Selective acetylenes' hydrogenation method

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

 

Background of the invention

The technical field

The present invention relates to the removal of acetylenic compounds from streams containing olefins, in particular of the threads containing diolefin.

Information relating to the present invention

Raw streams of commercial process of obtaining olefins and dienes contain various compounds as contaminants. To obtain acceptable quality olefin and diene products of acetylene impurities must be removed from these streams. The preferred method of removing acetylene impurities includes partial hydrogenation, often called selective hydrogenation. When obtaining commercial olefins and dienes to remove acetylene impurities in the stream of raw product used for the catalytic hydrogenation of acetylene compounds.

To obtain olefins, such as ethylene, propylene, butadiene, isoprene and the like, acetylene impurities such as acetylene, methylacetylene, vinylacetylene, ETHYLACETYLENE, 2-methyl-1-butene-3-in etc. in various raw mixed C2-C3the threads should be removed with minimum loss of useful materials, such as ethylene, propylene, butenes, butadiene, isoprene and the like, in the flows of raw materials. The preferred method of cleaning in a commercial practice is a selective guide the licensing of acetylene compounds using hydrogenation catalysts.

The difficulty in the catalytic hydrogenation of acetylene compounds arises from the fact that the hydrogenation must be carried out in the presence of a large excess of olefins or dienes, or both. In an industrial environment valuable olefin and diene products in the raw threads products are not inert. This is especially true in the case when the transformation of acetylene compounds, which leads to loss of valuable products. Therefore, during the selective hydrogenation of acetylene compounds to minimize the loss of olefins and dienes is highly desirable for commercial process of obtaining olefins such as ethylene, propylene and styrene and dienes, such as 1,3-butadiene and isoprene. The selectivity of the catalyst is often a determining factor when choosing a catalyst for obtaining olefins and dienes.

Acetylene compounds were subjected to hydrogenation using as catalysts for all metals of group VIII and copper, in particular, catalytic partial hydrogenation of acetylene compounds to olefinic compounds are of great importance for industrial production of olefins, dienes and refined chemical products. It is known that catalysts based on metals of group VIII (Pd, Pt, Rh, Ru, Ir and Os), and n is noble metals (Fe, Co and Ni and Cu are active in the hydrogenation of acetylene compounds and olefins. Catalysts based on noble metals of group VIII and catalysts based on Ni have a satisfactory catalytic activity when used in commercial hydrogenation process. However, more significant in the catalyst is selectivity in the hydrogenation of acetylene compounds due to excessive hydrogenation of olefinic compounds during hydrogenation of acetylene compounds.

The difficulty hydrogenation of acetylene groups in the molecule depends on the location of the triple bond in the molecule, by conjugation or olefinic group. Separate terminal triple bond is very easy for selective hydrogenation. Much more difficult for the selective hydrogenation is a triple bond, a conjugated double bond. The study of the hydrogenation of acetylene, methylacetylene and dimethylaniline (G.C. Bond et al., J. Catalysis 174, 1962) determined the following order of decreasing selectivity: Pd>Rh>Pt>EN>Os>Ir. Lchflags al. The report of the USSR Academy of Sciences 152 (6), 1383, 1962, describe the following procedure for internal acetylenes: palladium mobile>platinum mobile>rhodium mobile>Raney-Nickel>Raney cobalt for terminal acetylenes, and palladium mobile>Raney-Nickel>platinum black is ü> cobalt, Raney> rhodium mobile. Indicates that palladium on barium sulphate is more selective than the Raney Nickel in the hydrogenation of vinyl acetate in the liquid phase Catalytic Hydrogenation over Platinum Metals by Paul N. Rylander, p.75, Academic Press, 1967). Analysis of the product at 100% conversion of vinylacetylene shows that the product obtained with the participation of such catalysts as Raney Nickel, contains only half of butadiene (35%) and 23 times more butane (23%) compared with the product obtained with the palladium on the carrier of barium sulfate.

It is known that hydrogenation of acetylenes used catalysts of Pd, Ni, Cu and Co on the media (Handbook of Commercial Catalysts, pp.105-138, Howard F. Rase, CRC Press, 2000). The most preferred catalysts for commercial implementation of the selective hydrogenation of acetylenes are catalysts based on palladium such as Pd, Pd/Pb, Pd/Ag and Pd/Au on a carrier such as alumina, and copper catalyst on a carrier such as alumina. Pd-catalysts are most preferred due to its high activity and, presumably, superior selectivity compared with other metal catalysts.

The prior art is widely demonstrates that palladium catalysts have the highest selectivity among metals of group VIII in the selective hydrogenation of acetylenes. NIV one area was not detected higher selectivity of Nickel catalysts on palladievye catalysts. Palladium catalysts are actually used in all modern commercial processes for the selective hydrogenation of acetylenic impurities (vinylacetylene, ETHYLACETYLENE and methylacetylene) in untreated streams of butadiene and raw streams With3-olefin.

1,3-Butadiene is an important raw material for various polymers such as butadiene-styrene copolymer. One of the ways to obtain 1,3-butadiene is a joint production of various olefins by cracking petroleum fractions with water vapor. Raw mixed stream With4installation for steam cracking is subjected to selective hydrogenation order partial removal With4-acetylene compounds. Subjected to selective hydrogenation of the flow guide in the installation for separation of 1,3-butadiene, which used extracting the distillation of the solvent with the aim of separating 1,3-butadiene from other components in the mixed stream. Complete removal With4-acetylene compounds in the stream with a high yield of 1,3-butadiene is highly desirable to reduce the cost of production of 1,3-butadiene and receive first-class product for the manufacture of the polymer. Up to the present time a complete removal4-acetylenes in raw mixed streams by selective g is tiravanija without unacceptably high losses of 1,3-butadiene due to excessive hydrogenation of 1,3-butadiene was a technically impossible task. Therefore in the highest degree desirable is an improved inexpensive way of obtaining first-class 1,3-butadiene without high losses due to excessive hydrogenation in the use of highly active and selective catalysts.

Catalysts based on palladium for selective hydrogenation of C4-acetylene compounds are extremely active. However, their level of selectivity is not possible to completely remove4-acetylene without unacceptably high losses of 1,3-butadiene due to excessive hydrogenation. Another problem inherent catalysts based on palladium when carrying out the hydrogenation in the presence of a liquid phase, is the loss and migration of palladium due to formation of soluble complex compounds of Pd as a result of interaction of Pd atoms on the surface of the catalyst vinylacetylene. With the aim to minimize losses of palladium and reduce the catalytic polymerization of acetylene compounds used silver and gold. Catalysts based on palladium is described in U.S. patent 5877363 (1999) and EP 0089252 (1983). U.S. patent 5877363 (1999) describes a process for the selective hydrogenation of acetylenic impurities and 1,2-butadiene in mixed flows With4rich in olefins using catalysts of Pt and Pd on the media.

The catalyst based on copper is who I am extremely selective, therefore, the yield of 1,3-butadiene from the mixed flow is higher than when using catalysts based on palladium. However, since the activity of copper catalysts is very low compared with catalysts based on palladium, requires a large amount of catalyst, and a large reactor. The copper catalyst is rapidly sintered therefore it needs frequent repair. Such catalysts are described in U.S. patents 4440956 (1984) and 4494906 (1985).

During this study it was found that the selective hydrogenation of C3- and4-acetylene compounds in the raw stream of butadiene using commercial Pd catalyst (0.2 wt.%)-Ag (0.1 wt.%) on the medium decreases with increasing temperature hydrogenation; this effect is also observed H. Uygur et al. liquid-phase selective hydrogenation of methylacetylene/PROPADIENE (MAPD) in mixed traffic With3(J. Chem. Eng. Japan, 31, p.178, 1998). Such seemingly strange behavior is explained by the combined effect of very low activation energy (<0.5 to ccala) selective hydrogenation in the liquid phase, a higher solubility of hydrogen in the flow of raw materials at lower temperatures and the temperature dependence of the adsorption of acetylene compounds on the surface of palladium in a three-phase reaction system, including gaseous, liquid and solid catalysis is op. The concentration of hydrogen in the liquid phase has a stronger impact on the speed of the selective hydrogenation of acetylene compounds than the action of the activation energy.

According to R.S. Mann et al. (Can. J. Chem. 46, p.623, 1968) catalysts of Ni and Ni-Cu alloy are effective for hydrogenation of methylacetylene. Adding copper to Nickel in an amount up to 25 wt.% in the catalyst alloy catalytic activity increases. The selectivity of propylene and the amount of polymerization increased with increasing copper content in the alloy.

According To N. Gutmann and H. Lindlar (Organic Synthesis, Chapter 6) vinylacetylene and 2-methyl-1-butene-3-in with the labor selectively hydronauts with 1,3-butadiene and isoprene when using catalysts of palladium, Nickel or cobalt. However, the palladium catalyst on the carrier of calcium carbonate treated with acetate of mercury is suitable for selective hydrogenation.

Catalysts based on Nickel are effective for selective hydrogenation of acetylenic impurities in mixed flows of olefins. Documents convincingly confirm that Nickel catalysts in any form are highly active in the hydrogenation of olefins and benzene. As we know from traditional methods, due to the very high activity of Ni catalysts for the hydrogenation of olefins selective hydrogenation of acetylenes in mixtures of dienes or olefins is in preferably carried out by using pre-sulfatirovannah Nickel catalyst or in the presence of a retarding agent for Nickel catalysts, used in methods known in the art.

There is no description selective hydrogenation With4-acetylenes in the raw threads butadiene in the presence of a Nickel metal catalyst on the carrier in nesulfatirovannah, which is equal to or greater than the effect of a catalyst based on palladium. Nickel catalysts are described in U.S. patents 4504593 (1985) and 3691248 (1972).

In U.S. patent No. 4504593 described the use of bimetallic catalyst on a carrier comprising at least one metal from group VIII selected from Pt, Pd, Ni and Co, and at least one metal selected from the group comprising Ge, Sn and Pb, for the selective hydrogenation of acetylene hydrocarbons and diolefines in olefin mixtures monoolefins. This catalyst contains from 0.1 to 10 wt.% Ni, preferably from 1 to 5 wt.%, on a carrier, such as alumina (70 m2/g and 0.5 cm3/g of the total pore volume). Catalysts receive in two stages, introducing the second component (Ge, Sn or Pb) catalyst Ni-catalyst from the first stage. Selective hydrogenation is preferably carried out in the presence of sulfur compounds and nitrogen to obtain acceptable superior selectivity. However, this patent does not describe selective hydrogenation With4-acetylenes in mixed flows butadiene is in in the absence of sulfur activated catalyst, containing Ni metal.

U.S. patent No. 3793388 (1974) describes the selective hydrogenation of acetylene in the mixture of olefins in the presence of Nickel catalyst on a carrier of aluminum oxide. Aluminum oxide is characterized by the presence of the significant volume of pores having a diameter of at least A and surface area of at least 2 m2/, the Nickel Content in the catalyst is from about 0.5 to 8 mg per square meter of the total surface area of aluminum oxide.

In the patent GB 1182929 (1970) described the catalyst, which can be used for selective hydrogenation of acetylenic compounds in a mixture of olefins, for example in the flow of raw butadiene. This catalyst is an activated Nickel copper catalyst on the carrier. The mass of the copper component of the catalyst is greater than the mass of Ni, and the mass media than the mass of the active metal components. The finished catalyst is in the form of mixed oxides receive calcinaro a mixture of oxides at 850°C. the Catalyst to activate the restore at a temperature of from 180 to 600°using containing hydrogen gas. The metal content of active components in the activated catalyst is at least 25 wt.% the active metal components. The rest of the percentage is in the form of their oxides Selective hydrogenation is carried out in the gas phase at a temperature of from 100 to 250° And speed, which is about 1 in units of the average mass flow rate of feed per unit mass of catalyst (WHSV). The cycle time is about 420 hours.

U.S. patent 4748290 (1988) describes the catalyst from bored Nickel on a carrier of aluminum oxide designed for hydrogenation of acetylene and diolefins compounds in monoolefins connection. The interaction of arsenate of Nickel on the media connection borohydride activates the catalyst.

In U.S. patent 4831200 (1989) describes how the two-stage selective hydrogenation of polluting acetylene impurities in the raw thread butadiene. Acetylene impurities in the flows of raw materials partially hydronaut with the use of a catalyst based on palladium, described in U.S. patent 4533779, and then the remaining impurities hydronaut with the use of a catalyst based on copper, discussed above is described in U.S. patents 4493906 and 4440956.

The advantage of the proposed method lies in the increased selectivity when removing acetylenic compounds from hydrocarbon streams and increased output desired olefinic compounds. In particular, the use of this method provides a higher yield of 1,3-butadiene higher purity of the raw streams With4. A distinctive feature of the present invention enables the is is it allows the use of inexpensive and readily available catalyst at key stages of the process that provides the further advantage that other catalysts are sensitive to sulfur or heavy metals, such as catalysts based on palladium and copper, can also be used in subsequent stages of the process for further improvements. These and other advantages and features of the present invention will become clear from the further description.

Brief description of the invention

Briefly speaking, the present invention relates to a method for removing acetylenic compounds from hydrocarbon streams, including the contact of hydrogen and a stream of hydrocarbons containing acetylene compounds with a catalyst comprising azulfidinee a metallic Nickel catalyst on a carrier, in the conditions of hydrogenation for selective hydrogenation of a part of the mentioned acetylene compounds. In addition nesulfatirovannah metallic Nickel, the catalyst may contain metals such as Mo, Re and/or Bi. Azulfidinee Nickel metal contains the main part of the metal component on the carrier.

Brief description of drawings

Figure 1 is a graph showing the comparison of examples 1A and 1B, illustrating the deletion is of vinylacetylene.

Figure 2 is a graph showing the comparison of examples 1A and 1B, illustrating the removal of ETHYLACETYLENE.

Figure 3 is a graph showing the comparison of examples 1A and 2, illustrating the removal of vinylacetylene.

Figure 4 is a graph showing the comparison of examples 1A and 1B, illustrating the removal of ETHYLACETYLENE.

Figure 5 is a graph showing the comparison of examples 3 and 4, illustrating the removal of vinylacetylene.

6 is a graph showing the comparison of examples 3 and 4, illustrating the removal of ETHYLACETYLENE.

7 is a graph illustrating the removal of vinylacetylene in example 5.

Fig is a graph illustrating the removal of ETHYLACETYLENE in example 5.

Fig.9 is a graph illustrating the removal of vinylacetylene in example 6.

Figure 10 is a graph illustrating the removal of ETHYLACETYLENE in example 6.

Detailed description of the invention

During development of the present invention, it was found that azulfidinee Nickel catalysts unexpectedly exhibit higher selectivity than palladium catalyst, relative to acetylene compounds. In addition, azulfidinee Nickel catalysts also have other highly desirable properties required for the selective hydrogenation of 4-acetylenes compared to palladievye the catalysts for 1,3-butadiene. Acetylene impurities in various mixed flows, including2-C12-olefins, diolefin and styrene, are removed by selective hydrogenation. Selective hydrogenation is carried out, passing the material through a single catalytic reaction zone, or in a few catalytic reaction zones, depending on the nature of the raw materials and the purpose of the process. It was found that the catalyst based on Nickel in nesulfatirovannah as unexpectedly more effective for selective hydrogenation of acetylenic impurities, such as vinylacetylene, ETHYLACETYLENE and the like, and provides the lowest excess hydrogenation of dienes, such as 1,3-butadiene than the commercially preferred catalysts based on palladium. It is important that the active metal catalyst based on Nickel should not be subjected to preliminary solifidian or contain arsenic to selective hydrogenation to obtain the best characteristics compared with known methods. In the case of pre-sulfatirovnie catalyst based on Nickel or its use in the presence of sulfur compounds by selective hydrogenation to be carried out at higher temperature, which leads to lower output is 1,3-butadiene and a more rapid deactivation of the catalyst. However, as indicated above, the sulfur impurities are usually present in the flows of raw hydrocarbons, do not pose a serious problem for the described nesulfatirovannah Ni-catalyst in this process.

Optimal load for metal catalysts based on Ni and Pd are completely different. Catalysts based on palladium are more active than catalysts based on Nickel, based on the content of the active metal, loaded on the catalyst, because the Nickel content in the catalyst based on Ni is usually a value two orders of magnitude larger than the palladium content in the catalyst based on Pd. However azulfidinee a catalyst based on Nickel has a higher activity than the catalyst based on palladium, based on the weight of the catalyst or a given amount of catalyst under the same conditions of hydrogenation.

Toxic action of organic sulfur compounds such as mercaptans and heavy metals such as mercury-organic compounds, catalysts, such as catalysts containing palladium, copper and copper-zinc-silver-palladium, is reduced in the first reaction zone with nesulfatirovannah Ni-catalyst. Another objective of the first catalytic reaction zone is also a partial conversion of acetylene compounds, especially vinylacetylene, h is usually used to reduce the loss and migration of metallic palladium, as well as the rate of formation of toxic carbonaceous materials on the catalyst in the second and third catalytic reaction zone. When using a catalyst based on copper in the second catalytic zone of the first reaction zone using nesulfatirovannah catalyst based on Ni lengthens the cycle time of the catalysts based on copper. To achieve all these goals part nesulfatirovannah Ni-catalyst in a first catalytic reaction zone is used as the protective layer. Azulfidinee Ni-catalyst is present on the carrier in the amount of excess relative to the quantity required for selective hydrogenation, thus preventing contamination of a number of Nickel sulfur or other impurities. Azulfidinee Ni is preferably used in a quantity of at least 5%, preferably at least 10%in excess of the amount needed to carry out selective hydrogenation. This invention has the following advantages over known methods using a catalyst based on palladium or copper: a higher rate of reaction of selective hydrogenation, a higher yield of useful materials such as monoolefinic, diolefin or the other, the hydrogen economy and a longer period is of Tcl or service of the catalyst, or both.

According to the present method With4-acetylene impurities in a mixed stream of raw butadiene removed completely or to a content less than 30 ppm With all4-acetylenes (e.g., less than 20 ppm of vinylacetylene (BA) and 10 ppm of ETHYLACETYLENE (EA)), by selective hydrogenation with a high yield of 1,3-butadiene in accordance with this invention, providing an easier and less costly separating 1,3-butadiene from the mixed stream.

The catalysts are placed in one or more catalytic reaction zones, which are part of any physical installation. Examples of such installations in which chemical reactions occur that are relevant to this invention include any installation or any combination of reactor fixed bed reactor column type distillation reactor column type with extractive distillation solvent, the reactor operating at the boiling point reactor with irrigated layer, a reactor with a moving bed reactor with a "boiling" layer reactor fluidized bed reactor with agitator-tank etc.

Activation nesulfatirovannah catalyst based on Ni carried out at a temperature in the range from about 250 to 1000°F when the hydrogen pressure from ambient pressure to D. the effect of hydrogen of about 600 psi for 1 to 40 hours.

When using a single catalytic reaction zone is used azulfidinee a catalyst based on Nickel. Hydrogen mixed with the hydrocarbon feedstock before it enters the catalytic reaction zone or served in a catalytic reaction zone at several points along the specified reaction zone.

When using multiple catalytic reaction zones used a combination of nesulfatirovannah catalyst based on Nickel-promoted Pd-Cu-Zn-Ag-catalyst and, optionally, a catalyst based on copper. The raw material is first passed through a catalytic reaction zone with nesulfatirovannah a catalyst based on Nickel before applying the second catalytic reaction zone containing either the catalyst based on Nickel with low activity, either one or both of the promoted Pd-Cu-Zn-Ag-catalyst and catalyst based on copper. Hydrogen mixed with the hydrocarbon feedstock before it enters the catalytic reaction zone or served in a catalytic reaction zone at several points along these reaction zones.

During the selective hydrogenation of acetylene compounds in the catalytic reaction zones of heat, which leads to the appearance of overheating or unwanted servname the resultant temperature profile in the catalytic reaction zones. Raw materials are passed through a catalytic reaction zone (zone) in the form of gas phase, liquid phase or mixed phase of gas and liquid. The reaction temperature selective hydrogenation in a catalytic reaction zones is one of the most important process variables. The main difference is that this way of using nesulfatirovannah Ni requires lower temperatures for any of these reactions compared with the methods using other catalysts. In General, the temperature in the catalytic reaction zone is in the range from about 50 to 420°F, preferably from about 55 to 380°F. However, the temperature is determined by the specific gidriruemyi acetylene compounds extracted danami and/or olefins, the catalyst and the alleged physical phase hydrocarbons in a specific catalytic reaction zone. For C2-or3-acetylene mixed With2-or3-olefinic hydrocarbons, the temperature of the selective hydrogenation is from about 55 to 380°F. For C4-acetylene compounds in mixed butadiene stream temperature is from about 55 to 180°F. For C5-acetylene compounds mixed With5-diolefine hydrocarbon p is the current temperature is from about 60 to 350° F. For heavier acetylene hydrocarbons than With5-acetylene, heavier hydrocarbons than With5temperatures ranged from approximately 65 to 400°F.

Selective hydrogenation using nesulfatirovannah Ni-catalysts described in this invention is preferably carried out at low temperature hydrogenation in the range from 50 to approximately 180°F, more preferably from about 70 to 170°F, for C4-acetylene compounds in the raw stream of butadiene. To obtain a relatively uniform temperature throughout the catalytic reaction zone selective hydrogenation is preferably carried out in a catalytic distillation reactor or in a reactor with a fixed bed with an internal cooling system, such as a heat exchanger, or applying a combination of these two reactor systems.

The concentration of hydrogen in the catalytic reaction zones is another important variable. The concentration of hydrogen in the catalytic reaction zone depends on a number of factors, including the concentration of acetylene compounds in the stream of incoming raw materials in a particular reaction zone, specific acetylene connection (connection), the estimated degree of conversion of acetylenes when passing through a particular kata is eticheskuyu reaction zone, the temperature of a specific catalytic reaction zone, the pressure in the catalytic reaction zone, the catalyst is used in a particular reaction zone, and the specific physical device catalytic reaction zone. In General, as for the catalysts containing metals of group VIII, the minimum amount of hydrogen is at least 25 mol.%, preferably 40 mol.%, from all contents of all acetylenes in the flow of a specific catalytic reaction zone. However, as for the catalysts containing metals of group VIII, the minimum amount of hydrogen is at least 40 mol.%, preferably 60 mol.%, from all contents of all acetylenes in the flow of a specific catalytic reaction zone.

Manometer (gauge) pressure in the catalytic reaction zones is in the range from about 10 to 500 psi, preferably from about 30 to 350 psi. The pressure in the catalytic reaction zone is defined by the following specifications: specific physical device catalytic reaction zone, the presence or absence of solvent, the estimated temperature of the reaction of selective hydrogenation in a specific catalytic reaction zone, the used catalyst and the estimated phase (gas is, liquid or mixed phase of gas and liquid hydrocarbons in the catalytic reaction zone.

The flow rate of hydrocarbons in a particular reaction zone is determined by the following conditions: amount of catalyst specific physical device catalytic reaction zone, the estimated degree of conversion of acetylene compounds when passing through a particular reaction zone and the hydrogen concentration, temperature and pressure in a specific catalytic reaction zone.

Subjected to steam cracking of hydrocarbon streams to obtain olefins and dienes containing acetylenic impurities such as acetylene, methylacetylene, ETHYLACETYLENE, vinylacetylene, 2-methyl-1-butene-3-in or phenylacetylene, through one catalytic reaction zone or a series of two or three catalytic reaction zone to remove acetylene impurities. Because the goals, the concentration of acetylenes and composition of the catalysts in each catalytic reaction zone are different, the optimum hydrogen concentration in each reaction zone is also different. Therefore, the hydrogen concentration in each reaction zone, respectively, adjust by adding or removing hydrogen from a stream of incoming raw materials in each catalytic reaction zone. Variables method (temperature, is providing and the flow rate of hydrocarbons) in each catalytic reaction zone can be independently adjusted to better utilization of the catalyst in each reaction zone. An example of a flow of the raw material for this method is the raw stream With4butadiene from the installation for steam cracking. When using a single catalytic reaction zone is used only azulfidinee the catalyst based on Ni. In a given physical facility, where the hydrogenation may be optionally used a combination of a catalyst based on Nickel and the catalyst based on palladium catalyst based on Nickel and the catalyst based on copper or a catalyst based on Nickel and activated palladium catalyst based on copper, with an adjustment of the hydrogen content in each catalytic reaction zone or without it. One catalytic reaction zone may contain one, two or three different catalyst. It is important that the raw materials are always first passed through the layer nesulfatirovannah catalyst based on Nickel before it goes through the other layers of the catalyst.

The mixture of the raw stream With4butadiene from the installation for steam cracking and hydrogen is passed through a single catalytic reaction zone or a series of two or three catalytic reaction zone to remove acetylene impurities. Streams of raw4-butadiene usually contain impurities from methylacetylene, ETHYLACETYLENE, in which dilatation, PROPADIENE and 1,2-butadiene.

A catalyst in a first catalytic reaction zone includes azulfidinee Ni or, optionally, azulfidinee Ni and one or more elements selected from Mo, Re, and Bi, are on a porous carrier such as alumina, silica and the like, the Preferred Ni content in Ni-catalysts is from about 3 to about 75 wt.% by weight of the total catalyst, preferably from 4 to 60 wt.% Ni. The preferred Ni content in the Ni-Mo catalyst is from 5 to 60 wt.%, preferably from 5 to 45 wt.%, and Mo from 1 to 40 wt.%. Alternatively, the catalyst in a first catalytic reaction zone may include two different catalyst: Ni-catalyst and the above-described multi-component Ni-catalyst. Two different catalyst can be mixed together before their submission to the first catalytic reaction zone or, alternatively, the first can only be downloaded Ni-catalyst, and then another catalyst or Vice versa. Toxic effect of sulfur compounds in the stream of raw materials for catalysts in the second and third catalytic reaction zone is neutralized in a first catalytic reaction zone as a transformation in organic thioethers, and interaction with Ni-catalysts. Other important issues addressed in the first catalytic Rea the operating zone, are partial conversion of acetylene compounds, especially vinylacetylene in the flow of raw materials to minimize loss/migration Pd (in the case of Pd in the following catalyst) and reducing the rate of deposition of carbonaceous materials on the catalyst (catalysts) in the following catalytic reaction zone (or zones). The yield of 1,3-butadiene from the first catalytic reaction zone is preferably maintained at a level greater than about 97 wt.%, preferably about 98 wt.%. The yield of 1,3-butadiene, vinylacetylene or ETHYLACETYLENE determined as follows:

The output X (%)=100-(NF-NP)×100/NF,

NF= wt.% X in the flow of raw materials, NP= wt.% X in the product flow; where X represents 1,3-butadiene, vinylacetylene or ETHYLACETYLENE.

Because vinylacetylene the hydrogenation can be converted to 1,3-butadiene (1,3-BD), it is mathematically possible that the yield of 1,3-BD will be more than 100%, which means that the output will be more than 100% in the absence of hydrogenation of 1,3-BD. Concentration of the combined acetylene impurities in the product stream from the first reaction zone using nesulfatirovannah catalyst based on Ni is in the range from about 20 to 5000 weight ppm, depending on the concentration of acetylene impurities in the flow of raw materials. All acetylene impurities may be p the color turned into the flow of raw material by passing it through a single catalytic reaction zone in the presence of a catalyst based on Nickel. However, the loss of various olefins such as 1,3-BUTADIENES, butenes, propylene and ethylene, due to excessive hydrogenation may be too high to be economically viable for commercial production. In the first catalytic reaction zone is also the maximum isomerization of PROPADIENE in methylacetylene and 1,2-butadiene 1,3-butadiene.

The flow of product from the first catalytic reaction zone may be passed through a second catalytic reaction zone with the regulation or no regulation optimal hydrogen concentration at the optimum process conditions. In the product flow from the second catalytic reaction zone, the concentration of all4-acetylene impurities is in the range from 0 to approximately 350 weight ppm, depending on the concentration of acetylene impurities in the initial flow of raw materials to the first catalytic reaction zone, and operating conditions of the second catalytic reaction zone. The yield of 1,3-butadiene from the second catalytic reaction zone is more than about 98 wt.%. The catalyst in the second catalytic reaction zone is any of the known catalysts based on palladium or preferably an improved copper catalyst containing at least one is atall from group VIII, Ag, Au or mixtures thereof on a carrier of alumina with at least one of the properties such as the average pore diameter of more than 200E or apparent bulk density less than about 0,70 g/cm3such as a catalyst comprising Cu, Zn and optionally Ag on a porous carrier such as alumina or promoted Pd-Cu-Zn-Ag described in the patent application U.S. serial No. 09/827411 filed April 6, 2001 and is included here in its entirety. In the second catalytic reaction zone may be optionally used an improved multi-component palladium catalyst comprising Pd or Pd and other metals of groups 8 and at least two metals selected from Ag, Zn or Bi, is described in application for U.S. patent, serial No. 09/977666, filed October 15, 2001 and is included here in its entirety. The content of palladium and Nickel in an activated copper catalyst is from about 20 parts/million to 0.3 wt.% Pd and from 0 to 15 wt.% Ni. The copper content is from about 0.4 to 30 wt.%. The content of silver or gold is from 0 to about 5 wt.%. The zinc content is from 0 to 25 wt.%. Any known catalyst based on palladium or known catalyst based on copper in the second or subsequent catalytic reaction zone is in the eating of the present invention.

The third catalytic reaction zone is optional. The product stream from the second catalytic reaction zone is passed through a third catalytic reaction zone with the regulation or no regulation optimal hydrogen concentration at the optimum process conditions. In the specified catalytic reaction zone With the remaining4-acetylene impurities are removed completely. Therefore, the flow of product from the third catalytic reaction zone does not contain detectable With4-acetylene impurities. The yield of 1,3-butadiene from the third catalytic reaction zone is more than about 99 wt.%. The catalyst in the third catalytic reaction zone is an improved catalyst Cu-Zn-Ag, or the above-promoted Pd-Cu-Zn-Ag-catalyst, or, optionally, azulfidinee Ni, or the one and the other, known or copper catalyst described in U.S. patent 4440956 and 4494906. The content of palladium or Nickel in an activated copper catalyst in the third catalytic reaction zone is from about 10 parts per million to 0.3 wt.% Pd and 0.1 to about 10 wt.% Ni. The copper content is from about 0.3 to 10 wt.%. The content of silver and gold is from 0 to about 1 wt.%. The zinc content is from 0 to 10 wt.%

Any combination of two or three catalysts can be loaded in one reactor in any form or in any operating mode. However, the raw material is preferably first passed through a reaction zone with nesulfatirovannah a catalyst based on Ni. The first two reaction zones can be optionally combined in a single reactor with a progressive download of the first two catalysts, while a second, separate reactor may not necessarily serve the third catalytic reaction zone. Another option involves combining the last two reaction zones in a single reactor with a progressive download of the last two catalysts. Another option includes the use of three separate reactors as the three reaction zones. Selective hydrogenation of acetylenic impurities can be carried out in the reaction zones of different configurations. The implementation of the response in any combination of modes, such as a reactor with a fixed bed, catalytic column type distillation reactor, the catalytic reactor column type with extractive distillation solvent, the reactor operating at the boiling point of the reactor with a moving bed reactor with a fluidized bed and the like, is part of this invention. Examples of such combinations include only the fixed layer, the only cat who lytic reactor column type distillation, the only catalytic reactor column type with extractive distillation, three fixed layer, two fixed layer, a catalytic reactor with distillation for the first catalytic reaction zone and one or two reactor with a fixed bed for the second and third catalytic reaction zones, one or two reactor with fixed bed, catalytic reactor column type distillation for the last catalytic reaction zone, the reactor with a porous layer to the first reaction zone and the catalytic reactor column type with extractive distillation solvent for the second reaction zone.

The properties of any catalyst deteriorate during the time of his participation in the process for various reasons. One reason is the slow deposition of toxic carbonaceous materials on the catalyst surface. For the renewal of the cycle or the lifetime of the catalyst can be used a solvent to slow the speed of deposition of toxic carbonaceous materials on the catalyst. Therefore, heavy polymers must be soluble, at least to some extent in the solvent under the conditions of selective hydrogenation. Examples of such a solvent include4-C10-paraffin hydrocarbons, cyclohexane, methylcyclohexane, benzene, toluene, alkyl is Italy, furfural, dimethylacetamide, dimethylformamide, organic, formylmorpholine, and also ethers, such as tetrahydrofuran. The optional solvent may be deposited in a catalytic distillation system in the recirculation heavy components that typically make up a small part of the raw material, and are formed by oligomerization and polymerization during selective hydrogenation in the reactor. Heavy components before recirculation in the upper part of the catalytic distillation column can be subjected to hydrobromide for more effective removal of heavy polymers from the catalyst. This operation can be carried out using fixed bed by means of a separator for separating heavy components from the output from the reactor stream, or from raw materials. When using the fixed layer, the solvent is served with raw materials in the catalytic reaction zone. When carrying out the catalytic reaction distillation or catalytic reaction with the extractive distillation solvent is injected in the appropriate place in the top half of the column. Another alternative sequence of operations includes periodic washing of the catalyst with a solvent at an appropriate temperature in the range from 50 to 750°F pressure on the 0 to 500 psi, preferably in the presence of hydrogen.

Catalysts applicable in this invention can be obtained by precipitation of the catalyst components on the media, such as aluminum oxide, silicon dioxide, other forms of carbon, charcoal, ceramic materials, polymers, and various structured materials, such as materials for stuffing reactors fixed bed or distillation columns. The media nesulfatirovannah Ni-catalyst preferably has a surface area of more than 40 m2/, Can be used different methods of deposition, such as impregnation, spraying, drying the suspension by sputtering, deposition from the vapor, etc. All of these techniques are well known to specialists in this field of technology. The catalysts may not necessarily represent structured cushioning material obtained from Ni, Cu, Pd-Cu-Ag, Ni-Pd, Ni-Cu, etc. that can be placed in the area of selective reaction with hydrogen in any physical device.

For the deposition of components of catalysts for curly media using one or more different methods of deposition curly media, such as spheres, extrudates, tablets and the like, impregnated with inorganic or organic compounds of metals. Typically, inorganic salts deposited on carriers such as alumina, razloga the t to the metal oxide by calcination subjected to impregnation products at elevated temperatures in air. The metal oxides on the media to restore metal to activate the catalysts, with the use of reducing agents, such as hydrogen, carbon monoxide, ammonia, methanol and the like, at a suitable temperature. If necessary, activate the catalysts at low temperature can be used in low-temperature reducing agents such as hydrazine, aluminiumgie, formaldehyde and the like, for Example, an improved catalyst Cu-Zn-Ag described in the aforementioned application 09/827411, are impregnated gamma-alumina suitable form of water mixed with a solution of nitrate of copper, zinc and silver in a rotary device for impregnation, followed by drying and calcining at elevated temperatures. Promoted palladium Cu-Zn-Ag-catalyst receiving, depositing copper, zinc, silver, and palladium on a carrier having a suitable shape, such as calcinated at high temperature, porous transition alumina.

Another commonly used method involves the deposition of catalytic metal components from the mixed aqueous solution in the presence or in the absence of the material of the carrier, while the precipitate was washed with pure water and then dried, obtaining powders, which are used to produce different shapes using various methods, such as extrusion, extrusion is Ableton desired size and pressure casting. Molded materials are usually subjected to calcination at suitable temperatures. If necessary, the use of catalysts in the form of microspheres for a reactor with a fluidized bed of suspended matter derived from precipitation. The mixture is dried by spray to the desired particle size, and then calicivirus at elevated temperatures. The materials obtained by spray drying, can also be formed with obtaining catalysts in the form of extrudates or tablets. Alternatively, catalysts can be obtained by the method described in U.S. patent 6337300. The catalyst based on an alloy receive, removing the extractable metal component of the molded catalyst alloy.

In the following examples, all Nickel catalysts, Nickel is desulfuromonas metal.

Example 1A (comparative method)

Commercial Pd-Ag catalyst type "eggshell" (0.2 wt.% Pd and 0.1 wt.% Ag) on the media α-aluminum oxide (G68I produced UCI) is used to remove4-acetylene impurities in the raw thread butadiene obtained by cracking, by selective hydrogenation. 50 grams of the catalyst is mixed with 100 ml of glass beads having a diameter of 3 mm and a load positioned vertically in the reactor of stainless steel with upward flow and a porous layer (diameter of 1 inch, a length of 20 du the MOU). The average diameter of the catalyst extrudate is 2.5 mm, and a length of 6 mm At each end zone catalyst install two thermocouples for temperature control in the reactor. The catalyst was activated at 235°F, flowing 300 cm3/min 33%. gaseous hydrogen in nitrogen for 2.5 hours and then 300 cm3/min of hydrogen at 400°F within 2 hours at a gauge pressure of 15 psi. The reactor is cooled to ambient temperature. Selective hydrogenation of acetylenic impurities is carried out at a feed rate of the hydrocarbon of 6 ml/min and hydrogen flow - 165 MNC3/min at the beginning of the reaction to 100 NCM3/min to the end of the cycle when the total gauge pressure in the reactor 108 psi. The raw material consists of 0.95 wt.% vinylacetylene (VA), to 0.14 wt.% ETHYLACETYLENE (EA) and 0.20 wt.% methylacetylene, 72,11 wt.% 1,3-BD, to 0.12 wt.% 1,2-BD, 14,61 wt.% the butenes, the rest are mostly inert substances. Due to the exothermic heat of hydrogenation temperature at the end of the catalyst layer is higher than at the beginning of the specified layer. The temperature of hydrogenation is from 120 to 128°F at the end of the catalyst layer and 90°F at the beginning of the specified layer. A better quality product, obtained as a result of this experiment, contains 114 ppm BA and 230 ppm EA at the exit of 1,3-butadiene of 87.3%. Results the ATA presented in figure 1 and 2.

Example 1B (invention)

50 grams of the catalyst STC-400 (16 wt.% Ni on alumina)produced Synethix, mixed with 100 ml of glass beads having a diameter of 3 mm and a load positioned vertically in the reactor of stainless steel with upward flow and a porous layer (diameter 1 inch, length 20 inches). The catalyst was prepared in the activated and then passivated. The diameter of the catalyst is 1.2 mm for the diameter of a three-extrudates. At each end zone catalyst install two thermocouples for temperature control in the reactor. The catalyst was activated at 235°F, flowing 300 cm3/33 min.% gaseous hydrogen in nitrogen for 3 hours and then 300 cm3/min of hydrogen at 575°F for 3 hours at a gauge pressure of 15 psi. The reactor is cooled to ambient temperature. Selective hydrogenation of acetylenic impurities in the same raw materials as in example 1A, is carried out at a feed rate of the hydrocarbon of 6 ml/min and hydrogen flow of 100 NCM3/min at the beginning of the reaction to 38 NCM3/min to the end of the cycle when the total gauge pressure in the reactor 108 psi. The composition of the raw material is the same as in example 1A. Due to the exothermic heat of hydrogenation temperature at the end of the catalyst layer is higher than at the beginning of the specified layer. So the temperature value hydrogenation is from 120 to 124° F at the end of the catalyst layer and from 77 to 84°F at the beginning of the specified layer. A better quality product, obtained as a result of this experiment, contains 0 ppm BA and EA at the exit of 1,3-butadiene was 94.9%. The results are presented in figure 1 and 2.

The comparison of the results of the above two experiments presented in figure 1 and 2 shows the best characteristics nesulfatirovannah Ni-catalyst compared with a catalyst based on palladium.

Example 2

This example illustrates the selective hydrogenation of C4-acetylenes using a system of two successive reactors. 50 grams of the catalyst STC-400 (16 wt.% Ni on alumina) is loaded into the first reactor with a porous layer and activate the method described in example 1B. After stirring with 100 ml of glass beads having a diameter of 3 mm 40 grams of a commercial Pd-Ag catalyst type "eggshell" (G68I)used in example 1A, load into the second reactor with fixed bed (diameter 1 inch, length 20 inches) and activate the method described in example 1A. The composition of the raw material is the same as in example 1A. Selective hydrogenation of acetylenic impurities in the raw materials is carried out at a feed rate of the hydrocarbon material in the first reactor 6 ml/min and a constant flow rate of hydrogen 42 NCM3/min until the end of the experiment at about the eating gauge pressure in the reactor 108 psi. The stream coming from the specified first reactor is fed directly into the second reactor. However, prior to being fed into the catalytic reaction zone of the second reactor, the stream exiting the first reactor, mixed with gaseous hydrogen at different speeds from 100 to 50 NCM3/min. Temperature in the first hydrogenation reactor is about 120°F at the end of the catalyst layer and about 84°F at the beginning of the specified layer. The temperature in the second hydrogenation reactor is from about 120 to 125°F at the end of the catalyst layer and about 85°F at the beginning of the specified layer. The reaction product from the second reactor is subjected to analysis to determine the effectiveness of the system of two reactors. The results are presented in figure 3 and 4 demonstrate the higher efficiency of systems with two catalysts including Ni-catalyst and a catalyst based on palladium, compared to only a catalyst based on palladium, used in example 1A.

Example 3

50 grams of Ni-catalyst (28 wt.% Ni; L6564)produced CRI, is loaded into a reactor with a fixed bed in the same manner as described in example 1B. The catalyst was activated at 250°F within 2 hours, passing a mixture of 200 NCM3rpm N2and 100 NCM3rpm N2and then at 670°F within 4 hours - 300 NCM3/min H2. Catalysis is a torus is a three-extrudate with a diameter of 1.2 mm. The specific surface of the catalyst COUNCIL is about 120 m2/year Raw material consists of 0.98 wt.% vinylacetylene (VA), to 0.12 wt.% ETHYLACETYLENE (EA) and 0.08 wt.% methylacetylene, 72,52 wt.% 1,3-BD, to 0.12 wt.% 1,2-BD, 14,04 wt.% the butenes, the rest are mostly inert substances. Selective hydrogenation of acetylenic impurities in the raw materials is carried out at a feed rate of the hydrocarbon of 6 ml/min and at different flow rates of hydrogen from 100 to 40 NCM3/min, and when the total gauge pressure in the reactor 108 psi. The temperature in the hydrogenation reactor is from about 119 to 127°F at the end of the catalyst layer and from about 90 to 104°F at the beginning of the specified layer. The yield of 1,3-butadiene in the product containing 5 ppm BA and 0 ppm EA is 96,0%. The obtained results are shown in Fig.6. The efficiency of this catalyst is higher than the efficiency of the catalyst based on Pd in example 1A.

Example 4

This example illustrates the selective hydrogenation of C4-acetylenes using a system of two reactors. Ni-catalyst loaded in the first reactor with a fixed layer, and Cu-Zn-Ag-catalyst promoted with Pd, load into the second reactor with a fixed bed.

Cu-Zn-Ag-catalyst promoted with Pd receive in accordance with the aforementioned application No. 09/827411 using ACS is d aluminum (spherical shape, diameter 1/16"), by way of gelatinization with dripping oil. Physical properties of aluminum oxide are summarized in table 1. Aluminum oxide calicivirus at a temperature of 1100°C for 3 hours in air. Calcined alumina has the following physical properties: specific surface WET - 67,4 m2/g, an average pore diameter of - A, and total pore volume of N2- 0,701 cm3/, Apparent bulk density of aluminum oxide before calcination and after calcination is about to 0.48 and 0.62 g/cm3respectively. More than 90% of the pores have a diameter of more than 100E. PCA calcined alumina mainly shows the presence of theta-alumina with a number of Delta-aluminium oxide. This calcined alumina is used to produce the catalyst. Catalyst Cu-Zn-Ag-promoted palladium, receive, using a two-step impregnation method. The mix will get by dissolving 28.8 g of Cu(NO3)2·2,5H2O, 10 g of Zn(NO3)2·6H2O and 0.5 g AgNO3in 285 ml of water. For the first impregnation of the mixed salt solution is poured into 300 g of calcined alumina in a rotary device for impregnation and then dried at approximately 200°, vdova hot air. The dried product calicivirus at 450°C for 2 hours. The following is the composition of metal on a carrier of alumina-based compounds used: 2.5 wt.% Cu, 0.7 wt.% Zn and 0.1 wt.% Ag. Another mixed solution get, dissolving 2,275 g of Cu(NO3)2·2,5H2O 1,895 g Zn(NO3)2·6H2O, 0.25 g AgNO3and of 6.95 g of palladium nitrate solution (10 wt.% nitrate palladium 10 wt.% solution of nitric acid, purchased from Aldrich) in 70 ml of water. The obtained mixed solution is sprayed on the first product in a rotary device for impregnation, using the spray for about 15 minutes, and then dried at 200°within hours, vdova hot air. Product calicivirus at 350°C for 2 hours in air. A large part of the metal components from the second stage impregnation spray is deposited in a thin layer of a thickness of from about 0.04 to 0.06 mm Has the following composition of the metal in the final product on the basis of the used compounds: 2.72 wt.% Cu, 0.84 wt.% Zn, and 0.15 wt.% Ag and 0.10 wt.% Pd.

50 grams of the same Ni-catalyst (L6564), as in example 3, is loaded into the first reactor with a porous layer by the method described in example 1B, and activate in the same manner as in example 3. 50 grams of Cu-Zn-Ag-catalyst promoted with Pd received in accordance with the above description, the load in the second reactor with a porous layer after mixing with 100 ml of glass beads having a diameter of 3 mm and activate at 250°F within 2 hours, passing a mixture of 200 NCM3/m is n N 2and 100 NCM3rpm N2and then at 670°F within 4 hours 300 NCM3/min H2. The raw material consists of 1.07 wt.% vinylacetylene, to 0.12 wt.% ETHYLACETYLENE and 0.14 wt.% methylacetylene, 71,89 wt.% 1,3-BD, 0.08 wt.% 1,2-BD, 14,44 wt.% the butenes, the rest are mostly inert substances. Selective hydrogenation of acetylenic impurities in the raw materials is carried out at a feed rate of the hydrocarbon material in the first reactor 6 ml/min and at a constant flow rate of hydrogen 40 NCM3/min until the end of the experiment when the total gauge pressure in the reactor 108 psi. The stream coming from the specified first reactor is fed directly into the second reactor. However, prior to being fed into the catalytic reaction zone of the second reactor, the stream exiting the first reactor, mixed with gaseous hydrogen at different speeds from 25 to 5 NCM2/min. Temperature in the first hydrogenation reactor is about 120°F at the end of the catalyst layer and from about 99 to 119°F at the beginning of the specified layer. The temperature in the second hydrogenation reactor is from about 115 to 123°F at the end of the catalyst layer and from about 80 to 85°F at the beginning of the specified layer. The reaction product from the second reactor is subjected to analysis to determine the effectiveness of the system of two reactors. The yield of 1,3-b is Tatiana in the product, containing 0 ppm BA and 16 ppm EA is of 97.8%. The obtained results are shown in figure 5 and 6, showing a higher efficiency of the system of the two catalysts including Ni-catalyst and promoted Pd-Cu-Zn-Ag-catalyst, as compared with a catalyst based on palladium as described in example 1A, or only with Ni-catalyst described in example 3.

Table 1
Average bulk density, g/cm30,48
WET at one point, m2/g157,5
RESPONSE at several points, m2/g170,2
The area of the mesopores, m2/g170,2
The area of micropores, m2/g0
The total area of the adsorbing surface, m2/g172,6
Total pore volume (cm3/g for pores with radius less than

E when R/R0=0,9801
0,912
The total volume of pores for adsorption pore radius of 20 E0,852
The total pore desorption for pores with a radius of

17,5-E
0,930
The average diameter of pores, E.214,4

Example 5

Illustrated by selective hydrogenation With -acetylenes using a system of two successive reactors. Ni-catalyst loaded in the first reactor with a fixed layer, and Cu-Zn-Ag-catalyst promoted with palladium, load into the second reactor with a fixed bed.

Cu-Zn-Ag-catalyst promoted with Pd receive in accordance with the aforementioned application U.S. serial No. 09/827411. To obtain a Cu-Zn-Ag-catalyst promoted with Pd, apply the same calcined alumina as in example 4. Cu-Zn-Ag-Pd-catalyst was prepared using a two-step impregnation method. Mixed salt solution get by dissolving 28.8 g of Cu(NO3)2·2,5H2O, 10 g of Zn(NO3)2·6H2O and 0.5 g AgNO3in 285 ml of deionized water. The mixed solution was poured into 300 g of calcined alumina in a rotary device for impregnation and then dried at approximately 200°, vdova hot air. The dried product calicivirus at 450°C for 2 hours. Was calculated following the composition of the metal on a carrier of alumina-based compounds used: 2,53 wt.% Cu, 0.71 wt.% Zn and 0.10 wt.% Ag. Mixed salt solution get, dissolving 4,55 g of Cu(NO3)2·2,5H2O, 3,79 g Zn(NO3)2·6H2O and 1.47 g AgNO3in 40 g of water. A solution of palladium nitrate receive dissolve 1.47 g of palladium nitrate (42.8% of Pd) 40 the aqueous 1 wt.% solution of nitric acid. Mixed solution and a palladium nitrate solution is poured together. United mixed solution is sprayed on the first impregnated product in a rotary device for impregnation, using the spray for about 15 minutes, and then dried at 200°within hours, vdova hot air. Product calicivirus at 350°C for 2 hours in air. A large part of the metal components from the second stage impregnation spray is deposited in a thin layer with a thickness of approximately from 0.12 to 0.16 mm was calculated following the composition of the metal in the final product on the basis of the used compounds: 2.91 wt.% Cu, of 0.97 wt.% Zn, of 0.20 wt.% Ag and 0.20 wt.% Pd.

50 grams of the same Ni-catalyst (L6564), as in example 3, is loaded into the first reactor and activated in the manner described in example 4. 50 grams of the above-described Cu-Zn-Ag-catalyst promoted with Pd received in accordance with the above description, load into the second reactor and activated at 250°F for 3 hours, passing a mixture of 200 NCM3rpm N2and 100 NCM3rpm N2and then at 575°F for 3 hours 300 NCM3/min H2. Raw material has the same composition as in example 3. Selective hydrogenation of acetylenic impurities in the raw materials is carried out at a feed rate of the hydrocarbon material in the first reactor 6 ml/min and at a constant flow rate of odor is Yes 40 NCM 3/min until the end of the experiment when the total gauge pressure in the reactor 108 psi. The stream coming from the specified first reactor is fed directly into the second reactor. However, prior to being fed into the catalytic reaction zone of the second reactor, the stream exiting the first reactor, mixed with gaseous hydrogen at different speeds from 24 to 6 NCM3/min. Temperature in the first hydrogenation reactor is about 120°F at the end of the catalyst layer, and from about 76 to 119°F at the beginning of the specified layer. The temperature in the second hydrogenation reactor is from about 118 to 124°F at the end of the catalyst layer and from about 90 to 118°F at the beginning of the specified layer. The reaction products from the second reactor is subjected to analysis to determine the effectiveness of the system of two reactors. The yield of 1,3-butadiene in the product, containing 0 ppm BA and 14 ppm EA, is 97.5%. The obtained results are shown in Fig.7 and 8, showing a higher efficiency of dual catalysts including Ni-catalyst and promoted Pd-Cu-Zn-Ag-catalyst, as compared with a catalyst based on palladium as described in example 1A, or only with Ni-catalyst described in example 3.

Example 6

50 grams of Ni-catalyst (70 wt.% Ni; L65271), manufactured CI, loaded into a reactor with a fixed bed method described in example 1B. The catalyst was activated at 250°F for 3 hours, passing a mixture of 200 NCM3rpm N2and 100 NCM3rpm N2and then at 670°F for 5 hours - 300 NCM3/min H2. The catalyst is a three-extrudate with a diameter of 1.2 mm, the Composition of the mixture is the same as in example 3. Selective hydrogenation of acetylenic impurities in the raw materials is carried out at a feed rate of the hydrocarbon of 6 ml/min and at different flow velocities of hydrogen - from 105 to 60 NCM3/min, and when the total gauge pressure in the reactor 108 psi. The temperature in the hydrogenation reactor is from about 120 to 124°F at the end of the catalyst layer and about 80°F at the beginning of the specified layer. The yield of 1,3-butadiene in the product, containing 0 ppm BA and 14 ppm EA, accounts for 93.4%. The obtained results are shown in figures 9 and 10. The efficiency of this catalyst is higher than the efficiency of the catalyst based on Pd in example 1A.

1. Method of removing acetylenic compounds from hydrocarbon streams comprising bringing into contact of the stream of hydrocarbon containing a first concentration of acetylene compounds and olefins, with a catalyst consisting of nesulfatirovannah metallic Nickel on the media or who is and who nesulfatirovannah metallic Nickel on the carrier, modified metals such as Mo, Re, Bi, or a mixture thereof, and specified azulfidinee Nickel is present on the carrier in a quantity exceeding at least 5% of the amount needed for the selective hydrogenation in the presence of hydrogen in a first reaction zone at a temperature and pressure and hydrogen concentration, promoting the hydrogenation of acetylene compounds, and the allocation of the specified hydrocarbons having a second concentration of acetylene compounds, which is lower than the first concentration.

2. The method according to claim 1, wherein said catalyst consists of nesulfatirovannah Nickel metal modified metals such as Mo, Re, Bi or mixtures thereof.

3. The method according to claim 1, wherein in the specified reaction zone after said catalyst has also added a catalyst which is selective for the hydrogenation of acetylene compounds.

4. The method according to claim 3, wherein said additional catalyst consists of nesulfatirovannah metallic Nickel on the carrier or consists of nesulfatirovannah metallic Nickel on the carrier, modified metals such as Mo, Re, Bi or mixtures thereof.

5. The method according to claim 4, wherein said additional catalyst consists of nesulfatirovannah metallic Nickel is utilizator, modified metals such as Mo, Re, Bi or mixtures thereof.

6. The method according to claim 3, wherein said additional catalyst containing a catalyst based on Pd.

7. The method according to claim 3, wherein said additional catalyst containing a catalyst based on Cu containing at least one component is a metal of group VIII component is Ag, component - Au or mixtures thereof, on a carrier of alumina, having a surface area greater than 40 m2/g and having at least one of the following characteristics: an average pore diameter of more than 200Å or an apparent bulk density less than about 0,70 g/cm3.

8. The method according to claim 6, wherein said additional catalyst component contains - silver.

9. The method according to claim 6, wherein said catalyst based on Pd includes other metals of group VIII and at least two metals selected from Ag, Zn or Bi.

10. The method according to claim 7, wherein said additional catalyst comprises copper, zinc, silver, promoted Pd.

11. The method according to claim 1, comprising a first reaction zone defined as indicated in claim 1, containing the first catalyst, defined as indicated in claim 1, and additionally comprising a second reaction zone containing a second catalyst which is selective for the hydrogenation of acetylene compounds, under conditions of temperature and pressure, and conc is Tracii hydrogen, promoting the hydrogenation of acetylene compounds, adjusted separately for each of the reaction zones.

12. The method according to claim 11, wherein said second catalyst comprises nesulfatirovannah metallic Ni on the media.

13. The method according to claim 11, wherein said second catalyst comprises nesulfatirovannah metallic Nickel catalyst modified with metals such as Mo, Re, Bi or mixtures thereof.

14. The method according to claim 11, wherein said second catalyst includes a catalyst based on Pd or a catalyst based on Cu.

15. The method according to 14, wherein said second catalyst component contains a silver or component - gold.

16. The method according to 14, wherein said second catalyst comprises Pd or Pd and other metals of group VIII and at least two metals selected from Ag, Zn or Bi.

17. The method according to claim 11, wherein said second catalyst comprises a copper catalyst containing at least one component is a metal of group VIII component is Ag, component - Au or mixtures thereof, on a carrier of alumina with at least one of the following characteristics: an average pore diameter of more than 200Å or an apparent bulk density less than about 0,70 g/cm3.

18. The method according to 17, wherein said second catalyst contains copper, zinc and silver, promoted Pd.

19. The method according to claim 1, in which the specified hydrocarbons include butadiene and other4acetylene compounds, and the reaction zone temperature is from 70 to 170°F.

20. The method according to claim 1, wherein said catalyst consists of nesulfatirovannah metallic Nickel.



 

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7 cl, 1 dwg, 2 ex

FIELD: petroleum chemistry, chemical technology.

SUBSTANCE: method involves preparing flow of C2- and C3-olefin raw containing acetylenes, diolefins and some low-molecular light gases taken among the group comprising hydrogen, carbon monoxide and methane. Method involves separation of light gases and C2- and C3-acetylene and diolefin impurities are hydrogenated in a single flow of raw under a catalyst layer by addition of hydrogen to the raw flow to obtain the olefin raw flow containing significantly lower content of C2- and C3-acetylene and diolefin impurities and without significant reducing the amount of C2- and C3-olefins in the raw flow followed by separation of C2- and C3-olefins. Method provides reducing in formation of oligomers, enhanced selectivity in the hydrogenation process.

EFFECT: improved method for hydrogenation.

15 cl, 3 dwg, 2 ex

The invention relates to the simultaneous selective hydrogenation of vinylacetylene, ETHYLACETYLENE and 1,2-butadiene in the flow of C4rich olefin

The invention relates to the production of monomers for synthetic rubber, namely the process of purification of isoprene from acetylene hydrocarbons by hydrogenation

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: 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

The invention relates to a catalyst and method suitable for the catalytic hydrogenation of unsaturated hydrocarbon compounds

The invention relates to catalysts and methods for selective hydrogenation of acetylene hydrocarbons, in particular ethylene by selective hydrogenation of acetylene in the gas phase, and may find application in processes for purifying gas mixtures from impurities acetylene

The invention relates to the selective hydrogenation of diolefins and acetylene compounds in the stream enriched in olefins

FIELD: petrochemical processes.

SUBSTANCE: hydrocarbon fractions are brought into contact, in presence of hydrogen-containing gas, with catalyst containing palladium on porous carrier, which contains mesopores with diameters no less than 4 nm and no large than 20 nm constituting 80 to 98% of the total volume of pore within a range of 4 to 20 nm.

EFFECT: deepened hydrogenation process due to increased catalyst activity regarding diolefins and selectivity regarding aromatic hydrocarbons.

2 cl, 1 tbl, 10 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

The invention relates to a method for hydrogenation of alpha-methylstyrene contained in the alpha methylstyrene faction, formed when processing the products of the cleavage of cumene hydroperoxide
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