Palladium/silver hydrogenation catalyst and methods

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

 

Cross-reference to related applications

This application claims the priority of provisional patent application U.S. serial No. 60/388307 June 14, 2002

The technical field to which the invention relates

This invention relates to new catalysts and to methods of producing compositions palladium/silver on a medium having superior characteristics as a catalyst for hydrogenation. In another aspect this invention relates in General to methods for hydrogenation of hydrocarbons, in particular to the selective hydrogenation of acetylene to ethylene using a palladium/silver catalyst on a carrier obtained by the method of receiving according to this invention.

Background of invention

Selective hydrogenation of unsaturated hydrocarbons, in particular the hydrogenation of acetylene, which is present as an impurity in monoolefinic flows (for example, the flow of ethylene from thermal cracking of ethane), is carried out in industry with palladium/silver catalyst on aluminiumoxide media essentially in accordance with the description in U.S. patent No. 4404124 and separated from his U.S. patent No. 4484015, and descriptions of both patents are incorporated here by reference. The operating temperature of this method are chosen so that), the whole Wu acetylene hereroense to ethylene, while only a small number of ethylene hereroense to ethane. It is desirable to minimize the hydrogenation of ethylene to ethane in order to minimize losses of ethylene and avoid uncontrolled reactions, which are difficult to control, as noted in the above patents. Process for the selective hydrogenation of acetylene can most effectively be regulated when there is a great difference between the temperature at which hereroense essentially all of acetylene, and a higher temperature at which the transformation of the excess ethylene from ethane.

Brief description of the invention

In one embodiment, this invention provides an improved palladium-silver catalyst contained in the carrier, and the catalyst is combined with production by iodide component and then calcined, the catalyst gives good performance deactivation and selectivity in the hydrogenation of unsaturated hydrocarbons.

In another aspect of the invention is a method of obtaining includes the interaction of solid compositions (also called "basic catalytic composition" or "original catalytic composition")containing palladium, silver and the inorganic material of the carrier with a liquid composition containing ammonium iodide, in terms of interaction, which are effective for ameliorating the possible selectivity of the solid catalytic composition.

In yet another embodiment, the silver may contain more liquid compositions than in the solid core of the catalytic composition. The catalyst containing the iodide of ammonium, then preferably calcined at an elevated temperature.

In addition, in accordance with this invention a method of hydrogenation of unsaturated hydrocarbons in General, and selective hydrogenation of acetylene (preferably present in small quantity in atlantabased gas flow) gaseous hydrogen is performed with the catalyst obtained is described here by the way.

Description of the variants of the invention

The catalytic composition constituting the subject matter of this invention includes: (a) metallic palladium and/or at least one palladium compound (preferably a palladium oxide), (b) metallic silver and/or at least one compound of silver (preferably silver oxide), (C) ideny component and (d) material inorganic carrier selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide, Zirconia, aluminosilicates, zinc aluminate, zinc titanate, and mixtures of two or more components, preferably alumina, more preferably alpha-alumina. Typically, the catalytic composition contains an example is about 0.01 to 2 wt.% Pd, about 0.01 to 10 wt.% Ag, and the catalyst contains about 1-10000 hours/million by weight iodide component. In one embodiment, the catalytic composition contains about 0.01 to 0.6 wt.% Pd, approximately 0.02-5 wt.% Ag and about 10-1000 hours/million by weight iodide component. In yet another embodiment, the catalyst ideny component is present in an amount of about 15-500 hours/million by weight. The catalyst also has a mass ratio of Ag:Pd from about 1:1 to about 10:1, more preferably from about 5:1 to about 8:1. The catalyst particles can have any suitable shape (spherical, cylindrical, and three) and are preferably either spheres or cylinders. The catalyst particles can have any suitable particle size, and preferably have a size of from about 1 to about 10 mm and preferably about 2-6 mm, the catalyst Particles can have any suitable surface area typically in the range of about 1-200, preferably about 10-100 m2/g surface Area, considered here, is determined by the BET method (BET) (brunauer, Emmett and teller) with N2.

The catalyst particles can be obtained in any suitable way. Components (a), (b) and (C) can be deposited on and/or introduced into the inorganic material of the carrier in any suitable way and in any suitable order. E.g. the measures iodide can be introduced into the material of the carrier with subsequent impregnation ladidadidadida material of the carrier compounds of Pd and Ag (such as H2PdCl4and AgNO3) sequentially in any order or simultaneously, followed by drying and calcining the impregnated thus the composition. In an alternative embodiment, the composition of palladium catalyst on a carrier, such as a composition of Pd/Al2O3which is commercially available, can be impregnated with a compound of silver and iodide of ammonium or sequentially in any order or simultaneously, followed by drying and calcining the impregnated thus the composition.

In some embodiments of the present invention the starting material, also referred to here as the "base catalyst", to obtain the catalyst according to this invention can be any composition palladium - silver catalyst on the carrier obtained by combination of silver and palladium on a suitable carrier in the desired manner. The silver component is usually dispersed essentially homogeneous across the catalyst carrier. Palladium is preferably contained on the catalyst surface. The specified base catalytic composition may be fresh catalyst or can be used catalyst which has been subjected to oxidative regen the walkie-talkie as the catalytic composition. The base catalyst may contain any suitable material solid media as described above. In one embodiment, uses the composition of the palladium/silver/aluminum oxide described in U.S. patent No. 4404124, the description of which is included here by reference.

In accordance with this invention the source or base catalyst interacts with the liquid iodide composition, which contains the dissolved ideny component, such as, for example, iodide of ammonia (NH4I) or elemental iodine (I2)dissolved in water. Liquid iodine-containing composition contains any solvent which dissolves ideny component sufficiently for use in the method of the present invention. The solvent may be water or a polar solvent, such as alcohol, ester, a simple ester or the like, containing about 1-10 carbon atoms. Water or lower alkalemia alcohols are preferred solvents for the iodide component (components). Usually the concentration of iodide component in the liquid composition and the mass ratio of iodide component to the underlying catalytic composition is chosen so as to introduce enough iodine in elemental basis in a composition with effective catalyst.

The iodine catalyst may be provided by either the of a suitable iodide component, which can be dissolved in the liquid and deposited on the catalyst. Suitable iodides are the iodide of ammonium (NH4I), hydrogen iodide (HI), iodine (I2), of tetraalkylammonium iodides and mixtures thereof. Examples of tetraalkylammonium iodides include iodide of Tetramethylammonium, iodide of tetraethylammonium, tetrabutylammonium iodide, the iodide of methyldiethylamine. Ideny component is used essentially in the absence of alkali metal iodide such as potassium iodide. When production by iodide component is hydrogen iodide, it can be used in the form of a stable aqueous solution, such as, for example, 57% aqueous solution. As the iodide component can also be used salts of hydrogen iodide. Liquid jodido composition are chosen so that the final concentration of iodine in the catalyst is in the desired range from about 1 to about 10000 hours/million Suitable concentration of iodine in the liquid compositions are in the range from about 0.001 to 1.0 mmol/cm3preferably about 0.01 to 0.5 mmol/cm3and more preferably about 0.01 to 0.05 mmol/cm3iodide.

In this description, the terms "palladium" or "silver" means palladium or silver as elements, respectively, which may be provided in the composition in the form of a palladium component or silver component, which can be any of f the purpose ground receiving stations connection, salt or complex of palladium or silver. The term "iodine" refers to the iodine as an element that can be provided in the catalytic composition in the form of iodide component. Production by iodide component can be any functional compound, a salt, a complex of iodine or iodine.

If you are using a compound, salt or complex of iodine should be selected cation to cation did not become a significant part of the catalyst, i.e. the cation was removed in the process of roasting. Thus, in the catalytic composition after calcination will essentially be no harmful cations, such as alkali metals such as sodium and potassium.

The basic interaction of Pd/Ag catalyst composition on a carrier liquid iodide NH4The first composition may be carried out in any suitable manner. In the General case, the catalytic composition and liquid iodide composition interact or mingle over a period of time not less than about 1 second, preferably from about 10 seconds to about 10 hours, usually at ambient temperature, for example from about 60 to about 90°F (16-32°). More preferably the time period is approximately 0.02 to 2 hours, and the temperature is in the range of about 70-85°F (21-30°). Pressure interaction is not critical parameter and usually can be any pressure in the range of from below atmospheric to 100 psi. Due to economic considerations, the pressure in the process stage of the interaction may be approximately atmospheric, for example from about 10 psi to about 25 psi. In the implementation stage of the interaction, the temperature should be below the boiling point of the liquid, and the stage of interaction should be implemented in such a way as to provide the desired catalyst. The specified stage of interaction can be implemented as a periodic operation type, such as mixing, impregnation, spraying, or the initial wetting, or continuously (for example, when using a worm or a static mixer with closed blades or spraying the base of the catalytic composition, which is applied on a moving conveyor belt with a water composition).

If necessary, the catalytic composition is then separated from the aqueous compositions of any conventional separation technology solid/liquid, such as filtering, decanting the liquid, centrifuging, etc. Specified separation stage may be required only if the stage of the interaction consisted of soaking. Then the catalytic composition is dried, usually within a period of time from about 0.2 to about 20 hours, preferably from about 2 to about 6 hours, at a temperature of about 100-300°F (8-149° C), preferably in the range of about 200-266°F (94-130°). Preferably then heated or calcined dry catalytic composition is typically within a time period of about 0.2 to 20 hours, preferably about 1-6 hours at a temperature in the range of about 575-1300°F (300-705° (C), preferably in the range of about 750-1100°F (398-593°). As the stage of the drying stage and the calcination can be carried out in an oxidizing atmosphere or in an inert gas atmosphere (for example, N2, He, Ar, etc. and is preferably carried out in air atmosphere.

In another embodiment, the catalyst of this invention can be obtained from the components without using a basic catalyst. In this way the selected inorganic media (e.g., aluminum oxide) first interacts with the palladium component with a carrier impregnated with palladium. In this way, the palladium compound contained in the liquid composition (preferably water), is absorbed in the selected media preferably impregnation. Palladium component may be any compound, complex or salt of palladium, which are effective for impregnation of the carrier. Suitable palladium compounds include palladium chloride, palladium bromide, palladium nitrate, palladium oxide and palladium sulfate. Use the number of palladium compounds which is sufficient to ensure that the catalyst contains from about 0.01 to about 2 wt.% Pd. The impregnated carrier is dried and then calcined by heating at temperatures in the range of from about 575 to about 1300°F (300-705°C) for approximately 0.2 to 20 hours.

The obtained calcined intermediate compound then reacts with impregnation or immersion in a liquid composition (preferably water) a silver compound, salt or complex with the carrier impregnated with silver. Suitable silver compounds include silver nitrate, silver chloride, silver iodide, silver oxide and silver sulphate. Use this amount of silver compounds, which is sufficient to ensure that the catalyst contains from about 0.01 to about 10 wt.% Ag. After impregnation compound of silver carrier is then dried and again calcined under the same conditions with the formation of a basic catalyst containing inorganic carrier, impregnated with Pd and Ag.

The obtained calcined intermediate product then reacts with production by iodide component in amounts and under conditions described in this application. Saturated with iodide basic catalyst is then dried and calcined, as described above, to obtain the catalyst according to the invention.

It should be clear that the final stage of annealing is effective for hair removal the nitrogen from the composition, and much of the iodine introduced iodide impregnation. In General, up to 50 wt.%, up to 75 wt.% or even up to 90 wt.% iodine can be removed in the process stage of annealing. Therefore, the catalyst must be impregnated with a liquid composition containing a sufficient amount of iodide in order to have the remaining iodine on the carrier in an amount of about 1-10000 hours per million, preferably about 10-10000 hours/million iodine, defined as elemental iodine neutron activation analysis.

Also it should be clear that the catalyst according to the invention do not receive components of alkali metals, so that the catalyst is practically absent any iodides of alkali metals, such as KI.

Thus obtained catalyst composition, which was dried and optionally calcined can then be used in the hydrogenation of unsaturated hydrocarbons. According to a preferred variant, the catalyst used in the method of hydrogenation of acetylene, primarily to ethylene. Optionally, the first catalyst to the hydrogenation of acetylene, interacts with gaseous hydrogen or gaseous hydrocarbon is typically at a temperature in the range of from about 60°F to about 800°F (15-426° (C), preferably about 200-600°F (93-315°C), more preferably about 300-500°F (149-260° (C) and Naib is more preferably at about 400° F (204° (C) during the period of time of about 0.5-20 hours. In the process of the above mentioned interaction with H2or hydrocarbons (hydrocarbons) before starts the selective hydrogenation of acetylene compounds of palladium and silver (mainly oxides)which may be present in the catalytic composition stage after drying and optional stage of annealing (described above), substantially restored to metallic palladium and silver. When the specified optional reduction step is not carried out, the hydrogen gas present in the reaction mixture, performs the specified recovery of oxides of Pd and Ag during the initial phase of the reaction hydrogenation of acetylene according to this invention.

The catalytic compositions of the invention have better selectivity and speed of transformation and a lower degree of decontamination. Under the degree of decontamination refers to the reduction of the interest degree of conversion in a given time or over a given period of time. The percentage degree of reaction is defined as the percentage of acetylene, which hereroense to ethane and ethylene or oligomerized to butenes and heavier hydrocarbons. The catalysts of this invention provide excellent results in the hydrogenation of unsaturated hydrocarbons in General and especially selecting the hydrogenation of acetylene.

The method of hydrogenation of this invention can be implemented in conjunction fluid, which contains highly unsaturated hydrocarbon, in the presence of hydrogen with a catalytic composition described above. Preferably the liquid containing highly unsaturated hydrocarbon stream contains unsaturated alkene containing alkyne, diolefin or both of these components as impurities usually at the level of approximately 1 mg/kg (h/m) to about 50000 hours/million liquid. Unsaturated alkene in the liquid may be ethylene, propylene, butenes, or a combination of two or more of these components. Highly unsaturated hydrocarbon can be, for example, alkyne, diolefin or a combination of any two or more of these components. Examples of suitable alkynes include, but are not limited to, acetylene, propyne, 1-butyn, 2-Butin, 1 leptin, phenylacetylene, 1-octyn, 1-nonen, 1-decyn and a mixture of two or more of these substances. The preferred Alcina is acetylene. These alkynes, mainly hydronauts to the corresponding alkenes. For example, acetylene hereroense primarily to ethylene, propyne hereroense, mainly, to the corresponding butenes (1-butene, 2-butenes). Similarly, when the selective hydrogenation of diolefins diolefine hydronauts to the appropriate monoolefins, for example, 1,3-butadiene, Geri is : to butenes and selectively hereroense to pentenol.

Non-limiting examples of suitable diolefins, preferably containing 3-12 carbon atoms per molecule, which can be gidrirovanny in the method of the present invention include PROPADIENE, 1,2-butadiene, 1,3-butadiene, isoprene, 1,2-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,2-hexadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl-1,2-pentadiene, 2,3-dimethyl-1,3-butadiene, heptadiene, methylpentadiene, octadiene, methylheptane etc.

The supply flow of the fluid containing highly unsaturated hydrocarbon, for a method of hydrogenation of this invention may also contain other hydrocarbons, in particular monoolefinic and aromatic hydrocarbons that may be present in food at levels not less than 30 vol.%, include, but are not limited to, ethylene, propylene, 1-butene, 2-butene, isobutylene.

Feed stream, which may be liquid or gaseous under the conditions of hydrogenation of this method usually contains about 0.1 to 99.9 wt.%, at least one olefin. Feed stream may optionally contain other hydrocarbons (at the level of about 0.1 to 99.9 wt.%), in particular diolefine, aromatic hydrocarbons such as benzene, toluene, styrene, and ethylbenzene, which may be present at about 50-99 wt.% However, the scope of the present invention includes the use of power, which contains the eye is about 100%, at least one diolefin, such as essentially pure Dicyclopentadiene. Also the food may contain small amounts, generally less than approximately 0.05 wt.%, in particular from about 10 to about 400 hours/million, sulfur compounds as impurities. The corresponding sulfur compounds include, for example, H2S, carbondisulfide, carbon disulfide, mercaptans, organic sulfides, such as thiophene, organic di-, tri - and tetrasulfide. May also be present as impurities carbon monoxide and/or water (usually less than approximately 0.05 mol.% each).

Process for the selective hydrogenation of this invention is usually carried out with the cooperation of the feed stream containing at least one highly unsaturated hydrocarbon and molecular hydrogen, with the catalyst of the present invention, which may be contained in a fixed bed. Usually used about 1 to 10, preferably about 1 to 2, moles of hydrogen for each mole of highly unsaturated hydrocarbon present in the diet. The temperature necessary for the method for selective hydrogenation of the present invention largely depends on the activity of the catalyst and the desired degree of hydrogenation. Usually can be used, the reaction temperature in the range from about 50°F (10° (C) to about 550°F 287° C), preferably about 65-475°F (18-245°and most preferably 85-400°F (300-204°). A suitable reaction pressure is typically in the range of from about 15 to about 2000 pounds per square inch (psi), preferably from 50 to about 1500 psig, and most preferably from about 100 to about 1000 psi. Hourly average volumetric rate of liquid supply (LHSV) of hydrocarbon supply can vary in a wide interval. Typically, the volumetric rate is in the range from about 0.5 to about 100 l of hydrocarbon power per 1 liter of catalyst per hour, more preferably from about 2 to about 60 l/l/h Conditions of the method of hydrogenation must be such as to avoid significant hydrogenation of monoolefins, which are formed during the hydrogenation of highly unsaturated hydrocarbons originally present in the food, to saturated hydrocarbons, such as alkanes and cycloalkanes.

Process for the selective hydrogenation of acetylene according to this invention is carried out at the interaction of (a) the supply of gas, which contains acetylene, preferably ethylene stream containing acetylene as an impurity (usually at about 1-50000 h/mn2H2), and (b) gaseous hydrogen (C) a catalytic composition (compositions) of this izaberete the Oia. In General, these feed compositions contain about 0.5 to 1.5 wt.% acetylene, from about 8 to about 20 wt.% methane, from about 0.1 to about 0.3 wt.% hydrogen and the rest up to 100 wt.% - ethylene. In order best to achieve essentially complete removal of acetylene, must have at least one mole of hydrogen for each mol presence of acetylene. Gases (a) and (b) may be previously mixed before their interaction with the catalytic composition (C). In the scope of the present invention includes a case where the supply gas has additional gases, such as methane, ethane, propane, propylene, butane, butenes, carbon monoxide, hydrogen sulfide, if only they do not interfere in an appreciable degree of selective hydrogenation of acetylene to ethylene. Usually CO and H2S are present in trace amounts (preferably less than about 0.5 wt.% CO and less than about 50 hours/million H2S).

The temperature at which carry out the selective hydrogenation of acetylene to ethylene in the present invention largely depends on the activity of the catalyst and the desired degree of removal of acetylene. Usually use a temperature in the range from about 60°F (15° (C) to about 300°F (148° (C), preferably from about 80°F (27° (C) up to about 250°F (121°and most preferably from primer is 100° F (38° (C) up to about 250°F (121°). Can be any suitable reaction pressure. Typically, the total pressure is in the range of approximately 100-1000 pounds per square inch (psi). Hourly average volumetric gas flow rate (GHSV) may also vary in a wide interval. Typically, the volumetric rate is in the range of about 1000-10000 m3power at 1 m3of catalyst per hour, more preferably about 2000-8000 m3/m3/PM

Regenerative catalytic composition can be performed by heating the catalytic composition in air at a temperature which preferably does not exceed about 1300°F (704° (C)the burning of any organic substance and/or opplevelse substances that have accumulated in the catalytic composition. Not necessarily, subjected to oxidative regenerierung composition restore hydrogen or a suitable hydrocarbon (as described above) before its introduction in the selective hydrogenation of acetylene. Also in the scope of the present invention includes the processing subjected to oxidative regenerierung catalytic composition through the stages of drying and optional stage of annealing, i.e. in accordance with the method of the present invention before the catalyst is re-injected into the step in the selective hydrogenation of acetylene, either directly or after reduction with hydrogen or a suitable hydrocarbon, as described above.

The following examples are presented to further illustrate this invention and are not intended to limit its scope.

The following examples show the receipt of palladium - silver catalyst on the carrier by impregnation of dissolved NH4I and the use of this catalyst for the selective hydrogenation of acetylene to ethylene, as shown in the table below.

Examples

In the following examples, the catalyst And comparative examples 4-6 receive, as described in U.S. patent 4484015. The specified catalyst contains 0.04 wt.% palladium and 0.04 wt.% silver on aluminiumoxide media (granules 7/32 stranded"CH7/32") with a surface area of 5 m2/, the Catalyst is obtained by impregnation of the catalyst And a solution of NH4I in distilled water as described in examples 1-3. This solution is then added dropwise to the catalyst A. After the entire solution of NH4I added to the catalyst And the granules are thoroughly mixed. Wet granules are then reloaded into the cell and dried and calcined as described in examples 1-3.

Example 1

Obtaining catalyst Pd/Ag/NH4I

About 0,128 g NH4I dissolve in about 30,04 g of distilled water. Then using this solution the PCC is primarily 100,05 g base catalyst Pd/Ag/alumina (catalyst). After impregnation the catalyst is dried at 120° (248°F) and then calcined at 538° (1000°F) for 3 hours.

Neutron activation analysis shows that the catalyst contains 30,8 hours per million of iodine.

Example 2

Obtaining catalyst Pd/Ag/NH4I

0,0301 g NH4I dissolve in 7,60 g of water. Then 25,05 g of catalyst (Pd/Ag/alumina) is impregnated with a solution of NH4I. the Catalyst was then calcined at 539° (1002°F) for 3 hours and cooled to room temperature in the furnace.

Example 3

Obtaining catalyst Pd/Ag/NH4I

0,0660 g NH4I dissolve in 29,9 g H2About with the formation of the impregnating solution. Then, 100.0 g of catalyst (Pd/Ag/alumina) is impregnated with this solution NH4I. the catalyst is dried at a temperature of 120° (248°F) for 1 hour. The dried catalyst is then calcined in a furnace at 538° (1000° (F) within 3 hours after a slow ramping the temperature up to 220°With (448°F) and then to 400°C (752° (F) at a speed of 5°C/min (41°F/min).

Neutron activation analysis shows that the catalyst contains at 54.5 hours per million of iodine.

The following examples show the comparative catalysts that contain potassium iodide (examples 4-5) or ammonium fluoride (example 6) as a sealing to the position.

Comparative example 4

Obtaining catalyst Pd/KI

0.29 grams of potassium iodide dissolved in 64,01 g H2About with the formation of the impregnating solution. Then to 99.99 g Pd-containing catalyst having a 0.04 wt.% palladium is impregnated with a solution of KI. The resulting catalyst contains 32,06 KI solution. The catalyst was then dried at 120° (248°F) for 1 hour followed by calcination at 538° (1000° (F) within 3 hours, which includes a linear variation of temperature with a speed of 5°C/min (41°F/min).

Comparative example 5

Obtaining catalyst Pd/Ag/KI

100,04 g of catalyst (Pd/Ag/aluminum oxide) impregnated with the remainder (˜32 g) KI solution obtained in example 4. The catalyst was then dried at 120° (248°F) for 1 hour. The catalyst was then calcined at 538° (1000° (F) within 3 hours, which includes a linear variation of temperature with a speed of 5°C/min (41°F/min).

Comparative example 6

Obtaining catalyst Pd/Ag/NH4F

0,235 g NH4F dissolved in 7,45 g of water with the formation of the impregnating solution. Then 24,97 g of catalyst (Pd/Ag/alumina) is impregnated with this solution. The catalyst was then dried at 120°and calcined at 400°C (752°F) for 3 hours.

In these experiments, the catalysts of the examples have the hydrogenation of acetylene, contained in the exhaust products as food, which contains 1.2 to 1.3 wt.% acetylene, 13 wt.% methane, 0.2 wt.% hydrogen and the rest up to 100 wt.% - ethylene. Experimental conditions include pre-treatment recovery 20 grams of each catalyst, diluted with 40 g alund cuota (inert Al2O3placed in a reactor with a jacket with an inner diameter of 0,652 inches. The method includes restoring power at 400°F (204° (C) within two hours by a stream of hydrogen at 200 ml/min at atmospheric pressure. Use the molar ratio of hydrogen to acetylene 2:1.

The following table shows the use of the catalysts of examples 1, 2 and 3 of the invention, in the selective hydrogenation of acetylene contained in the ethylene stream. The catalysts of comparative examples 4, 5 and 6 are also used as test catalysts under the same conditions. The raw catalyst is tested under the same reaction conditions.

td align="center"> Pd-Ag-NH4I
Table
The catalytic compositionThe number of catalystRun numberThe rate of deactivation: loss of degree of conversion in %/hWeight gain wt.%/ day**Hours on streamTemperature *(°F)
Example 110,0060,059418140
Pd-Ag-NH4IExample 220,002is 0.135257120
PD-Ag-NH4IExample 330,0690,063425,0104
Pd-Ag (G83C)Industrial 141,145650,413866-72
Pd-KIExample 450,1940,5130853
Pd-Ag-KIExample 560,621

1,455

0,232
0,08528694

94

120
Pd-Ag-NH4FExample 670,3141,0512068

* The temperature at which the rate of deactivation.

** On the catalyst, which is determined by the mass increases, the deposited green oil. The formation of green oil is defined as the increase in the mass of catalyst after the experiment, divided by the duration of the run of the experiment.

As shown in the table, the catalysts according to the invention Ave who are greatly improved speed of decontamination, expressed as a loss (in percent) degree of conversion per hour. There are also a good degree of selectivity. The table shows that the rate of deactivation are below for methods that use catalysts according to the invention than in the control catalysts of examples 4-7, even at higher temperatures. This is unexpected, as it was expected that the use of higher temperatures will result in a higher rate of deactivation.

This invention has been described with reference to certain preferred options. However, since its obvious variants will be obvious to a person skilled in the art, the invention should not be limited to this.

1. Catalytic composition comprising a calcined mixture, where the mixture contains at least one palladium component, a silver component, the inorganic material of the carrier and iodine component selected from the group consisting of ammonium iodide, hydrogen iodide, iodine, iodide of tetraalkylammonium and mixtures thereof.

2. The catalytic composition according to claim 1 in which the catalytic composition has a palladium content of about 0.01 to 2 wt.%, the silver content of about 0.01 to 10 wt.% and the iodine content of about 1-10000 hours/million

3. The catalytic composition according to claim 1, where the inorganic material of the carrier chosen is from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide, Zirconia, aluminosilicates, zinc aluminate, zinc titanate, and mixtures thereof.

4. The catalytic composition according to claim 1 in which the catalytic composition has a palladium content of about 0.01 to 0.6 wt.%, the silver content of about 0.02 to 5 wt.% and the iodine content of about 10-1000 hours/million

5. The catalytic composition according to claim 1, where the mixture is calcined at a temperature of from about 575°F (300° (C) to about 1300°F (704°).

6. The catalytic composition according to claim 5, where the mixture is calcined for from about 0.2 to about 20 hours

7. The catalytic composition according to claim 1, where at least one palladium component is selected from the group consisting of palladium metal and palladium oxide.

8. The catalytic composition according to claim 1, where the iodine component is an ammonium iodide.

9. The catalytic composition according to claim 1, where the iodine component represents iodine.

10. The catalytic composition according to claim 7 in which the catalytic composition has a palladium content of about 0.01 to 2 wt.%, the silver content of about 0.01 to 10 wt.% and the iodine content of about 1-10000 h/m and where the material of the inorganic carrier selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide, Zirconia, aluminosilicates, zinc aluminate, titanate CIN is and mixtures thereof.

11. The catalytic composition according to claim 7, where the palladium content is about 0.01 to 0.6 wt.%, the silver content is about 0.02 to 5 wt.% and the iodine content of approximately 10-1000 hours/million

12. The composition obtained by the process comprising the following stages: the interaction of the source material containing palladium component, a silver component and the inorganic material of the carrier with a solution containing iodine component selected from the group consisting of ammonium iodide, hydrogen iodide, iodine, iodide of tetraalkylammonium and mixtures thereof, with the provision of the source material, peered with iodine, and annealing the specified source material, peered with iodine.

13. The catalytic composition according to item 12, where the material of the inorganic carrier selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide, Zirconia, aluminosilicates, zinc aluminate, zinc titanate, and mixtures thereof.

14. The composition according to item 12, where the iodine component is dissolved in a solvent selected from the group consisting of water and a polar solvent, with the formation of a solution.

15. The composition according to item 12, where the material of the carrier is alumina, and production by iodide component is ammonium iodide dissolved in water.

16. The composition according to item 12, where the annealing is carried out at a temperature elprimero 575° F (300°C) to about 1300°F (704°).

17. Catalytic composition comprising at least one palladium component, at least one silver component, iodine component selected from the group consisting of ammonium iodide, hydrogen iodide, iodine, iodide of tetraalkylammonium and mixtures thereof, and the inorganic material of the carrier.

18. The catalytic composition according to 17, in which essentially no alkali metal halide.

19. The composition according to item 12, where ideny component is an ammonium iodide.

20. The composition according to item 12, where ideny component represents the elemental iodine dissolved in water.

21. The catalytic composition according to 17, where the palladium component is a palladium metal, palladium oxide, or a mixture thereof.

22. The catalytic composition according to 17, where the catalytic composition has a palladium content of about 0.01 to 2 wt.%, the silver content of about 0.01 to 10 wt.% and the iodine content of about 1-10000 hours/million

23. The catalytic composition according to 17, where the material of the inorganic carrier selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide, Zirconia, aluminosilicates, zinc aluminate, zinc titanate, and mixtures thereof.

24. The catalytic composition according to 17, where the palladium content is about from 0.01 to 0.6 mA is.%, the silver content is about 0.02 to 5 wt.%, the content of elemental iodine is about 10-1000 hours/million and the material of the inorganic carrier selected from the group consisting of aluminum oxide, titanium dioxide, zirconium dioxide and mixtures thereof.

25. The catalytic composition according to 17, where the catalyst composition has been calcined.

26. The catalytic composition according A.25 where this catalyst composition was dried before roasting.

27. The composition according A.25, where the composition is calcined at a temperature of from about 575°F (300° (C) to about 1300°F (704°).

28. The composition obtained by the process comprising a stage of impregnation of the source material containing palladium, silver and at least one inorganic material of the carrier with a solution containing iodine component, and annealing the source material impregnated at a temperature of from about 575°F (300° (C) to about 1300°F (704°C) for approximately 0.2-20 h, where ideny component selected from the group consisting of ammonium iodide, hydrogen iodide, iodine, iodide of tetraalkylammonium and their the mixtures.

29. The composition according to p, where the iodine component is an ammonium iodide.

30. The method for the catalytic composition, which comprises the following stages:

(1) the interaction of (a) a solid composition, the content is soup palladium, silver and the inorganic material of the carrier, with (b) a liquid composition containing iodine component, for at least about 1 to obtain proteinopathy solid composition; and

(2) annealing proteinopathy solid compositions obtained in stage (1).

31. The method according to item 30, where the method is carried out essentially in the absence of iodide of potassium.

32. The method according to item 30, where the material of the inorganic carrier selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide, Zirconia, aluminosilicates, zinc aluminate, zinc titanate, and mixtures thereof, the liquid composition is water or a polar solvent and the time period is in the range from about 10 to about 10 o'clock

33. The method according to item 30, where the inorganic material of the carrier is aluminum oxide and the solid composition contains about 0.01 to 2.0 wt.% palladium and about 0.2 to 10 wt.% silver.

34. The method according to item 30, where ideny component provided in quantities sufficient to ensure the presence of iodine catalyst in an amount of from about 1 to about 10000 hours/million

35. The method according to item 30, where the stage calcination is carried out at a temperature of from about 575°F (300° (C) to about 1300°F (700°).

36. The method according to item 30, where the iodine component is selected from the group consisting of yo the IDA ammonium, of hydrogen iodide, iodine, iodide of tetraalkylammonium and mixtures thereof.

37. The method according to p, where ideny component is an ammonium iodide.

38. The method for the catalytic composition, which includes

(1) the interaction of the inorganic material of the carrier with a palladium component and calcination of the inorganic material of the carrier, proteinopathies with palladium;

(2) the interaction of the calcined material inorganic carrier, proteinopathies with palladium, a silver component and calcination of the inorganic material of the carrier, proteinopathies with palladium and silver; and

(3) the interaction of the calcined material inorganic carrier, proteinopathies with palladium and silver, iodine component and calcination of the inorganic material of the carrier, proteinopathies with palladium, silver and iodine, with the formation of the catalytic composition.

39. The method according to § 38, where the method is carried out essentially in the absence of iodide of potassium.

40. The method according to § 38, where the material of the inorganic carrier selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide, Zirconia, aluminosilicates, zinc aluminate, zinc titanate, and mixtures thereof.

41. The method according to § 38, where each stage of the interaction is done by the keys impregnation of the inorganic material of the carrier.

42. The method according to § 38, where the stage of interaction with iodine carried out by dissolving the iodine component in water or polar solvent to form a solution and impregnation of the inorganic material of the carrier specified solution for from about 10 to about 10 o'clock

43. The method according to § 38, which use a sufficient amount of palladium and silver for the inorganic material of the carrier contained about 0.01 to 2.0 wt.% palladium and about 0.2 to 10 wt.% silver.

44. The method according to item 43, where ideny component is provided in quantities sufficient to ensure the presence of iodine catalyst in an amount of from about 1 to about 10000 hours/million

45. The method according to § 38, where each stage calcination is carried out at a temperature of from about 575°F (300° (C) to about 1300°F (700°).

46. The method according to § 38, where the iodine component is selected from the group consisting of ammonium iodide, hydrogen iodide, iodine or mixtures thereof.

47. The method according to § 38, where ideny component is an ammonium iodide.

48. The method of hydrogenation of unsaturated hydrocarbons, which comprises the interaction of an unsaturated hydrocarbon with hydrogen in the presence of a catalyst according to claim 1.

49. Process for the selective hydrogenation of at least one alkyne containing from 2 to about 8 carbon atoms per molecule which is available is t in the supply stream, gaseous hydrogen to at least one of the corresponding alkene containing from 2 to about 8 carbon atoms per molecule, including the stage of interaction of the specified feed stream and the gaseous hydrogen with a catalyst according to claim 1.

50. The method according to § 49, where at least one alkyne selected from the group consisting of acetylene, propyne, butane-1, butyne-2, and mixtures thereof.

51. The method according to § 49, where at least one Alcina is acetylene and at least one alkene is ethylene.

52. The method according to § 49, where the feed stream contains at least one sulfur compound selected from the group consisting of hydrogen sulfide, carbondisulfide and mercaptans.



 

Same patents:

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

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

FIELD: organic synthesis catalysts.

SUBSTANCE: catalyst includes Cu and Mg compounds deposited on alumina as carrier and has copper compounds, expressed as Cu, from 2 to 8%, Mg/Cu atomic ratio ranging from 1.2 to 2.5, wherein concentration of copper atoms is higher in the interior of catalyst particle than on the surface (layer 20-30 Å thick) thereof and concentration of magnesium atoms prevails on the surface of catalyst particle, while specific surface of catalyst ranged from 30 to 130 m2/g. Oxychlorination of ethylene is carried out under fluidized bed conditions using air and/or oxygen as oxidants in presence of above-defined catalyst. Catalyst is prepared by impregnating alumina with aqueous Cu and Mg solutions acidified with hydrochloric acid solution or other strong acids using volume of solution equal or lesser than porosity of alumina.

EFFECT: increased activity of catalyst at high temperatures and avoided adhesion of catalyst particles and loss of active components.

8 cl, 2 tbl, 5 ex

FIELD: industrial organic synthesis and petrochemistry.

SUBSTANCE: isoamylenes are subjected to dehydrogenation in presence of overheated water steam and catalyst containing, wt %: potassium oxide and/or lithium oxide, and/or rubidium oxide, and/or cesium oxide, 10-40; cerium(IV) oxide 2-20; magnesium oxide 2-10; calcium carbonate 2-10; sulfur 0.2-5; and ferric oxide - the rest.

EFFECT: increased isoamylene dehydrogenation degree due to increased catalyst selectivity with regard to isoprene and prolonged service time of catalyst.

2 tbl, 22 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: catalyst contains, wt %: group VIII metal 0.01-2.0, group IVA metal 0.01-5.0, europium 0.01-10.0, cerium 0.10-10.0, halogen 0.10-10.0m and refractory inorganic oxide 63.00-99.86.

EFFECT: enabled preparation of catalyst with relatively high activity and selectivity, low carbon sedimentation velocity, and prolonged lifetime in naphtha reforming processes.

11 cl, 6 dwg, 4 tbl

FIELD: petroleum processing catalysts.

SUBSTANCE: invention provides reforming catalyst containing Pt and Re on oxide carrier, in particular Al2O3, wherein content of Na, Fe, and Ti oxides are limited to 5 (Na2O), 20 (Fe2O3), and 2000 ppm (TiO2) and Pt is present in catalyst in reduced metallic state and in the form of platinum chloride at Pt/PtCl2 molar ratio between 9:1 and 1:1. Contents of components, wt %: Pt 0.13-0.29, PtCl2 0.18-0.04, Re 0.26-0.56, and Al2O3 99.43-99.11. Preparation of catalyst comprises impregnation of alumina with common solution containing H2PtCl6, NH4ReO4, AcOH, and HCl followed by drying and calcination involving simultaneous reduction of 50-90% platinum within the temperature range 150-550оС, while temperature was raised from 160 to 280оС during 30-60 min, these calcination conditions resulting in creation of reductive atmosphere owing to fast decomposition of ammonium acetate formed during preparation of indicated common solution.

EFFECT: increased catalytic activity.

2 cl, 1 tbl, 3 ex

The invention relates to the field of physical chemistry

The invention relates to the refining and petrochemical industries

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The invention relates to the field of petrochemistry and oil refining and can be used in the preparation of reforming catalysts

The invention relates to a method for producing an activated catalyst composition in which a catalytic composition comprising a noble metal of group VIII and a compound of aluminum with hydrocarbon substituents on aluminiumoxide carrier containing up to 20 wt.% other components selected from the group comprising silicon dioxide, magnesium oxide, titanium oxide and zirconium oxide, activated by contact with hydrogen-containing gas at a temperature above 500oWith provided that at least when present in the catalytic composition, the compound of aluminum with a hydrocarbon Deputy is not a halide of aluminum compounds with hydrocarbon Deputy, you must activate the catalytic composition by contact with the halogen compound, either before or during the stage of activation

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention provides catalyst for oxidation of ethylene into ethylene oxide, which catalyst contains no rhenium and no transition metals and comprises up to 30% silver on solid support and promoter combination mainly consisted of (i) component containing alkali metal on amount from 700 to 3000 ppm of the mass of catalyst and (ii) component containing sulfur in amount from 40 to 100% by weight of amount required to form alkali metal sulfate and, optionally, a fluorine-containing component in amount from 10 to 300 ppm of the mass of catalyst. Ethylene oxide is produced via reaction of ethylene with molecular oxygen in presence of above-defined catalyst.

EFFECT: increased selectivity of catalyst.

9 cl, 3 tbl

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention provides catalyst for production of glyoxal via catalytic oxidation of ethylene glycol, wherein lower catalyst bed is composed of crystalline copper, upper bed of fibrous silver granules, and the two beds are modified with phosphorus. Crystalline copper particles are 1 to 100 μm in pore size and 5 to 50 μm in wall thickness. Fibrous silver granules are 0.01 to 3.00 mm in size with their specific surface being between 0.10 and 0,17 m2/g. Surface concentration of phosphorus is between 0.1 and 6% for lower bed and between 0.05 and 3.00% for upper one.

EFFECT: increased conversion and selectivity of ethylene glycol oxidation process and simplified catalyst bed formation.

4 cl, 4 ex

FIELD: supported catalysts.

SUBSTANCE: invention claims a method for preparation of catalyst using precious or group VIII metal, which comprises treatment of carrier and impregnation thereof with salt of indicated metal performed at working pressure and temperature over a period of time equal to or longer than time corresponding most loss of catalyst metal. According to invention, treated carrier is first washed with steam condensate to entirely remove ions or particles of substances constituted reaction mixture, whereupon carrier is dried at 110-130oC to residual moisture no higher than 1%.

EFFECT: achieved additional chemical activation of catalyst, reduced loss of precious metal from surface of carrier, and considerably increased lifetime.

5 cl, 9 ex

The invention relates to the chemical industry, in particular to methods of regeneration of silver catalysts for the preparation of formaldehyde from methanol

The invention relates to the field of chemical technology
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