence of hydrogen with a hydrogenation catalyst, wherein the hydrocarbon stream is served together with a stream of hydrogen at the effective partial pressure of hydrogen in the range of at least from about 0,007 to less than 4,922 kg/cm2absolute to a distillation column containing a hydrogenation catalyst, which is a component of a distillation structure, and selectively hydronaut viskontas the Kie connection 3 - 9 carbon atoms.

3. The method according to p. 1, characterized in that the hydrocarbon stream contains as a main component normal olefins, which emit in the quality of the products of hydrogenation.

4. The method according to p. 1, characterized in that the hydrocarbon stream has a volumetric rate of 0.1 - 35 h-1.

5. The method according to p. 2, characterized in that the pressure in the upper part of the column is in the range 0 - 24,61 kg/cm2excess.

6. The method according to p. 1, characterized in that the partial pressure of hydrogen is less than 3,515 kg/cm2absolute.

7. The method according to p. 6, characterized in that the partial pressure of hydrogen is less than 0,703 kg/cm2absolute.

8. The method according to p. 7, characterized in that the partial pressure of hydrogen is less than 0,492 kg/cm2absolute.

9. The method according to p. 5, characterized in that the partial pressure of hydrogen is less than 3,515 kg/cm2absolute.

10. The method according to p. 9, characterized in that the partial pressure of hydrogen is less than 0,703 kg/cm2absolute.

11. The method according to p. 10, characterized in that the partial pressure of hydrogen is minishell or compound of the metal of group VIII as a main catalytic component.

13. The method according to p. 12, characterized in that the catalyst contains palladium.

14. The method according to p. 5, characterized in that the pressure in the upper part is in the interval 3,515 - 10,55 kg/cm2absolute.

15. Process for the selective hydrogenation of highly unsaturated compounds containing diolefin and/or acetylene compounds rich in olefin stream comprising contacting the latter in the presence of hydrogen with a hydrogenation catalyst, characterized in that it comprises the stages of: a) feeding a first stream containing olefins, diolefin and/or an acetylene hydrocarbon compounds, and a second stream containing hydrogen to a distillation column in the feed area; b) simultaneously contacting flows into the distillation column at a partial pressure of hydrogen from 0,007 to less than 3,515 kg/cm2; (i) contacting the threads in the distillation reaction zone with a hydrogenation catalyst, made in the form, which acts as a distillation structure, providing the reaction essentially all diolefins and/or acetylene compounds with hydrogen with the formation of less unsaturated hydrocarbons in the reaction mixture, and (ii) the allocation of the olefins contained in the first thread 16. The method according to p. 15, wherein the first stream is introduced into the lower part of the distillation reaction zone or below it.

17. The method according to p. 15, characterized in that the threads are injected separately into the distillation column.

18. The method according to p. 15, wherein the first and second streams are mixed prior to entry into the distillation column.

19. The method according to p. 15, characterized in that the hydrocarbon stream contains aliphatic compounds with 3 to 9 carbon atoms.

20. The method according to p. 19, wherein the hydrocarbon stream is a C3-faction.

21. The method according to p. 19, wherein the hydrocarbon stream is a C4-faction.

22. The method according to p. 19, wherein the hydrocarbon stream is a C5-faction.

23. The method according to p. 19, wherein the hydrocarbon stream is a C6-faction.

24. The method according to p. 19, wherein the first and second streams unite before entering the distillation column.

25. The method according to p. 15, characterized in that the hydrogenation catalyst contains a metal or compound of a metal of group VIII as a main catalytic component.

26. The method according to p. 25, the MINIA.

27. The method according to p. 15, characterized in that the pressure in the upper part of the distillation column reactor is in the range 16,87 - 22,05 kg/cm2excess.

28. The method according to p. 27, wherein the first propylene stream contains.

29. The method according to p. 15, characterized in that the distillation structure is flexible, semi-rigid open mesh tubular material in the form of a wire mesh, filled with the powdered catalytic material hydrogenation.

30. The method according to p. 15, characterized in that it further includes a step (C) selection of the separated olefins from stage (b) (ii) together with alkanes and lighter compounds, including unreacted hydrogen from the distillation columns in the form of the head of a shoulder strap.

31. The method according to p. 15, characterized in that the distillation column operates at a pressure in the upper part of the column 0 - 17,58 kg/cm2excess.

32. The method according to p. 31, characterized in that the pressure is in the range 3,515 - 10,55 kg/cm2excess.

33. The method according to p. 15, characterized in that the temperature within the distillation reaction zone is in the range of 4.44 - 148,89oC.

34. The method according to p. 33, characterized Ter> 35. The method according to p. 15, characterized in that essentially all diolefin and acetylene compounds are removed from the hydrocarbon stream.

36. The method according to p. 15, characterized in that the first thread has a space velocity of 0.1 - 35 h-1.

37. The method according to p. 16, characterized in that the hydrogenation catalyst contains a metal or compound of a metal of group VIII as a main component.

38. The method according to p. 37, characterized in that the hydrogenation catalyst contains 0.1 to 5.0 wt.% oxide of palladium in the catalyst is aluminum oxide.

39. The method according to p. 37, characterized in that the distillation column operates at a pressure in the upper part of the column 0 - 17,58 kg/cm2excess.

40. The method according to p. 39, characterized in that the temperature within the distillation reaction zone is in the range of 4.44 - 148,89oC.

41. The method according to p. 40, characterized in that the pressure is in the range 3,515 - 10,55 kg/cm2excess.

42. The method according to p. 41, characterized in that the temperature within the distillation reaction zone is in the range 43,33 - 132,22oC.

43. The method according to p. 42, characterized in that the partial pressure of hydrogen is in the range 0,007 - 0,703 to that is 0.5 - 5.

45. The method according to p. 15, characterized in that essentially all of the highly unsaturated compounds hydronaut.

 

Same patents:

FIELD: chemistry.

SUBSTANCE: this invention relates to the catalyst used for alkylation of aromatic compounds by monoolefinic aromatic compounds, in particular to the catalyst used for the selective hydrogenization of diolefin and acetylene into olefins; this method describes the catalyst for the selective hydrogenization of diolefin and acetylene containing nondense medium containing gamma-aluminum oxide or theta-aluminum oxide with the volume of micropores less than 10% of the volume of the pores and the specific service 150 m2/g and the palladium on the medium in the amount of 50 - 5000 ppm.

EFFECT: catalyst has the minimal resistance to diffusion through the large pores and minimizes hydrogenization of olefines into paraffins.

9 cl

FIELD: chemistry.

SUBSTANCE: invention refers to the way of selective hydrogenation of diolefines and ethines that includes contacting of the olefinic flow containing along with olefines diolefines and ethines with the selective hydrogenation accelerant that contains a low-density bearer the density of which is lower than 0.5 g/cm with the micropores volume of no more than 10 % of the volume of the accelerant pores and with the specific surface area from more than 50 m²/g to 150 m²/g; the micropores are characterized by the pore diameter that does not exceed 100 Å, and more than half of the accelerant pore volume is comprised by the pores that have a diameter of at least 1,000 Å.

EFFECT: production of slightly branched alkyl benzenes.

9 cl

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for selective hydrogenation of acetylene and diene hydrocarbons to C2-C5+ hydrocarbon fractions. The catalyst is an alumina support on which there is an active palladium component and a promoter, said promoter being in attached in oxide form and palladium particles being in zero oxidation state in the electron stat of valence orbitals of their atoms. The catalyst is characterised by an absorption band of a carbon monoxide and palladium complex with wave number 2060-2100 cm-1 in the infrared spectrum of the adsorbed carbon monoxide, wherein the catalyst has the following composition, wt %: palladium 0.005-1, promoter 0.005-5, aluminium oxide being the balance.

EFFECT: high activity and selectivity of the catalyst for selective hydrogenation of alkyne and diene hydrocarbons to C2-C5+ hydrocarbon fractions owing to high dispersity and change in electron density and geometric characteristics of particles of the active component with more complete interaction with the promoter.

3 cl, 4 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing norbornane derivatives of general formula where R=H, R1=CN, or R-R1=-CH=CH-CH2-. The method involves hydrogenation of the norbornene derivative with hydrazine hydrate in the presence of a catalyst, and is characterised by that the catalyst used is nickel nanoparticles obtained from its nitrate (II) in situ, and the norbornene derivative used is dicyclopentadiene or 2-cyanonorbornene-5 and the process is carried out in the medium of isopropyl alcohol with molar ratio norbornene derivative: hydrazine hydrate: catalyst equal to 1:5.3-6:0.4-0.6 at temperature 80-82°C for 8 hours followed by extraction of the end product.

EFFECT: use of the present method enables to obtain desired compounds without using hydrogen gas, expensive catalysts and complex process conditions.

1 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing dicyclopentene (tricyclo-[5.2.1.02.6]decene-3), involving hydrogenation of dicyclopentadiene in a solution with hydrogen in liquid phase using fine catalysts of the platinum group at atmospheric pressure and moderate temperature of (30-80°C), followed by separation of the end product. The method is characterised by that hydrogenation is carried out in a toluene solution in the presence of an additive - functionally substituted aromatic compounds which are capable of being adsorbed on the surface of the catalyst, such as p-oxydiphenylamine, hydroquinone, β-naphthylamine, p-phenylenediamine, 2,6-di-tert-butyl-4-methylphenol, in amount of 1-5 wt % in terms of the catalyst used, and separation of the desired dicyclopentene is carried out by distilling toluene at low or atmospheric pressure.

EFFECT: use of the present method enables to obtain dicyclopenene of high purity.

1 cl, 6 ex

FIELD: chemistry.

SUBSTANCE: composition of the catalyst is formed in the following ratio, wt %: palladium 0.005-1, promoter 0.005-5, copromoter if necessary 0.005-5, carrier - the remaining part. The promoter on the carrier is fixed in the oxide form to the active component. Palladium particles are fixed on the carrier in the zero degree of oxidation in the electronic condition of valence orbitals of their own atoms. The catalyst is characterised by a band of an absorbing complex of carbon monoxide with palladium with the wave number of 2060-2100 cm-1 in the infrared spectrum of absorbed carbon monoxide. As the carrier applied is a highly-porous cellular carrier, produced from a metal or aluminium oxide, characterised by the porosity not less than 85%, the average size of the pores is 0.5-6.0 mm. On the highly-porous cellular carrier placed is a layer of aluminium oxide with the formation of a secondary carrier, on which the promoter and the active component palladium are successively placed. The secondary carrier aluminium oxide is characterised by the width from 10 mcm to 500 mcm, specific surface of not less than 20 m2/g, volume of the pores from 0.1 to 1.0 cm3/g and is made with the pores with a diameter over 5 nm, the volume of which constitutes 50-98% of the total volume of the pores. The secondary carrier in the general composition of the catalyst constitutes not less than 5 wt %.

EFFECT: improvement of thermo- and weight-exchange and diffusion characteristics with the elimination of a possibility to form local overheats of the catalyst layer and diffusion limits of the transport of initial compounds and reaction products.

4 tbl, 22 ex

FIELD: chemistry.

SUBSTANCE: one of versions includes stages, at which hydrocarbon supplied initial raw material is separated into first fraction of carbon-containing compounds which contain not more than 5 carbon atoms, and second fraction of compounds, which have lower pressure of steam in comparison with pressure of steam in first fraction; dienes and/or acetylenes from first phase are selectively hydrated with formation of respective monoolefins; paraffins from first fraction are converted with formation of respective monoolefins in conversion flow; and contact cooling of subjected to transformation monoolefins from conversion flow with application of liquid hydrocarbon flow, which contains admixtures, with admixtures having lower pressure of steam in comparison with pressure of steams of compounds from first fraction; where dienes and/or acetylenes from first fraction are subjected to selective hydration before transformation of paraffins from first fraction with formation of monoolefins and after extraction of first fraction from supplied initial hydrocarbon raw material.

EFFECT: application of claimed invention makes it possible to render minimal influence on selective hydration catalysts.

10 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing 1-butene and a 1,3-butadiene derivative. Method involves following steps: a) non-oxidatively catalytically dehydrogenating a feedstock gas stream containing n-butane, hydrogen, other low-boiling secondary constituents and high boilers, to form a product mixture containing unreacted n-butane, 1-butene, 2-butenes, 1,3-butadiene, hydrogen, other low-boiling secondary constituents and high boilers; b) removing hydrogen, other low boilers and high boilers, to give a product mixture containing n-butane, 1-butene, two 2-butenes and 1,3-butadiene; c) reacting some of 1,3-butadiene obtained in removing b), to form a derivative; d) removing 1,3-butadiene derivative obtained in reacting c); e) selectively hydrogenating 1,3-butadiene not derivatised in reacting c), to form 1-butene; and f) distillation removal 1-butene from hydrocarbon stream obtained in hydrogenating e), to leave a residual stream.

EFFECT: use of present method enables to obtain 1-butene and a butadiene derivative, without using expensive methods of separation.

14 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: method consists in the reduction of styrene derivatives with molecular hydrogen in the presence of nickel nanoparticles under heating and is characterized in that nickel nanoparticles immobilized on a zeolite are used as the catalyst, the reactants are fed directly to the catalyst by two streams, the first of which is hydrogen supplied at a flow rate 420-710 l/(kgcatH), the second - the styrene derivative, supplied at a flow rate of 0.55 l/(kgcatH), and the reaction is carried out at a temperature of 190-260°C.

EFFECT: simplification of the method for reducing styrene derivatives and reducing the reaction time.

4 ex

FIELD: chemistry.

SUBSTANCE: nickel nanoparticles immobilized on zeolite are used as the catalyst, the reactants are fed directly to the catalyst by two streams, the first of which is hydrogen supplied at a flow rate of 150-310 l/(kg⋅cath), the second - cyclodiene or cyclotriene supplied at a flow rate of 0.55 l/(kg⋅cath)⋅, and the reaction is carried out at a temperature of 180-240°C.

EFFECT: simplification of the method for recovering unsaturated cyclic compounds and a decrease in the reaction time.

3 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention provides a catalyst for selective hydrogenation of alkines and dienes in C2-C5+-olefin mixtures, said catalyst containing 0.005 to 1% palladium and 0.005 to 1% eleventh group metal both fixed on silica carrier. Eleventh group metal is uniformly spread throughput cross-section of catalyst grains while palladium is present in border layer in proximity of catalyst grain surface. According to invention, carrier material is mixed with eleventh group metal to form carrier, which is the calcined, impregnated with palladium-containing solution, and calcined once more. Selective alkine and diene hydrogenation process in presence of above-defined catalyst is also provided.

EFFECT: reduced conversion rate and reduced formation of oligomers.

10 cl, 3 tbl, 5 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to catalytic compositions palladium/silver on carrier, to methods for preparation thereof, and to unsaturated hydrocarbon hydrogenation processes. catalytic composition containing platinum, silver, and iodine component (options) is described as well as methods for preparation thereof comprising interaction of composition containing palladium, silver, and carrier with liquid composition containing iodine component followed by calcination. Alternatively, carrier is brought into consecutive interaction with palladium component, silver component, and iodine component using intervals for intermediate calcination after each interaction. Hydrocarbon hydrogenation process is also described, in particular selective hydrocarbon of acetylene into ethylene, in presence of above-defined catalytic composition.

EFFECT: increased hydrogenation process selectivity and reduced degree of catalyst deactivation.

52 cl, 1 tbl, 6 ex

FIELD: gas treatment.

SUBSTANCE: invention relates to improved method for removing acetylene compounds from hydrocarbon streams, which method comprises bringing hydrocarbon stream containing a first concentration of acetylene compounds and olefins with catalyst being consisted either of supported non-sulfided metallic nickel or the same modified with metals such as Mo, Re, Bi, or mixture thereof, said non-sulfided nickel being present on support in quantity by at least 5% superior to quantity required for selective hydrogenation of acetylenics. Hydrogenation is carried out in first reaction zone at temperature and pressure as well as hydrogen concentration favoring hydrogenation of acetylenics, after which hydrocarbon material is discharged containing second concentration of acetylenics inferior to its first concentration.

EFFECT: improved acetylenics removal selectivity and increased yield of target olefin compounds.

20 cl, 10 dwg, 1 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to catalysts of hydration, method of their production and use for hydration such as selective hydration of acetylene admixtures in non-purified olefinic and diolefiniuc flows. Described is a selective catalyst of hydration for selective hydration of acetylene admixtures in non-purified olefinic and diolefinic flows, containing only nickel or nickel and one or more elements chosen from the group consisting of Cu, Re, Pd, Zn, Mg, Mo, Ca and Bi, applied on carrier, which is alumunium oxide with the following physical characteristics: BET surface area from 30 to approximately 100 m2/g, total volume of pores on nitrogen from 0.4 to approximately 0.9 cm3/g and the average pore diameter from approximately 110 to 450 Å , where the said catalyst contains from approximately 4 to approximately 20 weight % of nickel. Described are the method of catalyst production, which includes impregnation of carrier represented by aluminium oxide and having the aforesaid physical characteristics, with soluble salts of only nickel or nickel and one or more elements chosen from the group consisting of Cu, Re, Pd, Zn, Mg, Mo, Ca and Bi, from one or more solutions, obtaining impregnated carrier, where the said catalyst contains from approximately 4 to approximately 20 weight % of nickel. Also described is the method of selective hydration of acetylene compounds, which includes contact of original raw material containing acetylene compounds and other unsaturated compounds, with the described above catalyst.

EFFECT: increased degree of 1,3-butadien extraction with full or nearly full conversion of C4-acetylenes.

25 cl, 1 dwg, 1 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention refers to selective removal of acetylenic compounds from the hydrocarbon flows using the specific catalysts on the base of Ni. The catalyst for selective hydrogenation of s contains 1) Ni precipitated with promoting quantity of Pd to the carrier - aluminium oxide containing spinel-type mixed oxides MAI2O4 whereat M is any bivalent cation and 2) promoted Pd. Method for selective hydrogenation of compounds provides the contact of the said s with described above catalyst in the presence of hydrogen at temperature and pressure suitable for at least partial hydrogenation of the said compounds to more saturated products.

EFFECT: increasing of process selectivity.

21 cl, 8 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention refers to xylene isomerisation in feed stock containing nonequilibrium mixture of two or more xylenes and optionally ethylbenzene characterised by that feed stock flow contacts with layered catalyst in catalytically effective amount in isomerisation environment including temperature within 100° to 550°C, absolute pressure within 10 kPa to 5 MPa and hydrogen to hydrocarbons molar ratio within 0.5:1 to 6:1, required for isomerisation product flow containing xylenes, where paraxylene takes at least 23 wt %, orthoxylene at least 21 wt %, and methaxylene at least 48 wt %. Said catalyst has an alpha-alumina frame of principal dimension at least 300 mcm coated with a layer of MFI molecular sieve structure with aperture diameter 4 to 8 angstrom, and an alumina or gamma-alumina binding material of thickness 250 mcm and less, and at least one hydrogenating metal component chosen of the group including Pt and Mo, as the binding material represents aluminium phosphate, and Re, as the binding material is represented by gamma-alumina. At least 75 wt % of hydrogenating metal component in the catalyst is accumulated in the layer wherein total amount of formed toluene and trimethylbenzene is 3 wt % and less of total xylenes and ethylbenzene in feed stock flow.

EFFECT: reduced loss of aromatic hydrocarbons and good balance approximation in isomerisation process.

7 cl, 4 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: described is a catalyst which contains 0.01-1.0 wt % palladium in form of particles with controlled size ranging from 1.5 to 20 nm, deposited on bidispersed silica gel. A method of preparing the palladium catalyst is described, which is characterised by that, a dried support which contains an alkali metal in amount of not more than 0.01 wt, bidispersed silica gel with specific surface area of 150-350 m2/g, total pore volume of 0.8-1.2 cm3/g with complete absence of micropores, volume of mesopores with radius of approximately 50 Ǻ 0.60-0.85 cm3/g and volume of macropores with radius of 1000-5500 Ǻ - 0.15-0.30 cm3/g, is impregnated with an aqueous solution of stabilised palladium nitrate at certain pH values, with subsequent drying, calcination in air and reduction. Also described is a method of purifying olefins from impurities of polyunsaturated hydrocarbons through catalytic hydrogenation in the presence of the catalyst described above.

EFFECT: increased degree of purity of olefins from polyunsaturated hydrocarbons up to 0,1 ppm, reduced loss of olefin material and prevention of formation of undesirable oligomers which lead to deactivation of the catalyst.

7 cl, 1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: this invention relates to the catalyst used for alkylation of aromatic compounds by monoolefinic aromatic compounds, in particular to the catalyst used for the selective hydrogenization of diolefin and acetylene into olefins; this method describes the catalyst for the selective hydrogenization of diolefin and acetylene containing nondense medium containing gamma-aluminum oxide or theta-aluminum oxide with the volume of micropores less than 10% of the volume of the pores and the specific service 150 m2/g and the palladium on the medium in the amount of 50 - 5000 ppm.

EFFECT: catalyst has the minimal resistance to diffusion through the large pores and minimizes hydrogenization of olefines into paraffins.

9 cl

FIELD: chemistry.

SUBSTANCE: invention relates to selective heterogeneous nickel catalysts for hydrogenation of unsaturated hydrocarbons and sulphur removal and methods for production and use thereof. Described is a selective heterogeneous catalyst containing nickel on a support which is a diatomite powder having the following physical properties: BET surface area 20-50 m2/g, particle size less than 10 mcm - no more than 15 wt %, greater than 71 mcm - no more than 40 wt %, 10-71 mcm - the balance, or crushed shale taurite, having the following physical properties: BET surface area 12-16 m2/g, particle size less than 10 mcm - no more than 40 wt %, or a mixture thereof in ratio of 50:50. The catalyst has the following composition, wt %: nickel 52.0-54.0, aluminium oxide 2.5-3.8, iron oxide 1.3-1.7, sodium oxide 0.5-1.5, calcium oxide 0.1-0.6, magnesium oxide 0.25-0.8, sulphide sulphur 0.1-0.5, silicon dioxide - the balance. Also described is a method of producing said catalyst by mixing a support with 5-6% aqueous nickel sulphate solution, adding to the obtained suspension 25-27% calcined soda solution until achieving molar ratio of calcined soda to nickel sulphate of 1.6-1.7:1.0, at medium pH 9.0, or in two steps: at the first step to molar ratio calcined soda to nickel sulphate of 0.8-0.9:1.0, at medium pH 6.0-7.0, at the second step to molar ratio calcined soda to nickel sulphate of 1.6-1.7:1.0, at medium pH 9.0-10.0. Further, the method includes steps of filtering, washing, drying and pelletising without steps of reducing with hydrogen and passivation with a nitrogen-air mixture. Before use, activation of the fresh catalyst or recovery of the catalyst after 1500-3000 hours of contact thereof with the material is carried out directly in the hydrogenation reactor in a current of circulating hydrogen at 230-500°C for 5-50 hours. Also described is a method of using said catalyst.

EFFECT: achieving high activity, selectivity and stability of hydrogenating unsaturated hydrocarbons and sulphur removal.

6 cl, 6 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: composition is described, comprising an extruded inorganic support containing a metal or metalloid oxide, and, at least, one catalytically active metal of group 10. The extruded inorganic substrate has pores, a total pore volume and a pore size distribution. The pore size distribution profile has, at least, two peaks of pore diameters, each peak having a maximum. The first peak has the first maximum of pore diameters of more than 1000 nm to 6000 nm, and the second peak has the second maximum of pore diameters of less than about 120 nm; and about 15% or more of the total pore volume of the extruded inorganic substrate are within the range of the first peak of the pore diameters. The composition has a total pore volume of 0.1-0.6 cm3/g.

EFFECT: good activity and increased selectivity of the catalyst.

72 cl, 8 dwg, 3 tbl, 2 ex

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