The catalyst for hydrogenation of unsaturated hydrocarbons

 

The invention relates to the field of chemical technology. Described is a catalyst for hydrogenation of unsaturated hydrocarbons containing a catalytically active amount of Pd and, if necessary, Ag on the media; this catalyst is characterized by the fact that the carrier is a molded product with a three-form cross-section, and these lobes are provided with through-holes. Describes how to obtain a catalyst in which the carrier is impregnated with a solution of salts of Pd and, if necessary, Ag, these salts restore using a reducing agent, and then soaked in this way, the carrier is washed, dried and calicivirus and, if recovery is incomplete, still available oxides of Pd and Ag restore in a hydrogen-containing atmosphere to the corresponding metals. Technical result: obtained a catalyst having a relatively low flow resistance and allow the hydrogenation of unsaturated hydrocarbons at high space velocities. 2 C. and 16 h.p. f-crystals, 3 tab., 1 Il.

This invention relates to a catalyst for the hydrogenation of unsaturated hydrocarbons.

From Europe the 3 carbon atoms to the corresponding ethylene compounds (alkenes), to use the catalyst on the carrier in the form of beads or extrudates, which contain palladium and silver. At least 80% of palladium and at least 80% of the silver is located at the periphery of the catalyst. The catalyst preferably contains alumina as a carrier and 0.01-0.5 wt.% palladium 0.001 to 0.002 wt.% silver. On the basis of the form of media activity and selectivity in the calculation of the weight is relatively low. In addition, you can only work with a relatively small volume velocity and pressure loss in the catalyst layer are relatively high.

From EP-A-0689872 known containing Pd and Ad catalyst for selective hydrogenation of acetylene. This catalyst is obtained by processing the media (preferably alumina), in the form of balls or cylindrical tablets (catalyst particles), an alkaline solution of a reducing agent for Pd and Ad.

From EP-A-0693315 known catalyst on the carrier for the hydrogenation of diolefins, which contains palladium, silver and fluoride of an alkali metal. As the carrier used is preferably spherical particles or cylindrical extrudates.

From EP-A-0738540 known catalyst for the hydrogenation of C2-C10-alkynes (pred palladium, silver, at least one chemically bound alkali metal (preferably K), chemically bound fluorine and one inorganic carrier (preferably alumina), in tablet form.

EP-A-0732146 describes catalysts, carriers which are molded product with a three-form cross-section and passing through (through) holes. These catalysts contain as catalytically active components of the connection, iron oxide - molybdenum oxide. In particular, the catalysts used for the oxidation of methanol to formaldehyde, although are some other, not backed up by examples of the application (for example, hydrogenation of acetylene and olefins).

EP-A-464633 describes catalysts, carriers which are molded product with a three-form cross-section and passing through (through) holes (EUR. Fig.5). These catalysts contain as catalytically active component, a mixture of elements of group VIII and 1B of the periodic system, in particular palladium and gold. They are used for the conversion of olefins organic carboxylic acids and oxygen to unsaturated esters, in particular to obtain the vinyl is pestaway shape of cross-section and at least three through-hole-long as well as a certain ratio of the height of the grains and the distance between the axes of the channels. This material is used for oxidative hydrogenation of methanol to obtain formaldehyde.

In addition, applicants are listed under the names G-58 G-83 catalysts for selective hydrogenation of diolefins and alkynes to monoolefins or alkenes, which contain palladium and silver on having the form of granules media or media in the form of solid tablets or extrudates (for example, Datenblatter "Girdler Catalyst G-58, G-58 D, G-58 H, G-58 I and G-83 for Selective Hydrogenation", von Januar 1998).

Catalysts on such drives usually have the disadvantage that their activity and selectivity are relatively low and the hydrogenation can be carried out only at relatively low space velocities. In addition, these catalysts have a relatively high resistance to flow.

The objective of the invention is to overcome these disadvantages. It has been unexpectedly discovered that these disadvantages can be overcome by the use of a catalyst carrier which has a certain form.

Thus, the purpose of this invention is the catalytic hydrogenation of unsaturated hydrocarbon compounds containing catalytically predstavljaet a molded product with a three-form cross-section, the petals provided with a through-hole.

The catalyst of this invention usually has a geometric surface (GO) about 0.2-3 cm2preferably approximately 0.7-1.9 cm2in particular ~ 0.9-1.5 cm2on the moldings.

The ratio between the length (l) and diameter (d) of a three-molded product is as follows:

R1=l/d=2-4.

The ratio between the geometric surface of the molded product and the volume of the solid part of the molded product (Vf) is preferably:

R2=GO/Vf=0,5-20 (mm-1), in particular 1,4-5 (mm-1).

Preferably Pd is present in amounts from about 0.01 to 1.0 wt.%, and Hell in amounts from about 0.1 to 0.5 wt.% based on the material of the carrier, and the weight ratio between Pd and Ad is approximately 0.1 to 5.0.

The penetration depth of the catalytically active component (Pd and, if necessary, Ad) in a molded product in the media after the restoration of approximately 60-300 μm, based on 80% of the active component.

The size of the crystallites Pd crystallite after recovery is about 2-15 nm calculated at 80% Pd-Krista is m BET) and the value of Pd crystallite (dPd) is the following:

R3=BET-O/dPd=0.1 to 10.

The magnitude of the Pd crystallite determined by the adsorption method WITH a similar method described in Journal of Catalysis 25, 148-160 (1972).

As the carrier used is preferably aluminum oxide, in particular-aluminum oxide. It is usually not in pure form, but may include other modifications of aluminum oxide, such as-aluminum oxide. However, it can also be applied to the titanium oxide, zirconium oxide, silicon dioxide, silicon carbide or talc.

BET-surface of the carrier is approximately 1-300 m2/g, preferably about 10-300 m2/g, in particular approximately 30-80 m2/g BET surface is determined by the method of single point nitrogen adsorption according to DIN 66132.

Approximately 40% of the specific surface (BET surface) are in pores with a diameter of approximately 1570-80 nm and approximately 60% is in pores with a diameter of approximately 80-14 nm. Pore volume and distribution of specific surfaces on certain values then determined in accordance with DIN 66133 (Nd-porosimetry).

Used as a carrier having a three is in a three-molded product is designated as (l). The diameter of one petal is marked as dl, and the diameter of the hole in one petal is designated as d2.

Preferably the diameter (d) having the form of a three-section of the molded product is equal to approximately 3-10 mm, length (l) of approximately 3-15 mm and the diameter of the hole in one petal (d2) about 0.5-5 mm

The catalysts of this invention preferably also contain small amounts of alkali and/or alkaline earth metals, in particular about 0.01 to 0.1 wt.% (calculated for oxides).

In contrast to the well-known catalysts, the catalysts of this invention have a high activity and selectivity. In addition, there may be used a higher flow rate of approximately 12000-15000 (parts by volume reactive substances in the gaseous state at a volume fraction of catalyst per hour=GHSV), in comparison with a bulk velocity of only about 3000-8000 when applying granules, solid tablets or extrudates. In addition, the catalysts of this invention exhibit lower pressure loss (up to 60% with respect to the particles of the medium in the form of granules or in the form of tablets (115 or 100%)).

The purpose of this invention is also a method of obtaining a certain H2PdCl4or gNO3), and these salts restore using a reducing agent (for example, Na-formate, NaBH4, hydrazine, formaldehyde, ascorbic acid, citric acid, Na-acetate, oxalic acid and so on), namely preferably in an alkaline medium at temperatures between approximately 20 and 100°C, preferably in the range of from 40 to 60°C.

Preferably, the recovery is carried out in an aqueous-alkaline solution. In this embodiment, the method of Pd and, if necessary, Ad-oxide fixed on the surface of the carrier and there reduced to the corresponding metals. In this way the penetrating ability of the metals can be reduced to approximately 60-300 microns.

Alternatively, the restoration of the reducing agent can be carried out in a nonaqueous solvent, if the reducing agent is decomposed by water. This is especially true for NaBH4and other hydrides or double hydrides, such as LiAlH4, LiBH4, CaH2or L3.

The impregnated carrier is usually washed, dried and calicivirus. In that case, if the recovery is incomplete and Pd and Ad are still partly in the form of their oxides, their is reactivated by heating in a hydrogen-containing atmosphere until the line is restorable connections first imposed only hydrogen.

Molded products are usually obtained through the fact that the material of the carrier is mixed with water, a binder vesectomy (such as carboxymethylcellulose) and/or lubricant (which imparts lubricity agent (for example, an alkali earth metal stearate or aluminum stearate).

Obtaining molded products are produced in a tablet press with a rotating plate, the perimeter of which is placed a few holes with a three section. In these openings (matrix) is filled with the mixture and held from below by stamp, by means of which during rotation of the rotating plate three pins, which are places of manufactured holes, move up. Upon further rotation of the rotating plate comes stamped with a three-form cross-section, which is provided with holes in which are pins in the lower die when the upper pressure stamp. Extruded molded product upon further rotation of the rotating plate after pulling the bottom of the stamp, and further movement of the upper stamp is removed from the matrix. “Fresh” molded product is dried and calicivirus. In a molded product having pores of a desired size.

Then moulded products probity solution to palladium and silver was deposited in the form of their respective oxides. Then to the solution was added a solution of reducing agent, which reduces the oxide to the corresponding metal. But you can also apply an alkaline solution of a reducing agent.

After deposition of oxides or metals, catalytically active component (components) molded product is washed to remove soluble salts (such as NaCl and NaNO3). Then the molded product is dried and calicivirus, then still present oxides catalytically effective component (components) is reduced to the corresponding metals. Recovery usually occurs in an atmosphere of hydrogen at temperatures of from about 20 to about 450°C. Recovery can also occur in the reactor, with the introduction before the introduction of the subject to hydrogenation of compounds of hydrogen or hydrogen-containing gas.

The purpose of this invention is, finally, the application of the above catalysts for hydrogenation of unsaturated hydrocarbons, in particular for selective hydrogenation of diolefins to monoolefins or acetylenes to olefins.

Example 1

1000 wt.h. boehmite is mixed with 10 wt.h. water and 40 wt.h. steer latochnovo press, cross-sections which correspond to the form presented (d=6 mm, d1=4 mm, d2=1.5 mm, l=6 mm). Then, as described above, the press-molded product and the push of a tablet press. The obtained molded product is dried for two hours at 120°C and calicivirus 4.5 hours at 1075°C, and the boehmite in the most part transformed into-aluminium oxide (along with this, in a small part in-aluminum oxide). The geometric surface is 1.3 cm2one molded product. Then determine the BET surface according to DIN 66132 up to 30 m2/m is Then determined in accordance with DIN 66133 pore volume to 0.35 ml/g, and pore distribution. 40% BET-surface (specific surface of the solid body) is in pores with a diameter 1750-80 nm, 60% of the BET surface accounted for by pores with a diameter of 80-14 nm.

To 1000 wt.h. molded quickly add a solution of H2PdCl4(0,345 wt.h. Pd) in 1150 wt.h. distilled water and slowly stirred for 5 minutes. Mixture is allowed to stand at rest for approximately 60 minutes and then allowed to drain colored solution.

The wet product is immediately mixed with warm (40°C) 5% solution of sodium formiate and leave to stand for 2.5 Casale this product calicivirus at 540°C for two hours.

1000 wt.h. calcined product are added to a solution of 3.13 wt.h. The gNO3in 1150 wt.h. distilled water and slowly stirred for 5 minutes. Mixture is allowed to stand for two hours and then allowed to drain the solution. Product calicivirus 2.5 hours at 540°C.

Thus obtained molded product was placed in a tubular reactor, which is first washed with nitrogen. Then miss hydrogen for 8 hours at a temperature of 400°C, allowing palladium and silver on the molded product is fully restored. Then passed through the reactor a mixture of 1,1 vol.% acetylene and 1.5 vol.% hydrogen in ethylene at a temperature of 50°C, a pressure of 2.5 MPa and a flow rate of 14,000 litres of mixture per kg of catalyst per hour. Acetylene is converted to ethylene by 84% with a selectivity of 93%.

Comparative example 1

The catalyst in the form of granules on the media from-Al2About3with a diameter of 2-4 mm, geometric surface 0.3 cm2, a specific surface area of solids (BET surface) 30 m2/g, pore volume of 0.39 ml/g and the distribution of volumes of pores of 40% between 1750 and 80 nm and 60% between 80 and 14 nm impregnated with a solution of N2PdCl4/gNO3example 1 and in the same manner as in example 1, the efficient hydrogenation of acetylene into ethylene, when applied to the same conditions of carrying out of the way. When flow rate 8000 (liters reactant per liter of catalyst per hour) acetylene was converted to 57% with a selectivity of 65% ethylene.

Comparative example 2

The mode of operation of the comparative example 1 was repeated with the deviation that the catalyst used in the form of tablets 4×4 mm, and all other conditions remained unchanged. Acetylene was converted to 48% with a selectivity of 76% in ethylene.

The catalysts according to example 1 and comparative examples 1 and 2 was measured in a separate tube to determine the pressure loss (with nitrogen as the gas to be measured), it was obtained the following correlation for pressure drop: example 1 - 60%; comparative example 1 is 115%; comparative example 2 is 100%.

Example 2

The mode of operation of example 1 was repeated with the deviation that the media was caliciviral for 4.5 hours at 1020°C, and the thus treated carrier was coated with 0.3 wt.% palladium. The catalyst had a BET surface 70±5 cm2/g, pore volume of 0.4 ml/g with 4,71% of the surface area in pores with a diameter 1750-80 nm and 76% in pores with a diameter of 80-14 nm. The rest of the surface was accounted for by pores with a diameter of <14 nm.

The catalyst is molded product fo rasego Dien gasoline pyrolysis (2 mol H21 mol of diene) at 30°C and then at 60°C, a pressure of 3.0 MPa and a flow rate of 8 parts by volume of liquid pyrolysis gasoline on a volumetric portion of catalyst per hour (LHSV). The composition of gasoline pyrolysis before selective hydrogenation are shown in table I.

The conversion of styrene and diene, as well as the selectivity in respect of the diene after selective hydrogenation are shown in table II.

Comparative example 2

The mode of operation of example 2 was repeated with the difference that the catalyst in the form of granules with a diameter of 2-4 mm, coated palladium and 0.3%, with a geometric surface of 0.3 cm2BETH surface 70±5 cm2/g, pore volume of 0.5 ml/g and the distribution of volumes since the catalyst of example 2 were loaded with fuel for the pyrolysis are shown in table I when the temperature first 30°C and later 60°C, a pressure of 3.0 MPa and LSHV 4. The conversion of styrene and diene, as well as the selectivity in respect of the diene after selective hydrogenation are shown in table III.

Example 3

In accordance with the mode of operation of example 1 of European patent EP-0314024-A1 commercial Dios.% isopropylacetate within 45 minutes. After a few hours of drying at 110°With the weight of Tio3crushed, mixed with aluminum stearate as agent tableting and pressed as described in example 1, a molded product (press articles) with a three-form cross-section (parameters as in example 1).

Tio2-molded product was caliciviral 3 hours at 550°C in okikawa atmosphere.

The geometric surface of the carrier was 1.3 cm2on the moldings, BET surface 36 m2/g, pore volume of 0.39 ml/g, 3.7% of the BET surface was accounted for by pores with a diameter 1750-80 nm, 95,8% for pores with a diameter of 80-14 nm.

TiO2the carrier was impregnated by spraying with 8% aqueous solution of sodium formate (per 100 g of the carrier 30 ml formate). Then the preprocessed so the carrier was impregnated by spraying an equal volume of a 2.5% aqueous solution of PdCl2. For full recovery of noble metals on a carrier-molded product was layered solution formate, was aspirated and washed to remove chloride. After drying at 100°With was caliciviral 6 hours to a final temperature of 400°C. After this was taken promotion silver. For this purpose, containing palladium TiO2-molded product is impregnated is URS 360°C. The palladium content was of 0.21 wt.%, the silver content of 0.12 wt.%.

The catalyst was used at a pressure of 0.15 MPa, a temperature of 120°C and 15 LHSV h-1with the molar ratio of N2/Dien 2:1 for selective hydrogenation of liquid diesterase mixture with the composition:

is 85.7 mol.% paraffins;

- 11,1 mol.% monoolefins;

- 0,85 mol.% dienes;

- 2,40 mol.% aromatic compounds.

The conversion of dienes was 80% with a selectivity of 85%.

Comparative example 3

The mode of operation of example 3 was repeated with the difference that instead of having the form of a three-section of the molded product was used massive tablet with dimensions of 4.5×4.5 mm, which in the same manner as in example 3 was applied catalytically effective metal. The media had a BET-surface 33 m2/g and a pore volume of 0.2 ml/year 51% of the BET surface was accounted for by pores with a diameter 1750-80 nm, 87.3 per cent was accounted for by pores with a diameter of 80-14 nm. This catalyst contained 0,213 wt.% Pd and 0.27 wt.% Hell.

The catalyst used for selective hydrogenation used in example 3 diesterase mixture (LHSV=10 h-1T=120°C, pressure=0.15 MPa, a molar ratio of N2:Dien=4:1).

The conversion of the diene was 70% with a selectivity of 60%.

pd) is the following:

R3=BET-O/dpd=0.1 to 10.

2. The catalyst p. 1, characterized in that it further comprises a media Hell.

3. Catalyst under item 1 or 2, characterized in that the ratio between the length (1) and diameter (d) having the form of a three-section of the molded product, is as follows:

R1=1/d=2-4.

4. The catalyst according to any one of paragraphs.1-3, characterized in that the geometrical surface (GO) is about 0.2-3 cm2preferably approximately 0.7-1.2 cm2in particular ~ 0.9-1.5 cm2on the moldings.

5. The catalyst according to one of paragraphs.1-4, characterized in that the ratio between the geometric surface of the molded product and the volume of the solid part of the molded product Vfequal to

R2=GO/Vf=0,5-20 mm-1in particular 1.4 to 4 mm-1.

6. The catalyst according to one of paragraphs.1-5, characterized in that the Pd is present in amounts of priblizenie between Pd and Ad is approximately 0.1 to 5.0.

7. The catalyst according to one of paragraphs.1-6, characterized in that the size of crystallites Pd crystallite after recovery is about 2-15 nm calculated at 80% Pd-crystallite.

8. The catalyst according to one of paragraphs.1-7, characterized in that the carrier is an alumina, in particular-aluminum oxide.

9. The catalyst according to one of paragraphs.1-8, characterized in that the specific surface area of the carrier is approximately 1-300 m2/g, preferably 10-300 m2/g, in particular 30-80 m2/year

10. The catalyst according to one of paragraphs.1-9, characterized in that approximately 40% of the specific surface area is in pores with a diameter of approximately 1750-80 nm and approximately 60% is in pores with a diameter of approximately 80-14 nm.

11. The catalyst according to one of paragraphs.1-10, characterized in that the diameter d having the form of a three-section of the molded product is approximately 3-10 mm, length 1 of approximately 3-15 mm and the diameter of the hole in one petal d2approximately 0.5-5 mm

12. The catalyst according to one of paragraphs.1-11, characterized in that the catalyst also contains small amounts of alkali and/or alkaline earth metals, in particular of priblem, the media is impregnated with a solution of Pd salts, these salts restore using a reducing agent, and then soaked in this way, the carrier is washed, dried and calicivirus.

14. The method according to p. 13, characterized in that it further carrier is impregnated with a solution of salts of Hell.

15. The method according to p. 13 or 14, characterized in that in the case of incomplete recovery still available oxides of Pd and Ad restore in a hydrogen-containing atmosphere to the corresponding metals.

16. The method according to PP.13-15, characterized in that the recovery is carried out in an alkaline medium at temperatures of about 20 to 100°C, preferably in the range of approximately 40 to 80°C.

17. The method according to any of paragraphs.13-16, characterized in that the recovery is carried out in an aqueous-alkaline solution.

18. The catalyst according to one of paragraphs.1-12, characterized in that it is designed for selective hydrogenation of diolefins to monoolefins or acetylenes to olefins.



 

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