Catalyst for selective hydrogenation of unsaturated olefins and a method for preparation and application of catalyst

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: catalyst contains following active components: Pd (0.001-1%), Bi (0.001-5%), at least of Ag, Cu, Zn, K, Na, Mg, Ca, Be, Sn, Pb, Cd, Sr, Ba, Ra, Mn, Zr, Mo, and Ge (0.001-10%), and at least one of rare-earth metals deposited on porous inorganic carrier (the balance.). Catalyst is capable of selectively and rapidly hydrogenating strongly unsaturated hydrocarbons such as alkynes. Catalyst is suitable for industrial cracking process and is characterized by favorable long regeneration period, long service time, and low cost.

EFFECT: improved performance characteristics of catalyst at low cost.

23 cl, 5 tbl, 22 ex

 

The technical field to which the invention relates.

The present invention relates to a catalyst for selective hydrogenation of unsaturated olefins, method of production and use of the catalyst, more particularly to a catalyst for selective hydrogenation of acetylene and diolefins compounds having from two to four carbon atoms into the corresponding olefins, and its use in the process of thermal cracking of petroleum hydrocarbons.

The level of technology

It is well known that the cracking of petroleum hydrocarbons with water vapor (steam cracking) is the most important method of obtaining monomers such as ethylene, propylene, for the production of polyolefins. Scheme of the process is that after mixing of petroleum hydrocarbons with steam water vapor mixture is subjected to thermal cracking in the cracking furnace at a temperature of 750-870°with the formation of H2, CO, CO2and a mixture of saturated and unsaturated aliphatic hydrocarbons having one to three carbon atoms, and aromatic hydrocarbons. By passing through a sequence of fractionation columns the flow of raw material fractions are: hydrocarbons containing more than 10 carbon atoms, H2and CH4C2With3With4With5-C10. In the fractions With2-C10content is tsya unsaturated hydrocarbons, such as monoolefinic, alkynes, diolefin, and other Alkynes and diolefine in the fractions With2With3are toxic impurities that hinder the progress of the polymerization of ethylene and propylene. These impurities reduce the activity of the catalyst for polymerization and increase the consumption of catalyst, moreover, degradation of the polymeric product. It is necessary to strictly control the amount of alkynes and diolefins, such as acetylene present in the cracking products. In recent years, newly developed high-performance catalysts for polymerization of ethylene restrictions on the concentration of alkynes and polyolefins are becoming more stringent. For example, for the fraction of C2after 1980, the content of the acetylene was limited to 10-6mol.% or less, and for some processes, with special requirements, such as high density polyethylene, the content of acetylene in purified ethylene was limited to 10-7mol.% or less.

Therefore, a common problem is to increase the efficiency of removal of highly unsaturated hydrocarbons such as acetylene, from the products of cracking. Usually removal of the ethylene-ethane fraction accepted way catalytic selective hydrogenation.

In the process of selective hydrogenation to remove acetylene n is necessary to turn the whole acetylene and should not place excessive hydrogenation, to avoid loss of ethylene. Consequently, the hydrogenation catalyst is required as an excellent activity and high selectivity. Moreover, adsorbed on the catalyst surface acetylene easily dimerized during hydrogenation with the formation of unsaturated hydrocarbons With4such as butadiene-1,3, and such hydrocarbons With4can consistently interact with acetylene or ethylene and other unsaturated hydrocarbons with the formation of oligomers With6-C24known as the so-called green oil. Part of the so-called green oil which goes along with the raw stream is removed in the absorber of green oil, and the other part may remain on the catalyst surface and to cover the active centers of the catalyst, which leads to a gradual decrease in activity and selectivity of the hydrogenation, reduction of the working cycle of the catalyst, requires more frequent regeneration of the catalyst, which reduces the service life of the catalyst, and thus increase operating costs. Therefore, the catalyst for selective hydrogenation, with its superior performance, should have high activity, selectivity and low tendency to the formation of green oil, especially low should be the number of green oil, holding Ivanovo on the catalyst.

The prior art generally known to many applied palladium catalysts, in which other added components socializaton. For example, in U.S. patent 4404124 described silver as a component of socializaton, in document EP 89252 component of socializaton is gold, DE 1284403 and in U.S. patent 4577047 this component is chromium, in U.S. patent 3912789 - copper, in U.S. patent 3900526 - iron, in U.S. patent 3489809 - rhodium, in U.S. patent 3325556 - Li, in Chinese patent 1151908 component of socializaton potassium is, moreover, described other components of socializaton include lead, zinc and other

In the above disclosed components socializaton some of them reduce the selectivity of the palladium catalyst due to the increase of its activity, some of the components of socializaton can improve the selectivity of palladium catalysts or reduce the number of the resulting green oil, but significantly reduced their activity. So now the total industrial applications received only palladium-silver (Pd-Ag) catalyst. However, with respect to activity and selectivity of Pd-Ag catalyst is still unsatisfactory, especially in terms of controlling formation of green oil on the catalyst surface.

In connection with the above drawbacks in the application for the Chinese patent I disclosed a catalyst for selective hydrogenation of alkynes, in which the main component of the catalyst is Pd, and components socializaton are Bi and Ag. When using this catalytic system in the process of selective hydrogenation of alkynes markedly reduced the number of the resulting green oil, the catalyst has a high activity and selectivity, thereby reducing the deposition of carbon and increases the service life of the catalyst.

However, the above-mentioned catalyst is still unsatisfactory. With increased operating capacity alkynes during the industrial use of the catalyst and increased adverse reactions at more severe reaction conditions, such as high volumetric rate (7000-20000 h-1) and a high content of alkynes, activity, selectivity, a period of regeneration and service life specified catalyst is not satisfactory and further improvements are needed. Typically, the catalytic activity of the catalyst decreases due to deposition of carbon on its surface after the selective hydrogenation of alkynes over a long period, and the catalyst must be regenerated by heating at about 500°With the current of air in order to restore activity and selectivity, if these indicators do not meet the technological requirements even when the surface is elevated temperature. The temperature at which the regenerated catalyst should be carefully monitored. But even in this case, the technical characteristics of the catalyst, such as specific surface area, etc. also change significantly after conducting a 3-5-fold regeneration. Low reproducibility and stability of the catalyst may lead to a deterioration of its properties, finally, its reuse will be possible will need to replace the old catalyst with a new one.

It is known that rare earth metals can be used in catalytic hydrogenation, in which the main active component is Pd. For example, in U.S. patent 5426253 disclosed a method of hydrogenation of 2,2-dichloro-1,1,1,2-Tetrafluoroethane and 2-chloro-1,1,1,2-Tetrafluoroethane or their mixtures in 1,1,1,2-Tetrafluoroethane, which is the main active component of the selected catalyst is a metal of group VIII selected from the group consisting of Pt, Pd, Ni, Rh, Co, Ru and Ir. Moreover, the catalyst contains at least one of the following metals: Cu, Ag, Au, La, CE and Nd, which are disclosed for use as socializaton to give the catalyst corrosion resistance in hydrogenations and dechlorination of galoiduglyerodov (discussed in this patent), to protect the active catalyst surface from the influence of the hydrogen chloride formed when d is chlorination.

As a result of implementation of numerous experiments, the authors present invention discovered that by using media, which also caused the main active component Pd, component socializaton Bi, rare earth metals and at least one of the metals Ag, Cu, K, Na, Sr, Mn, Zr, Mo, Co, Ge, or a combination of two or more of these metals, get the catalyst on which the acetylene hydrogenation is carried out with high activity and high selectivity at high flow rate, and specified acetylene, is in the faction With2formed during thermal cracking of petroleum hydrocarbons. Moreover, the catalyst of the present invention has the advantage of good stability properties of the catalyst are little changed after repeated regeneration, physical parameters can be easily adjusted, and, with the addition of rare earth metals, the catalyst has an improved period of regeneration and life.

The invention

The purpose of this invention is the development of a catalyst for selective hydrogenation for selective hydrogenation of unsaturated olefins.

Another object of this invention is to develop a method of producing this catalyst.

An additional objective of this invention is the provision applies is of the specified catalyst in the process of thermal cracking of petroleum hydrocarbons for selective hydrogenation fraction C2 or C3 fraction, including highly unsaturated hydrocarbons such as acetylene and other olefins.

A catalyst for selective hydrogenation for selective hydrogenation of unsaturated hydrocarbons of the present invention mainly includes the following active components are deposited on a porous inorganic carrier:

1) at least one of Pt, Pd, Ni, Ru, Co, Rh;

2) at least one of Ag, Cu, Zn, K, Na, Mg, Ca, Be, Sn, Pb, Cd, Sr, Ba, Ra, Fe, Mn, Zr, Mo and Ge;

3) at least one of rare earth metals and

4) Bi

in which rare earth metal selected from scandium, yttrium and lanthanides in group IIIB of the Periodic table of elements.

The method of preparation of the catalyst of the present invention includes the following stages: first, at the same time cause the component rare earth metal, or first simultaneously applied component rare earth metal and a connection To either Na and then applied sequentially or simultaneously with other active ingredients.

Detailed description of the invention

It is understood that this invention is not limited to the specific structures, stages, and modification of these structures, stages and materials can be made in the spirit of the present invention. You should specify that in the description, the terms are only descriptive, but they cannot be considered as referring the existing scope of the invention.

A catalyst for selective hydrogenation of this invention for selective hydrogenation of unsaturated olefins mainly includes the following active components are deposited on a porous inorganic carrier:

1) at least one of Pt, Pd, Ni, Rh, Co and Ru;

2) at least one of Ag, Cu, Zn, K, Na, Mg, Ca, Be, Sn, Pb, Cd, Sr, Ba, Ra, Fe, Mn, Zr, Mo and Ge;

3) at least one of rare earth metals and

4) Bi

in which rare earth metal selected from scandium, yttrium and lanthanides, including La, CE, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.

Calculated on the total weight of the metal elements, the number of active component 1) for each 100 wt.% catalyst (in the subsequent interest is calculated on the weight ratio of metal elements) is 0.001-1%, preferably 0,008%to 0.3%, more preferably from 0.01 to 0.15%. The preferred component 1) is Pt or Pd.

Calculated on the total weight of the metal elements, the number of the active component 2) for each 100 wt.% the catalyst is 0.001-10%, preferably from 0.01 to 2%. The preferred component 2) is at least one of Ag, K, Na, Zn, Sn, Pb and Cd, more preferably Ag, or Ag, or Ag and Na.

Especially it should be noted that in accordance with the operating requirements of the final catalyst, two or more metals, such as Ag and an alkaline metal or Na may COI is to Lisovets together, and this is done with a clear purpose of improving the characteristics of the catalyst.

The weight percent (wt.%) the active component 3) for each 100 wt.% the catalyst is 0.01-5%, preferably 0.05 to 3%, more preferably 0.1 to 1.5%. The preferred rare earth metal is La, CE, Nd, Pm, Eu, Y or mixtures thereof, more preferably La and/or Nd. The content of rare earth metal introduced into the carrier has a direct impact on the characteristics of the final catalyst of the invention. Usually, when the content of rare earth metal is less than 0.01%, its stabilizing effect and the promoting effect on the catalyst may not be as obvious, and the purpose of the invention may not be achieved. However, when the content of rare earth metal is higher than 5%, so a large number of not only increases the cost of the catalyst, but also significantly affects its characteristics, such as activity and selectivity of the catalyst.

The weight percentage of the active component 4) for each 100 wt.% the catalyst is 0.001-5%, preferably 0.005 to 1%.

Porous inorganic carrier of the invention can be well-known carrier of the prior art. For example, hard-shelled land, spinel, silicon dioxide, titanium dioxide, aluminium oxide or mixtures thereof. A preferred carrier of the invention which is aluminum oxide or silicon dioxide. It can be in the form of granules, gears, areas, laminated or tape form, the preferred form of wheels or spheres, the preferred form of gear (this form provides the advantage of low pressure drop over the layer at high flow rate). Specific surface area of the carrier is 1-200 m2/g, preferably 2-120 m2/g, more preferably 2-50 m2/year

It should be noted that the media in the form of gears preferably used in the catalyst of the invention for industrial use. As a result of increasing the volumetric rate at selective hydrogenation, with the increase of the pressure drop in the catalyst bed can have a significant impact on the normal operation in the following parts of the installation. When the space velocity increases, the pressure drop in the catalyst bed, is made as of the media in the form of gears and carrier spherical shape, will increase to some extent, but the effect of velocity on pressure drop for spherical media will be higher than for a carrier in the form of gears. Therefore, when the hydrogenation with high bulk velocity selection of the media in the form of gears is preferred relative to the spherical media.

To obtain the catalyst of the invention MoE is but to use well-known traditional methods, such as impregnation or spraying, in order to apply these active components on the carrier sequentially or simultaneously. The preferred method of obtaining is the following: first put the component rare earth metal or rare earth component metal and potassium or sodium component, and then put other active components, sequentially or simultaneously.

The most preferred method involves the following stages:

1) add a solution of salt of rare earth metal to the material forming the carrier, during the formation of the carrier, or the carrier impregnated after the formation of the carrier in an aqueous solution of salts of rare earth metal, drying and calcination; preferably a salt solution of rare earth metal is nitrate solution;

2) sequential or separate impregnation specified media, the salt solution component 1), a salt solution of component 2) and a salt solution component 4) after drying at 100-300°for 5-24 h calcination at 350-900°for 4-20 hours to obtain a catalyst.

When the active component 1) is palladium, suitable examples of salts of palladium include (but are not limited to) palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium nitrate, sulfate, palladium acetylacetonate, palladium, and mixtures Luba is two or more salts of palladium. For reasons of convenience, the preferred compound of palladium is palladium chloride and/or nitrate palladium.

When the active component 2) is silver, suitable examples of silver salts include, but are not limited to, silver nitrate, silver fluoride, silver perchlorate, and mixtures of any two or more silver salts. For reasons of convenience, the preferred compound of silver is an aqueous solution of silver nitrate.

When the active component 2) is potassium or sodium, suitable examples of compounds of alkali metal include, but are not limited to, potassium nitrate (or sodium), CWC3(or NaXO3) (where X is a halogen atom), a phosphate of potassium (or sodium), hydrogen phosphate potassium (or sodium), potassium carbonate (or sodium), potassium bicarbonate (or sodium), organic acid salts of potassium (or sodium), potassium hydroxide (or sodium), molybdate potassium (or sodium), potassium sulfate (or sodium), arsenate potassium (or sodium) and a mixture of any two or more salts of potassium (or sodium). For reasons of convenience, the preferred compound of the alkali metal is an aqueous solution of potassium hydroxide (or sodium).

When the active component 3) is a rare earth metal, suitable examples of compounds of rare-earth metal include, but are not limited to, nitrates, halides, salts of organic KIS is from and mixtures of any two or more compounds of rare-earth metals. For reasons of convenience, the preferred compound of rare earth metal is an aqueous nitrate solution.

When the active component 4) is bismuth, suitable examples of salts of bismuth include (but are not limited to, bismuth nitrate and chloride of bismuth.

It should be noted that it is advantageous to impregnate the carrier with the maximum amount of salt solution of the active component, which can be absorbed by the media.

By scanning electron microscopy (SEM) is clearly found that the active component 1), such as palladium in the catalyst of the invention is uniformly dispersed on the catalyst surface and forms a very thin layer of palladium, typically a thickness of 1 to 30 μm. In connection with the process of selective hydrogenation, which is usually limited by diffusion, used according to the invention the catalyst with a thinner layer of palladium will stand high activity and selectivity.

The catalyst according to the invention can be used in all processes for the selective hydrogenation of highly unsaturated hydrocarbons to the corresponding olefins, it is particularly suitable for the selective hydrogenation of the fraction C2 petroleum hydrocarbon thermal cracking, containing such highly unsaturated hydrocarbons like acetylene, with the formation of olefins. Used in the estuaries and the ü the term "highly unsaturated hydrocarbons" refers to hydrocarbons containing a triple bond and/or two or more double bonds. The term "selective hydrogenation of the fraction C2 of petroleum hydrocarbons process of thermal cracking" throughout the description of the invention refers to as "hydrogenation of the head of the faction"and "hydrogenation of terminal faction", as is well known to specialists in this field of technology. The catalyst of the invention can also be used to remove traces of acetylene from purified ethylene in order to obtain a product which meets the standard for ethylene polymerization purity.

When conducting the specified hydrogenation catalyst for selective hydrogenation according to the invention demonstrates the following outstanding results:

1) a synergistic effect of a number of active components in the catalyst of the present invention provides increased activity and selectivity, reduction of the resulting green oil, reducing the deposition of carbon in long-term use and, thus, longer service life over a longer interval and increases the lifetime of the catalyst;

2) on the catalyst has a very thin layer of palladium (1-30 μm). For a thin layer of palladium this type of facilitated diffusion of reagents, especially at high flow rate (increases the concentration of reagents and took the foreseen operational capacity of the material), when this catalyst has high activity and selectivity. Such indicators are highly desirable in the manufacturing process of cracking;

3) improved stability of the catalyst, thus, will increase both the activity and selectivity of the catalyst;

4) in addition, the media adopted the form of gears enables stable operation of the catalyst at high flow rate, which greatly increases the operational capacity of the catalyst.

Briefly, the catalyst according to the invention is capable of hydrogenation of alkynes or diolefins with high activity and high selectivity at high flow rate, moreover, is supported by the low rate of formation of green oil, the catalyst has the best long period of recovery, long service life and low cost.

Examples and Comparative examples

Example 1

In a glass put 20 g of particles of aluminum oxide cog shape. Accurately weighed this amount of lanthanum nitrate in order to obtain the catalyst of this example containing 0.5 wt.% lanthanum. Preparing an aqueous solution of lanthanum nitrate by dissolving solid lanthanum nitrate in water and dilution water taken in relation to the maximum possible absorption of h is CI alumina cog shape. These aluminium oxide particles after drying for 4 h at 120°and calcining 4 h at 1100°impregnated With an aqueous solution of lanthanum nitrate and get the aluminum oxide coated with lanthanum. Weigh appropriate amount of palladium nitrate solution to obtain a final catalyst containing 0.03 wt.% palladium. The palladium nitrate solution was diluted with water, taken in a volume corresponding to the maximum absorption of particles of aluminum oxide cog shape. Aluminum oxide coated with lanthanum-impregnated with a dilute aqueous solution of palladium nitrate and after drying for 4 h at 120°get the catalyst Pd-La, deposited on alumina. Weigh an appropriate amount of solid nitrate of silver in order to obtain a final catalyst containing 0.07 wt.% silver. Solid silver nitrate is dissolved in water, the volume of which is equal to the above solution of palladium nitrate. The catalyst Pd-La, deposited on alumina, is impregnated with an aqueous solution of silver nitrate and after drying at 120°get the catalyst Pd-La-Ag deposited on alumina. Weigh an appropriate amount of solid nitrate of bismuth in order to obtain a final catalyst containing 0.03 wt.% bismuth. Solid bismuth nitrate is dissolved in water, the volume of which is equal to the above amount of rest the RA of palladium nitrate. The catalyst Pd-La-Ag deposited on alumina, is impregnated with an aqueous solution of nitrate of bismuth and after drying at 120°and calcining 4 h at 450°To obtain a catalyst containing 0.03 wt.% Pd-0.5 wt.% La-0.07 wt.% Ag-0.03 wt.% Bi aluminum oxide.

Comparative example 1

In accordance with the same method described in example 1, to obtain a catalyst containing 0.03 wt.% Pd - 0.07 wt.% Ag - 0.03 wt.% Bi aluminum oxide, except that the particles of aluminum oxide cog forms are not impregnated with an aqueous solution of lanthanum nitrate.

Comparative example 2

In accordance with the same method described in example 1, to obtain a catalyst containing 0.03 wt.% Pd - 0.5 wt.% La - 0.07 wt.% Ag aluminum oxide, except that Pd-La-Ag catalyst is impregnated with an aqueous solution of nitrate of bismuth.

Example 2

In the aluminum oxide cog of the form, enter the lanthanum nitrate, potassium hydroxide, palladium nitrate, silver nitrate and bismuth nitrate by impregnation and drying, to obtain a catalyst of Pd-La-Ag-K-Bi deposited on alumina. After calcination of the catalyst Pd-La-Ag-K-Bi deposited on alumina, 4 h at 450°To obtain a catalyst containing 0.03 wt.% Pd - 0.1 wt.% To - 0.5 wt.% La - 0.07 wt.% Ag - 0.03 wt.% Bi aluminum oxide.

Example 3

In accordance with the same method described in example 2, which are square-catalyst, containing 0,033% wt. Pd - 0.1 wt.% To - 0.03 wt.% La - 0.33 wt.% Ag - of 0.005 wt.% Bi aluminum oxide.

Comparative example 3

In accordance with the same method described in example 2, to obtain a catalyst containing 0.03 wt.% Pd - 0.1 wt.% To - 0.07 wt.% Ag - 0.03 wt.% Bi aluminum oxide, except that the particles of aluminum oxide cog forms are not impregnated with an aqueous solution of lanthanum nitrate.

For the evaluation of the catalysts of examples 1-3 and comparative examples 1-3 using microstroke for testing. The volume loading of the catalyst is 1 ml when the layer height is 20 mm, the Test is carried out in the following conditions: the ratio of N2to alcino is equal to 1.3, temperature 130°C, the concentration of alkyne at the entrance of 0.51%, the volumetric rate of 10000 h-1. The results are presented in table 1.

Pd-Ag-Bitd align="left"> 95
Table 1
Number exampleComparative example 1Comparative example 2Comparative example 3Example 1Example 2Example 3
Media*Aluminium oxideAluminium oxideAluminium oxideAluminium oxideAluminium oxideAluminium oxide
The components of the catalystPd-La-AgPd-Ag-Bi-KPd-La-Ag-BiPd-La-K-Ag-BiPd-La-K-Ag-Bi
Wt.% Pd0.03; palladium nitrate0,03; palladium nitrate0,03; palladium nitrate0,03; palladium nitrate0,03; palladium nitrate0,033; palladium nitrate
Wt.% rare earth metal0,5; lanthanum nitrate0,5; lanthanum nitrate0,5; lanthanum nitrate0,03; lanthanum nitrate
Wt.% To0.1; potassium hydrate0.1; potassium hydrate0.1; potassium hydrate
Wt.% Ag0,07; silver nitrate0,07; silver nitrate0,07; silver nitrate0,07; silver nitrate0,07; silver nitrate0,33; silver nitrate
Wt.% Bi0,03; nitrate of bismuth0,03; nitrate of bismuth0,03; nitrate of bismuth0,03; nitrate of bismuth0,005; nitrate of bismuth
The Pd layer thickness, µm**5-705-405-301-20
The conversion of acetylene, %909510010092
The selectivity for ethylene, %807587859282
* Particles in the form of gears

** The thickness of the Pd layer is determined by the initial recovery of the catalyst by the way, traditional in the field of catalysis, and then measured by the method of SAM.

As can be seen from the results of table 1, when using the catalysts of the present invention Pd-La-Ag-Bi/alumina and Pd-La-Ag-K-Bi/alumina improved noticeably as the conversion of acetylene, and the selectivity for ethylene.

Example 4

Accurately weighed 300 g of spherical particles of aluminum oxide. In accordance with the same method described in example 1, to obtain a catalyst containing 0.03 wt.% Pd - 0.5 wt.% La - 0,186 wt.% Ag - 0.12 wt.% Bi aluminum oxide.

Example 5

In accordance with the same method described in example 4, except for the changed amount of lanthanum nitrate, get the catalyst containing 0.03 wt.% Pd - 1.0 wt.% La - 0,186 wt.% Ag - 0.12 wt.% Bi aluminum oxide.

Comparative example 4

In accordance with the same method described in example 4, except that the alumina is not impregnated with an aqueous solution of lanthanum nitrate, get the catalyst containing 0.03 wt.% Pd - 0,186 wt.% Ag 0.12 wt.% Bi aluminum oxide.

Comparative example 5

In accordance with the same method described in example 4, except that the alumina is not impregnated with an aqueous solution of lanthanum nitrate and the catalyst Pd-La-Ag/alumina is not impregnated with an aqueous solution of nitrate of bismuth, get the catalyst containing 0.03 wt.% Pd - 0.18 wt.% Ag aluminum oxide.

Example 6

Aqueous solution of lanthanum nitrate pour the powder of aluminum oxide, to obtain the traditional way the media in the form of gears. This medium is successively impregnated with aqueous solutions of palladium nitrate, silver nitrate and nitrate of bismuth, after drying and calcination get the catalyst containing 0.03 wt.% Pd - 0.5 wt.% La - 0,186 wt.% Ag - 0.12 wt.% Bi aluminum oxide.

Example 7

In accordance with the same method described in example 6, to obtain a catalyst containing 0,031 wt.% Pd - 2.5 wt.% La - 0,186 wt.% Ag - 0.03 wt.% Bi aluminum oxide.

Example 8

In accordance with the same method described in example 6, to obtain a catalyst containing 0.03 wt.% Pd - 0.1 wt.% To - 0.5 wt.% La - 0,105 wt.% Ag - 0.06 wt.% Bi aluminum oxide.

Example 9

In accordance with the same method described in example 6, to obtain a catalyst containing 0.03 wt.% Pd - 0.1 wt.% To - 0.5 wt.% La - 0.07 wt.% Ag - 0.03 wt.% Bi aluminum oxide.

The catalysts of comparative example 4, compare inogo of example 5 and examples 4-9 choose to conduct the hydrogenation experiments.

In a tubular reactor poured 200 ml of catalyst at the top and bottom catalyst layer placed glass beads. After purging with gaseous nitrogen and recovery of the catalyst with hydrogen is mixed with hydrogen fraction, taken from the top of deethanizer finite fraction of the hydrogenation in the cracking process to produce ethylene, and then pass the mixture through the reactor from top to bottom. This fraction contains from 0.8 to 1.1 mol.% acetylene, 15-20 mol.% ethane, the rest falls on the ethylene. The hydrogenation process is carried out in the following conditions: the ratio of H2/alkyne is 1.5, the temperature at the inlet of the reactor 35°C, space velocity of 10,000 h-1. The results are presented in table 2.

Table 2
Number exampleMediaThe components of the catalystComponent 1, wt.%Component 2, wt.%Component 3, wt.%Component 4, wt.%The content of the acetylene at the outlet (10-6mol)The selectivity for ethylene, %
Comparative example 4Spheres of aluminum oxidePd-Ag-BiThe palladium chloride, 0,03Silver nitrate, 0,186Nitrate of bismuth; 0,12<145
Compare the local example 5 Spheres of aluminum oxidePd-AgThe palladium chloride, 0,03Silver nitrate, 0,183329
Example 4Spheres of aluminum oxidePd-La-Ag-BiThe palladium chloride, 0,03Silver nitrate, 0,186The lanthanum nitrate, 0,5Nitrate of bismuth; 0,12<152
Example 5Spheres of aluminum oxidePd-La-Ag-BiThe palladium chloride, 0,03Silver nitrate, 0,186The lanthanum nitrate, 1,0Nitrate of bismuth; 0,12<150
Example 6The aluminum oxide in the form of gearsPd-La-Ag-BiThe palladium chloride, 0,03Silver nitrate, 0,186The lanthanum nitrate, 0,5Nitrate of bismuth; 0,12<149
Example 7The aluminum oxide in the form of gearsPd-La-Ag-BiThe palladium chloride, 0,031Silver nitrate, 0,186The lanthanum nitrate, 2,5Nitrate of bismuth; 0,03<135
Example 8The aluminum oxide in the form of gearsPd-La-K-Ag-BiThe palladium chloride, 0,03Silver nitrate, 0,105; hydroxy is potassium, 0,1The lanthanum nitrate, 0,5Nitrate of bismuth; 0,06<161
Example 9The aluminum oxide in the form of gearsPd-La-K-Ag-BiThe palladium chloride, 0,03Silver nitrate, 0,07; potassium hydroxide, 0,1The lanthanum nitrate, 0,5Nitrate of bismuth; 0,03<160

As can be seen from the results of table 2, when using the catalysts of the present invention, the selectivity of the catalyst due to the presence of a component of rare metal increases by more than 10%, in conditions of high flow rate 10000 h-1that is quite significantly catalyst for industrial applications.

In the above conditions, after the catalysts of comparative example 2, comparative example 4, example 4 and example 5 will work within 943 h, carefully measure the total number of collected green oil and the weight gain of the catalyst (i.e. the total weight of green oil and carbon deposits for each of the catalyst). These data are shown in the following table 3.

Table 3
Number exampleComparative example 2Comparative example 4Example 4Example 5
The weight gain of the catalyst after work during 943 h (g)16,2014,669,249,01
Weight of green oil after work during 943 h (g)120,1115, 8mm107,496,6
Color green oilLight yellowLight yellowColorlessColorless

Lighter color of green oil indicates a lower molecular mass of green oil, therefore, it can be easier to remove during regeneration of the catalyst. The smaller the magnitude of the gain of the catalyst indicates that it has a longer period of operation. From the results shown in table 3, it is clear that the weight gain of the catalyst is reduced by more than 30%, and the amount of green oil after operation of the catalyst decreases, apparently due to the presence of a component of rare earth metal and bismuth.

Example 10

Molded in the form of gears particles aluminiumoxide media (20 g) is impregnated with an aqueous solution of lanthanum nitrate in order to obtain a carrier coated with lanthanum containing 0.1 wt.% La. In accordance with the above-mentioned method of producing the catalyst carrier coated with lanthanum sequentially impregnated with aqueous solutions of palladium chloride, NITR is the silver and nitrate of bismuth and after drying and calcination get the catalyst, containing 0.03 wt.% Pd - 0.1 wt.% La - 0.18 wt.% Ag - 0.10 wt.% Bi aluminum oxide.

Examples 11-15

Get five catalysts in accordance with the same method described in example 1, except that instead of the aqueous solution of lanthanum nitrate in each sample using, respectively, aqueous solutions of cerium nitrate, neodymium nitrate, praseodymium nitrate, europium nitrate, yttrium nitrate.

For the evaluation of the catalysts of examples 10-15 use microstroke for testing. The volume loading of the catalyst is 1 ml when the layer height is 20 mm, the Test is carried out in the following conditions: the ratio of N2to alcino equals 1.5, the process temperature is 90°C, the concentration of alkyne at the entrance of 0.4 mol.%, space velocity of 10,000 h-1. The results are presented in table 4.

Table 4
Number exampleExample 10Example 11Example 12Example 13Example 14Example 15
Media*Aluminium oxideAluminium oxideAluminium oxideAluminium oxideAluminium oxideAluminium oxide
The components of the catalystPd-La-Ag-BiPd-Ce-Ag-BiPd-Nd-A-Bi Pd-Pr-Ag-BiPd-Eu-Ag-BiPd-Y-Ag-Bi
Wt.% Pd0,03; palladium chloride0,03; palladium chloride0.03 palladium chloride0,03; palladium chloride0,03; palladium chloride0,03; palladium chloride
Wt.% Ag0,18; silver nitrate0,18; silver nitrate0,18; silver nitrate0,18; silver nitrate0,18; silver nitrate0,18; silver nitrate
Wt.% rare earth metal - socializaton0.1; lanthanum nitrate0.1; cerium nitrate0.1; neodymium nitrate0.1; praseodymium nitrate0.1; europium nitrate0.1; yttrium nitrate
Wt.% Bi0,10; nitrate of bismuth0,10; nitrate of bismuth0,10; nitrate of bismuth0,10; nitrate of bismuth0,10; nitrate of bismuth0,10; nitrate of bismuth
The conversion of acetylene, %658183616990
The selectivity for ethylene, %827778828171
* Particles in the form of gears

Example 16

In particles of aluminum is xenova media in the form of gears (300 g) sequentially introducing a lanthanum nitrate, the potassium hydrate, palladium chloride, silver nitrate and bismuth nitrate by impregnation of the corresponding aqueous solutions, followed by drying. After annealing gives a catalyst containing to 0.032 wt.% Pd - 0.1 wt.% K - 1 wt.% La - 0.03 wt.% Ag - 0.03 wt.% Bi aluminum oxide.

Examples 17

Particles aluminiumoxide media in the form of gears (300 g) simultaneously impregnated with aqueous solutions of potassium carbonate and lanthanum nitrate, then dried and calcined to obtain a carrier coated with potassium and lanthanum. This K-La-media simultaneously impregnated with aqueous solutions of palladium nitrate, silver nitrate and bismuth nitrate. After annealing gives a catalyst containing to 0.032 wt.% Pd - 0.1 wt.% To - 0.3 wt.% La - 0.01 wt.% Ag - 0.03 wt.% Bi aluminum oxide.

The catalysts of examples 16 and 17 experience in industrial setting on a branch flow of raw materials. In a tubular reactor poured 200 ml of catalyst. After purging the reactor with gaseous nitrogen through the reactor miss a fraction of C2-C3, taken from the top of depropanizer head of the faction of the hydrogenation process in the cracking process to produce ethylene. This fraction contains 0.4 to 0.7 mol.% acetylene, of 0.4-0.6 mol.% methylacetylene + PROPADIENE (MAPD), 500-2000 hours/million of carbon monoxide, 8-14 mol.% hydrogen, 25-31 mol.% methane, 4-6 mol.% ethane, 45-50 mol.% ethylene and a small amount of propane. The decree of the config above, the process of hydrogenation is carried out in the following conditions: inlet temperature to the reactor 70° C, space velocity of 20000 h-1. The results are presented in table 5.

Table 5
Number exampleExample 16Example 17
Media*Aluminium oxideAluminium oxide
Wt.% the main catalyst Pd0,032; palladium nitrate0,032; palladium nitrate
Wt.% rare earth metal socializaton1; lanthanum nitrate0,3; lanthanum nitrate
Wt.% To0.1; potassium hydrate0.1; potassium carbonate
Wt.% Ag0,03; silver nitrate0,01; silver nitrate
Wt.% Bi0,03; nitrate of bismuth0,03; nitrate of bismuth
The content of the acetylene at the outlet (10-6mol)<1<1
The selectivity for ethylene, %>70>50
Conversion MAPD, %>50>50
Selectivity for MAPD, %>70>70
* Particles in the form of gears

In table 5 the results show that the catalyst of the present invention can be used for sovan not only for the removal of acetylene from raw materials, but also to remove methylacetylene and PROPADIENE that are simultaneously present in the raw materials.

Industrial applicability

The specific composition of the catalyst for selective hydrogenation according to the invention provides a synergistic effect numerous active components contained therein. The activity, selectivity and stability of the catalyst is increased, and the formation of green oil is reduced and, thus, increases the service life of the catalyst and the production costs are reduced. The catalyst according to the invention is very suitable for industrial process of cracking and has broad prospects for industrial applications.

1. A catalyst for selective hydrogenation for selective hydrogenation of unsaturated hydrocarbons, which mainly contains the following active components are deposited on a porous inorganic carrier, calculated on the total weight of the catalyst, wt.%:

1) 0.001-1% Pd;

2) 0.001-10% of at least one of Ag, Cu, Zn, K, Na, Mg, Ca, Be, Sn, Pb, Cd, Sr, Ba, Ra, Mn, Zr, Mo, Ge;

3) 0.01-5% of at least one of rare earth metals and

4) 0.001-5% Bi;

in which rare earth metal selected from scandium, yttrium and lanthanides in group IIIB of the periodic table of elements.

2. The catalyst according to claim 1, in which the active component (1) which leaves 0,008-0.3% based on the total weight of the catalyst.

3. The catalyst according to claim 2, in which the active component (1) is 0.01 to 0.15% calculated on the total weight of the catalyst.

4. The catalyst according to claim 1, in which the active component (2) is 0.01-2%, based on the total weight of the catalyst.

5. The catalyst according to claim 1, in which the active component (3) is 0.05-3%, based on the total weight of the catalyst.

6. The catalyst according to claim 5, in which the active component (3) is 0.1-1.5% based on the total weight of the catalyst.

7. The catalyst according to claim 1, in which the active component (4) is from 0.005 to 1% calculated on the total weight of the catalyst.

8. The catalyst according to claim 1, in which the active component (1) is Pd.

9. The catalyst according to claim 1, in which the thickness of the layer of palladium in the catalyst is 1-30 μm.

10. The catalyst according to claim 1, in which the active component (2) is silver.

11. The catalyst according to claim 1, in which the active component (2) are silver and potassium.

12. The catalyst according to claim 1, in which the active component (2) are silver and sodium.

13. The catalyst according to claim 1, in which the rare earth metal selected from the group consisting of La, CE, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or mixtures thereof.

14. The catalyst according to item 13, in which the rare earth metal is La and/or Nd.

15. The catalyst according to claim 1, wherein the carrier is selected from the group consisting of hard-shelled land, spinel, silicon dioxide, deoxidation, aluminum oxide, or combinations of two or more of these substances, and the carrier has the form of granules, gears, areas, laminated or tape form and has a specific surface area 1-200 m2/year

16. The catalyst according to item 15, in which the carrier is selected from the group consisting of Al2O3, TiO2or SiO2has the form of gears, spherical or tape form and has a specific surface area 2-120 m2/year

17. The catalyst according to item 16, in which the carrier has the form of a gear and has a specific surface area 2-50 m2/year

18. A catalyst for selective hydrogenation for selective hydrogenation of unsaturated hydrocarbons, which mainly contains the following active components are deposited on a porous inorganic carrier, wt.%:

1) Pd;

2) Ag or Ag and Na;

3) at least one lanthanide;

4) Bi;

in which the active component (1) is 0.01 to 0.15%, active ingredient (2) is 0.01-2%, active ingredient (3) is 0.1-1.5% and the active component (4) is from 0.005 to 1% calculated on the total weight of the catalyst.

19. The catalyst p in which media are selected from the group consisting of hard-shelled land, spinel, silicon dioxide, titanium dioxide, aluminum oxide or combinations of two or more of these substances, and the carrier has the form g is anal, gears, areas, laminated or tape form and has a specific surface area 1-200 m2/year

20. The catalyst according to claim 19, in which the carrier is selected from the group consisting of silicon dioxide, titanium dioxide or aluminum oxide, which has the form of gears, spherical or tape form and has a specific surface area 2-120 m2/year

21. The catalyst according to claim 20, in which the carrier has the form of a gear wheel and has a specific surface area 2-50 m2/year

22. The method of producing catalyst according to any one of claims 1 to 21, in which the first applied component rare earth metal, or first simultaneously applied component rare earth metal component or To Na and then applied sequentially or simultaneously with other active ingredients.

23. The use of the catalyst according to any one of claims 1 to 21 in the method for selective hydrogenation of alkynes and diolefins having from two to four carbon atoms in the fraction of C2 or C3 of petroleum hydrocarbons process for thermal cracking to olefins.



 

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