Catalyst of selective hydrogenation, method of production of such catalyst and method of selective hydrogeneration of alkynes with the use of such catalyst

FIELD: catalysts of selective hydrogenation of alkynes of C4 fractions.

SUBSTANCE: proposed catalyst contains 1-30 mass-% of copper used as first active component, 0.001-5 mass-% of palladium used as second active component, at least 0.001-6 mass-% of one metal selected from Al, Pt, Pb, Mn, Co, Ni, Cr, Bi, Zr and Mo as co-catalyst; the remainder being one carrier selected from aluminum oxide, silicon dioxide and titanium oxide. Method of production of catalyst includes impregnation of carrier calcined preliminarily with solutions of active components depending on their content in catalyst. Alkynes are removed from C4 fractions enriched with alkynes by means of selective hydrogenation with the use of said catalyst.

EFFECT: enhanced selectivity and stability of catalyst.

31 cl, 2 tbl, 13 ex

 

The present invention relates to a hydrogenation catalyst, more specifically it relates to a catalyst for selective hydrogenation of alkynes With4-factions. The present invention also relates to a method for obtaining a specified catalyst, its use in the selective hydrogenation and the regeneration method of the specified catalyst.

With4-faction manufactured by the petrochemical industry, are a mixture of several alkanes and olefins containing 4 carbon atoms, in which 1,3-butadiene, considered as one of the important industrial components, is approximately 40-60 wt.%, and alkynes, present as impurities, including methylacetylene (MA), ETHYLACETYLENE (EA), vinylacetylene (VA), and others, comprise up to 0.5-2.5% by weight. Thus, there is a need in the hydrogenation of alkynes in C4-factions with the aim of obtaining 1,3-butadiene of high purity that meets the requirements of polymerization.

One way of removing alkynes based on catalytically selective hydrogenation of alkynes using catalysts in such a way to turn alkynes, such as VA, EA, MA, and others, butadiene, butene and butane, although the latter is formed in a relatively small number, thus making4-alkynes useful. The hydrogenation catalyst used in the om removal method alkynes, must have a high activity and selectivity, and therefore can effectively remove alkynes with little loss of 1,3-butadiene. In addition, it is desirable that the catalyst had good operational stability over time at low current investments.

In U.S. patent No. 4 101 451 sent for review January 19, 1977, and then issued to the Dow Chemical Company, discusses how to improve the activity of activated copper catalyst suitable for selective hydrogenation of alkynes in the liquid streams containing olefins. In the working examples of this patent was used the catalyst, in which salts of Cu, Ni, Co, Cr, Mn or Ag were deposited on the carrier material of Na2O, containing γ-aluminum oxide.

In the patent JP 57-185228 discusses how selective hydrogenation alkenovich compounds. Catalysts containing Al2O3as the carrier and palladium and copper or palladium and silver as the active components used in the examples of the hydrogenation of alkynes in C4-factions.

It turned out that when the catalysts, which are widely adopted in the prior art, are used for removal of alkynes from C4-fractions by selective hydrogenation, problems arise because of the impossibility of effective selective hydrogenation enriched what kinami 4-fractions, in which the content of alkynes is, for example, up to 2 wt.%, on the one hand, and due to the low probability of full hydrogenation to obtain satisfactory removal of alkynes, for example, to content 25 mind, or even to the content of alkynes 15 mlnd as required in the process described in the art, on the other hand. Thus, we need to search for a catalyst that can consistently and effectively remove-rich alkynes alkynes With4-fractions by selective hydrogenation.

Thus, an object of the present invention is to provide a new catalyst that can be used for removing alkynes-rich alkynes With4-fractions by selective hydrogenation with high efficiency, good selectivity, and outstanding stability and long service life.

Another object of the present invention is to develop a method of producing a catalyst which can be used for removing alkynes-rich alkynes With4-fractions by selective hydrogenation with high efficiency, good selectivity, and outstanding stability and long service life.

Another object of the present invention is the use of this catalyst for the removal of alkynes from obogs is the R alkynes With 4-fractions by selective hydrogenation.

And another object of the present invention is the development of the regeneration method of the above-mentioned catalyst.

These and other objects of the invention are achieved by creating a surprising and unexpected way catalyst containing 1-30 wt.%. copper as a first active component, 0.001 to 5 wt.%. palladium as a second active component, 0.001 to 6 wt.%, at least one metal selected from Ag, Pt, Pb, Mn, Co, Ni, Cr, Bi, Zr and Mo as socializaton, and the rest of the number, at least one carrier selected from aluminum oxide, silicon dioxide and titanium oxide, all percentages given above and hereinafter, is calculated based on the total weight of the catalyst except in specified cases.

Preferably the catalyst in accordance with the present invention contains 3 to 20% wt. copper, 0.05 to 3 wt.%. palladium, 0.01 to 4 wt.%, at least one metal selected from Ag, Pt, Pb, Mn, Co, Ni, Cr, Bi, Zr and Mo as socializaton based on the total weight of the catalyst.

More preferably the catalyst in accordance with the present invention contains 3 to 20% wt. copper, 0.05 to 1 wt.%. palladium, 0.01 to 1 wt.%, at least one metal selected from Ag, Pt, Pb, Mn, Co, Ni, Cr, Bi, Zr and Mo as socializaton, based on the total weight of catalysis is ora.

As a variant of the present invention, the mass ratio of Cu/Pd in the final catalyst is in the range of 20-60.

As a variant of the present invention, the carrier used in the catalyst of the present invention, optionally treated with salts of alkali metals, salts of alkaline earth metals or mixtures thereof, so as to enhance the catalytic selectivity and reduce the surface acidity of the medium and to control the polymerization of butadiene by reducing the possibility of the formation of polymers.

Preferably specified alkali metal selected at least one metal from the group including Li, Na, K, Rb and Cs, and the alkaline earth metal selected at least one metal from the group consisting of Be, Mg, CA, Sr and BA.

More preferably the specified alkali metal selected at least one metal from the group consisting of Li, Na and K, as specified alkaline earth metal selected at least one metal from the group consisting of Be, Mg and CA.

Preferably the amount of these salts of alkali metals, salts of alkaline earth metals or mixtures thereof, expressed as elemental metal is 0.001-3 wt.%, preferably of 0.05-0.5 wt.%. based on the total weight of the catalyst.

The catalyst in accordance with this is their invention has a specific surface area 100-350 m 2/g, which is determined by using a device for measuring the surface area of the model g-1.

The catalyst in accordance with the present invention has an average pore diameter of 30-200when you define using the detector adsorption type Sorptomatic 1990 (Ex FISONS Corp.), where as the adsorption gas is used N2.

Preferably the catalysts of the present invention as a carrier uses aluminum oxide, titanium oxide or silicon dioxide in the form of bars, strips, plates, cylindrical pellets, granulated powders or spheroidal particles.

More preferably the catalysts of the present invention as a carrier uses aluminum oxide, titanium oxide or silicon dioxide in the form of spheroidal particles with a diameter of 2-5 mm

The present invention also relates to a method of preparation of the catalyst in accordance with the present invention, which involves the following stages:

(1) forming the carrier substance is selected at least from aluminum oxide, silicon dioxide or titanium dioxide, calcined at 200-900°C;

(2) the carrier obtained in stage (1), soaked in any order solution of copper nitrate and a solution of palladium nitrate, palladium chloride or palladium acetate so that the copper content reaches 1-30% wt. and the palladium content with the hat of 0.001-5 wt.%. based on the total weight of the catalyst;

(3) the pH value of the solution of palladium nitrate, palladium chloride or palladium acetate used in stage (2), bring to 3-6 aqueous solution of ammonia, solutions of sodium bicarbonate or sodium carbonate;

(4) the carrier obtained in stage (2), calcined at 300 to 500°C for 4-10 hours;

(5) the carrier impregnated in any order the solution of salt of at least one metal selected from Ag, Pt, Pb, Mn, Co, Ni, Cr, Bi, Zr and Mo as socializaton simultaneously with the copper salt solution in stage (2) or separately.

In accordance with a variant of the method of the present invention the specified media form into bars, strips, plates, cylindrical pellets, granular powders or spheroidal particles, preferably spheroidal particles.

More preferably, in the process of preparation of the catalyst in accordance with the present invention as a carrier uses aluminum oxide, titanium oxide or silicon dioxide in the form of spheroidal particles with a diameter of 2-5 mm

In accordance with a variant of the method of the present invention at the stage of (1) forming the carrier substance calcined at 300-800°C for 1-8 hours.

In accordance with a variant of the method of the present invention at the stage (3) the pH value was adjusted to 3-5 with an aqueous solution of ammonia or a solution and sodium bicarbonate or sodium carbonate.

In accordance with a variant of the method of the present invention, the carrier is impregnated in any order the solution of salt of at least one metal selected from Ag, Pt, Bi, Pb, and Zr as socializaton simultaneously or separately with a solution of salt of copper on stage (2).

In accordance with a variant of the method of the present invention at the stage (2), the carrier is impregnated with a solution of palladium nitrate, palladium chloride or palladium acetate, preferably after it is impregnated with silver nitrate solution.

In accordance with a variant of the method of the present invention after a stage (1) it optionally includes a stage of impregnation of the carrier obtained in stage (1), a solution of salts of alkaline or alkaline earth metal or mixtures thereof.

In accordance with a variant of the method of the present invention, the mass ratio of Cu/Pd in the final catalyst is in the range from 20 to 60.

Preferably, salts of alkali metals, salts of alkaline earth metals or mixtures thereof, expressed as elemental metal, comprised of 0.001-3 wt.%, preferably of 0.05-0.5 wt.%. based on the total weight of the catalyst.

In accordance with a variant of the method of the present invention after impregnation with solutions of salts of alkaline or alkaline earth metal or mixtures thereof obtained, the carrier is dried and then calcined at 350-500°in ECENA 6-10 hours.

The present invention also relates to the use of the catalyst in accordance with the present invention for removing alkynes-rich alkynes With4-fractions by selective hydrogenation, which includes transmission With4fractions from 0.5 to 2.5% wt. alkynes and hydrogen in a fixed bed, which is filled with a catalyst in accordance with the present invention, where the temperature input is in the range of 20-50°the reaction pressure is in the range from 0.6-1.0 MPa, a volumetric hourly rate of liquid (OCSI) installed at 2-60 h-1(V/V) and the molar ratio of hydrogen to alkynes is in the range 1-6.

In accordance with the use of catalysts of the present invention related to alkynes, which can be removed by selective hydrogenation using catalysts of the present invention, it is possible to mention methylacetylene, ETHYLACETYLENE and vinylacetylene.

In accordance with the use of these catalysts related to used a fixed layer, it can be called a single-stage layer, two-layer, or any other conventional catalytic layers the art that is suitable for extending the service life of the catalyst.

Under the words "enriched alkynes" throughout the text of this application podrazumevao the SJ such content alkynes, which reaches up to 2.5% wt. in C4-factions, which must be processed.

The present invention is additionally illustrated by the following examples, but these examples should not be construed as limiting the present invention. The scope of protection, which is intended for the present invention is defined by the attached claims.

Obtaining catalyst

Commercially available spheroidal particles of Al2O3or TiO2with a diameter of 2-3 mm, annealed at 636°C for 6 h, and then optionally impregnated with a solution of salts of alkaline or alkaline earth metal. The resulting carrier is dried and calcined at 350°C for 6 h and then impregnated with the prepared solution of nitrate of copper so that the copper content is 1-30% wt. based on the weight of the catalyst. The resulting carrier calcined at 300-600°C for 4-10 hours Then the resulting carrier is impregnated with the prepared solution of palladium nitrate, palladium chloride or palladium acetate, the pH value of which was brought to 3-5 aqueous solution of ammonia or solutions of sodium bicarbonate or sodium carbonate so that the resulting product contains 0.001 to 5 wt.%. palladium at a mass ratio of Cu/Pd in the final catalyst being in the range of 20-60 based on the total weight of the catalyst. The media is ova calcined at 350° C for 6 hours a Carrier impregnated in any order the solution of salt of at least one metal as socializaton selected from the group consisting of Ag, Pt, Pb, Mn, Co, Ni, Cr, Bi, Zr and Mo, simultaneously or separately with the above solution of nitrate of copper. The strength of the catalyst particles is 0.6-1.0 MPa on the particle.

In the examples, the hydrogenation is carried out in a reactor with a fixed bed, which operates with the following parameters:

Temperature input (°)20-50
The reaction pressure (MPa)0,6-1,0
OCSI (h-1about/about)2-60
H2/alkynes (mol/mol)1-6

Experimental conditions and results are presented in table 1.

As shown in table 1, examples 7 and 13 is carried out in a reactor with a two-stage fixed bed. Examples 14, 15 and 16 are comparative experiments. Properties of the catalyst, which is devoid of the first active component Cu, studied in example 14. Properties of the catalyst not containing the selected socializaton in accordance with the present invention, such as Ag, studied in example 15. Properties of the catalyst not containing the second active component Pd, studied in example La compare with each other the results of the experiments, obtained using the catalysts of the above-mentioned 3 comparative examples, and the results of example 13, representing the present invention, are shown in table 2, showing appropriate changes in residual alkynes and losses of butadiene in time for each case.

As can be seen from table 1, the catalyst in accordance with the present invention can be used for processing enriched alkynes With4-factions, and can be reduced content of alkynes in the treated With4-factions to less than 15 mlnd, and loss of 1,3-butadiene to values below 1.5% wt. The data of comparative example 14 indicates that the catalyst based on palladium that does not contain copper, has a lower activity, and the content of alkynes in the treated With4-factions still up to 4500 mlnd Comparative example 16 shows that the catalyst based on copper, not containing palladium, has a slightly higher activity than in example 14, which is still very low, with significant loss of 1,3-butadiene. Comparative example 15 shows that the activity of the catalyst based on copper can be significantly increased by the addition of palladium. Example 13 shows that the activity of copper-palladium catalyst can be greatly improved by the odd add a component of socializaton, and the loss of 1,3-butadiene can be further reduced in comparison with comparative example 15.

From table 2 it is seen that the catalyst of this technology has low activity and short service life, whereas the activity and selectivity of catalysts in accordance with the present invention can be stored after long experience.

The catalyst proposed by the present invention demonstrates the advantages of the catalysts based on copper, base metal, and catalysts based on palladium, precious metal, by getting rid of their respective disadvantages. First, the catalyst in accordance with the present invention has such a high activity that even enriched alkynes (0.5 to 2.5% wt.) With4-fraction can be effectively providerone. On the contrary, the catalysts commonly used in the prior art, can be used only when the selective hydrogenation of C4-fractions, in which the content of alkynes is less than 0.2% wt. Secondly, the catalyst in accordance with the present invention has good selectivity, i.e. butadiene undergoes no or practically not subjected to hydrogenation during hydrogenation of alkynes. Thirdly, the surface acidity of this media may be the effect of the EIT reduced by processing the media salts of alkali metals, salts of alkaline earth metals or mixtures thereof, which contributes to the inhibition of polymerization of dienes and reduce the formation of polymers, thus reducing the loss of butadiene. In addition, the present catalyst has a long life and a period of regeneration and can be easily regenerated in a simple way with the restoration of its initial activity.

For qualified in the field of specialist it is obvious that the invention is not limited to the details presented above are illustrative examples and that the present invention can be implemented in other specific forms without deviating from its essential features, and all the changes that are equivalent to the values and the interval of the claims, therefore, as implied covered it.

1. A catalyst for selective hydrogenation, characterized in that it contains is based on the total weight of the catalyst 1-30 wt.% copper as a first active component, 0.001 to 5 wt.% palladium as a second active component, 0.001 to 6 wt.%, at least one metal selected from Ag, Pt, Pb, Mn, Co, Ni, Cr, Bi, Zr and Mo as socializaton, and the rest of the number, at least one carrier selected from aluminum oxide, silicon dioxide and titanium dioxide.

2. The catalyst according to claim 1, characterized in that it contains 3-20 wt.% copper ,05-3 wt.% palladium, 0.01 to 4 wt.%, at least one metal selected from Ag, Pt, Pb, Mn, Co, Ni, Cr, Bi, Zr and Mo as socializaton based on the total weight of the catalyst.

3. The catalyst according to claim 1, characterized in that it contains 3-20 wt.% copper, 0.05 to 1 wt.% palladium, 0.01 to 1 wt.%, at least one metal selected from Ag, Pt, Pb, Mn, Co, Ni, Cr, Bi, Zr and Mo as socializaton based on the total weight of the catalyst.

4. The catalyst according to claim 1, characterized in that the specified media treated with salts of alkali metals, salts of alkaline earth metals or mixtures thereof.

5. The catalyst according to claim 4, characterized in that said alkali metal is selected at least one metal selected from the group consisting of Li, Na, K, Rb and Cs, and the alkaline earth metal selected at least one metal from the group consisting of Be, Mg, Ca, Sr and BA.

6. The catalyst according to claim 5, characterized in that said alkali metal is selected at least one metal from the group consisting of Li, Na and K, as specified alkaline earth metal selected at least one metal from the group consisting of Be, Mg and Ca.

7. The catalyst according to claim 4, characterized in that the said salts of alkali metals, salts of alkaline earth metals or mixtures thereof, expressed as elemental metal is 0.001 to 3 wt.% based on the total weight of the catalyst.

8. Kata is isator according to claim 7, characterized in that the said salts of alkali metals, salts of alkaline earth metals or mixtures thereof, expressed as elemental metal, 0.05 to 0.5 wt.% based on the total weight of the catalyst.

9. The catalyst according to claim 1, characterized in that the mass ratio of Cu/Pd in the final catalyst is in the range of 20-60.

10. The catalyst according to claim 1, characterized in that it has a specific surface area of 100-350 m2/year

11. The catalyst according to claim 1, characterized in that it has an average pore diameter of.

12. The catalyst according to claim 1, characterized in that the medium contains aluminum oxide, silicon dioxide or titanium oxide in the form of bars, strips, plates, cylindrical pellets, granulated powders or spheroidal particles.

13. The catalyst according to claim 1, characterized in that the medium contains aluminum oxide, titanium oxide or silicon dioxide in the form of spheroidal particles with a diameter of 2-5 mm

14. The method of producing catalyst according to any one of claims 1 to 13, characterized in that

(1) forming the carrier substance is selected at least from aluminum oxide, silicon dioxide or titanium dioxide, calcined at 200-900°C;

(2) the carrier obtained in stage (1), soaked in any order solution of copper nitrate and palladium nitrate solution, chloride of pallid what I or palladium acetate so, the copper content reaches 1-30 wt.% and the palladium content is 0.001-5 wt.% based on the total weight of the catalyst;

(3) the pH value of the solution of palladium nitrate, palladium chloride or palladium acetate used in stage (2), bring to 3-6 aqueous solution of ammonia, solutions of sodium bicarbonate or sodium carbonate;

(4) the carrier obtained in stage (2), calcined at 300 to 500°C for 4-10 h;

(5) the carrier impregnated in any order the solution of salt of at least one metal selected from Ag, Pt, Pb, Mn, Co, Ni, Cr, Bi, Zr and Mo as socializaton simultaneously with the copper salt solution in stage (2) or separately.

15. The method according to 14, characterized in that the carrier is formed into bars, strips, plates, cylindrical pellets, granular powders or spheroidal particles.

16. The method according to 14, characterized in that as the carrier uses aluminum oxide, titanium oxide or silicon dioxide with a diameter of 2-5 mm in the form of spheroidal particles.

17. The method according to 14, characterized in that in stage (1) forming the carrier substance calcined at 300-800°C for 1-8 hours

18. The method according to 14, characterized in that in stage (3) the pH of the solution of palladium nitrate, palladium chloride or palladium acetate adjusted to 3-5 with an aqueous solution of ammonia, or solutions of sodium bicarbonate or sodium carbonate.

19. The method according to 14, characterized in that the carrier is impregnated in any order the solution of salt of at least one metal selected from Ag, Pt, Pb, Bi and Zr, as socializaton simultaneously or separately with a solution of salt of copper on stage (2).

20. The method according to 14, characterized in that in stage (2), the carrier is impregnated with a solution of palladium nitrate, palladium chloride or palladium acetate after he soaked in a solution of nitrate of copper.

21. The method according to 14, characterized in that it further includes, after stage (1) stage of impregnation of the carrier obtained in stage (1), a solution of salts of alkaline or alkaline earth metal or mixtures thereof.

22. The method according to item 21, characterized in that said alkali metal is selected at least one metal from the group consisting of Li, Na, K, Rb and Cs, and the alkaline earth metal selected at least one metal from the group consisting of Be, Mg, Ca, Sr and BA.

23. The method according to item 22, characterized in that said alkali metal is selected at least one metal from the group consisting of Li, Na and K, as specified alkaline earth metal selected at least one metal from the group consisting of Be, Mg and CA.

24. The method according to item 21, wherein the salts of alkali metals, alkaline earth metals and mixtures thereof, expressed as elemental metal, accounted for the amount of 0.001-3 wt.% based on the total weight of the catalyst.

25. The method according to paragraph 24, wherein the salts of alkali metals, alkaline earth metals and mixtures thereof, expressed as elemental metal, 0.05 to 0.5 wt.% based on the total weight of the catalyst.

26. The method according to item 21, wherein after impregnation with solutions of salts of alkaline metal or alkaline earth metal, or mixtures thereof specified carrier is dried and then calcined at 350-500°C for 6-10 hours

27. The method according to 14, characterized in that the mass ratio of Cu/Pd in the final catalyst is in the range of 20-60.

28. Method of removing alkynes-rich alkynes With4-fractions by selective hydrogenation, characterized in that it includes a transmission With4fractions from 0.5 to 2.5 wt.% alkynes and hydrogen in a fixed bed, which is filled with a catalyst according to any one of claims 1 to 13, where the temperature input is in the range of 20-50°the reaction pressure is in the range from 0.6-1.0 MPa, a volumetric hourly rate of the fluid installed at 2-60 h-1(V/V) and the molar ratio of hydrogen to alkynes is in the range 1-6.

29. The method according to p, wherein the alkynes, which can be removed by selective hydrogenation using the catalyst according to any one of claims 1 to 13 represent methylacetylene, ETHYLACETYLENE and vinylacetylene.

30. The method according to p or 29, otlichayushiesya, the specified fixed layer is a single-stage layer, two-layer, or any other conventional catalytic layers the art that is suitable for extending the service life of the catalyst.

31. The method according to p, characterized in that a volumetric hourly rate of a liquid in a fixed bed filled with a catalyst according to any one of claims 1 to 13, is in the range of 2-40 h-1(on/about).



 

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3 tbl, 22 ex

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13 cl, 2 tbl, 17 ex

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