CA1142506A - Hydrogenation catalyst - Google Patents
Hydrogenation catalystInfo
- Publication number
- CA1142506A CA1142506A CA000334271A CA334271A CA1142506A CA 1142506 A CA1142506 A CA 1142506A CA 000334271 A CA000334271 A CA 000334271A CA 334271 A CA334271 A CA 334271A CA 1142506 A CA1142506 A CA 1142506A
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- Canada
- Prior art keywords
- noble metal
- catalyst
- inorganic base
- aqueous solution
- support
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention relates to a novel noble metal supported catalyst and its preparation an use for the hydrogenation of unsaturated hydrocarbons. The catalyst is obtainable by impregnating an aluminium oxide support material having an internal surface area (BET) of less than 80 m2/g to saturation with an aqueous solution containing an inorganic base, drying the material in a stream of warm air an impregnating it in a manner which is in itself known with a noble metal salt solution, 0.1 to 50 gram equivalents of organic base being employed per gram equivalent of noble metal. The catalysts of this invention show both high activity and high selectivity, coupled with a relatively low cost as a result of the smaller amounts of valuable noble metal used.
The present invention relates to a novel noble metal supported catalyst and its preparation an use for the hydrogenation of unsaturated hydrocarbons. The catalyst is obtainable by impregnating an aluminium oxide support material having an internal surface area (BET) of less than 80 m2/g to saturation with an aqueous solution containing an inorganic base, drying the material in a stream of warm air an impregnating it in a manner which is in itself known with a noble metal salt solution, 0.1 to 50 gram equivalents of organic base being employed per gram equivalent of noble metal. The catalysts of this invention show both high activity and high selectivity, coupled with a relatively low cost as a result of the smaller amounts of valuable noble metal used.
Description
S(~6 .
~ he present invention relates to a novel, highly active noble metal supported catalyst and its preparation and use for the hydrogenation of hydrocarbons.
The petrochemical base products ethylene, propylene, butadiene, isoprene, benzene, toluene and many others are nowadays obtained world-wide by thermal or catalytic crack-ing of natural gases or petroleum fractions. The cracking processes, however, produce, in addition to the desired hydrocarbons, more or less large amounts of more highly unsaturated hydrocarbons, so that purification steps -usually of a hydrogenating type - generally have to be employed These hydrogenating purification processes for unsaturated hydrocarbons are therefore of great economic sigrlficance throughout the petrochemical industry and the processes are chosen on the one hand according to select-ivity, activity, price and the life of the catalysts used and, on the other hand, according to the expenditure on investment costs, on personnel and auxiliary energy sources for operation of the processes. Hydrogenation pro-cesses for unsaturated hydrocarbons operate in the gasphase or the liquid phase, the gas phase essentially being restricted to the low-boiling C2- and C3-hydrocarbons, since ir, the case of the higher-boiling hydrocarbons temperatures which are high and unfavourable for the reac-tion have to be employed to keep these substances in thegas phase.
For this type of hydrogenation of unsaturated con-stituents in hydrocarbon fractions, nickel, cobalt or tungsten catalysts or corresponding mixed catalysts on inert supports are used. Furthermore, because of their high selectivity a~d because of the advantageous tempera-ture and pressure conditions which they make possible, noble metal catalysts of group VIII of the periodic table, cuch as are described in Chemical Engineering Progress, ~me69, No. 5 (1973) pages 65-~8, are particularly advan-tageously employed ~atalysts used are, for example, according to German Patent Specification 1,518,827, Le A 17 320 tl~A,50~i palladium-on-lithium aluminium spinel with internal surface areas of up to 100 m2/g or also, according to U.S. Patent Specification 3,842,137, palladium on aluminium oxide supports with a surface area of about 90 m2/g. DT-OS
(German Published Specification) 2,059,978 describes how a palladium catalyst for the hydrogenation of hydrocarbons is obtained by steam and high temperature pretreatment of an alumina support with a surface area of more than 120 m2/g and subsequent impregnation of the support with a salt of the noble metal An improvement in the characteristics of noble ~.etal catalysts of this type can also be achieved by the addition of promoters. Thus, according to DT-OS
(German Published Specification) 2,546,513 rare earths are mixed into a catalyst in which palladium is used as the active material and alumina/SiO2 with an internal surface area of more than 200 m2/g is used as the support. DT-OS (~erman Published Specification) 3,947,510 describes a process according to which a diolefineis hydrogenated to an olefineon a palladium supported catalyst with the addition of an aqueous solution of a zinc salt to the diolefineto be hydrogenated.
A highly active hydrogenation catalyst which con-tains a noble metal of group VIII of the periodic table on aluminium o~ide as the support has now been found, which is obtainable by impregnating an aluminium oxide support material with an internal surface area (BET) of less than 80 m2/g,in accordance with its absorbency, to saturation with an aqueous solution containing an inorganic base, drying the material in a stream of warm air to a residual moisture content of less than 2~ by weight and impregnating it in a manner which is in itself known with a noble metal salt solution, 0.1 - 50 gram equivalents of inorganic base being employed per gram equivalent of noble metal for impregnation, and subjecting the catalyst thus obtained to ~5 optional reduction, washing with water and drying.
In general, the support used to prepare the cata-lysts according to the invention is an aluminium oxide with a BET surface area of less than ~0 m2/g, preferably less than 20 m2/g and very particularly preferentially less than Le A 17 320 114250~
,,, 10 m2/g. ~upport materials of this type in general have an absorbency of 20 - 60 ml of water per 100 g of support.
They are usually in the form of spheres, extrudates or tablets with a diameter of 2 - 8 mm.
Inorganic bases which can be used are, in general, sodium hydroxide, potassium hydroxide and lithium hydroxide, as well as the corresponding carbonates and bicarbonates.
The apprGpriate procedure for the pretreatment of the aluminium oxide support with an aqueous solution of an inorganic base is first to determine the absorbency of the support for water and then to carry out the impregnation with the amount of base solution which corresponds to the maximum absorbency, so that saturation is just achieved.
This method has the advantage that the amount to be applied can be accurately determined. The concentr~tion of the base solution is appropriately determined by the amount of inorganic base to be applied and this, in turn, is calcul-ated from the amount of noble metal to be applied, 0.1 - 50 and preferably 0.1 - 20 gram equivalents of base being employed per gram equivalent of noble metal. Very preferentially, the ratio of 0.1 - 5 gram equivalents of base per gram equivalent of noble metal is chosen.
Drying of the support in a stream of warm air is effected by conventional meth~ods in fixed beds through ~5 which the stream of warm air is passed. Drying to a residual moisture content of less than 2% by weight is carried out to constant weight and is an essential step in obtaining the hydrogenation catalyst according to the invention. The stream of warm air is appropriately at a temperature of 80-150C. In general, residual moist-ure contents of less than 2% by weight and preferentially of less than 1% by weight are obtained. These absolute residual moisture contents correspond to values of less than 10~, preferably less than 4% and particularly preferentially ~5 less than 1% of the absorbency of the support.
Noble metals which can be used for the process according to the invention are the corresponding elements of group VIII of the periodic table, for example palladium, platinum, rhodium and iridium. Palladium and platinum Le A 17 320 S~
are preferably used as the catalytically active constituent.
Palladium is very particularly suitable. The noble metal is applied in the form of a solution of a commercially available salt to the pretreated support.
Advantageously, the method used to apply the noble metal salt is that already described, according to which the amount of liquid containing the noble metal in the form of a commercially available salt is so measured that it corres-ponds to the absorbency of the base-treated support to saturation. Other methods of application, such as spray-coating or covering with a layer of the noble metal salt solution are also possible. The concentration of the metal salt solution is so adjusted that the finished catalyst contains up to 10 g and preferably up to 5 g of noble metal per litre of support.
The noble metal used is preferably palladium, in general in the form of the salt Na2[PdC14], or also in the form of another salt. In general, the impregnation by the noble metal has taken place after a waiting period of about 30 minutes and the catalyst can then, depending on the intended use form, be employed direct or reduced accord-ing to known methods with hydrazine, formaldehyde or hydrogen, washed with water and dried.
The catalysts according to the invention are suit-able for the hydrogenation of unsaturated constituents inmixtures of hydrocarbons o~ all types. The invention accordingly also relates to the use of the new catalysts for the hydrogenation of unsaturated hydrocarbons contain-ing from 3 to 10 carbon atoms. Preferably, they are used for the hydrogenation of acetylenes, diolefines and olefines in hydrocarbons of the C3- to C10-boiling range or in mixtures of hydrocarbons containing 3 to 10 carbon atoms.
They are suitable ~or hydrogenation reactions in the liquid or trickle phase. Due to the low noble metal content and also due to the simple mode of preparation, which necessitates neither expensive treatment of the support nor doping with promoters which are expensive or difficult to apply, particularly inexpensive catalysts are provided.
Coupled with this, the activity and selectivity of the Le A 17 320 sa-~
catalysts according to the invention are exceptionally high, so that high product throughputs with low catalyst and reactor volumes are achieved. In industrial opera-tion, the activity of the catalysts prepared according to the invention remains virtually constant over an operating period of several thousand hours. If necessary, after an extremely long period in operation, the activity can be restored by simply heating in air to 500C, in a manner which is in itself known, so that the catalyst is again usable The high degree of flexibility of the catalysts according to the invention in use is to be singled out:
not only can unsaturated hydrocarbons with 3 - 10 carbon atoms be hydrogenated but it is also possible selectively to hydrogenate acetylenic impurities in the indicated C3-to C10-boiling range without changing the diolefinic and olefinic hydrocarbons, for example to hydrogenate methyl-acetylene and propadiene to propylene. Furthermore, acetylenic and diolefinic hydrocarbons can also be hydro-genated selectively without hydrogenation of the olefinic constituents taking place. For example, vinylacetylene, ethylacetylene and 1,3-butadiene, as the unsaturated con-stituents of, for example, a C4 fraction obtained from the thermal cracking of naphtha or light benzine, can be so hydrogenated that vinylacetylene and ethylacetylene are converted quantitatively to n- and i-butane and the 1,3-butadiene is converted virtually completely selectively to n- and i-butene. If necessary, it is also possible to hydrogenate all of the acetylenic, diolefinic and olefinic components to the corresponding paraffins.
A further advantage, which is not to be under-estimated, of the catalysts according to the invention is the very small amounts in which they form higher-boiling by-products, which, in the case of similar hydrogenation processes, are known to those skilled in the art by the term "Green Oil1' and, because of the large amounts in which they are formed, frequently necessitate a so-called oil wash of the hydrogenated product in these processes.
Thus, the formation of Green Oil not only lowers the yield of the desired productsbut also makes the process involved Le A 17 320 and expensive.
The examples which follow are intended to illustrate the catalyst according to the invention and its use in more detail.
Example 1 a) Preparation of the catalvst:
One litre of an aluminium oxide support, consisting of 3 mm e~trudates with a BET surface area of 4 m2/g, an absorbency of 28 ml of H20 per 100 g of support and a bulk density of 1,161 g/l, was impregnated with 325 ml of an aqueous NaOH solution which contained 1.2 g, corresponding to 0.03 gram equivalent, of NaOH. The solution was com-pletely absorbed by the support within 2 minutes. The moist support was poured into a vertical glass tube with a capacity of about 2 1 and then treated from bottom to top with warm air at 105 to 120C at a rate of 20 m3/hour.
Drying of the support was carried out to constant weight, which was the case after 30 minutes. After cooling to room temperature, the residual moisture content of the dried support was 0.11% by weight, corresponding to about 0.39%
of the absorbency.
The pretreated, dry support was impregnated, in accordance with its absorbency, with an aqueous solution of sodium tetrachloropalladate containing 2 g of Pd, corresponding to 0.037 gram equivalent, and left to stand for 15 minutes. In order to reduce the palladium, the support was covered, in a glass beaker, with 400 ml of a 10% aqueous solution of hydrazine hydrate. The cata-lyst was then washed in a running stream of distilled water until no further sodium and chloride ions and no further hydrazine were detectable in the wash water; this was the case after 10 hours. Subsequent drying was carried out in a stream of warm air, as described above for drying of the support. The catalyst prepared in this way contained 2 g of Pd per litre of support (~
0.172~ by weight).
b) Use:
The catalyst was employed for the selective hydro-genation of acetylenic impurities in a stream of propylene Le A 17 320 S(~6 having the composition indicated in column 1 of Table I, such as is obtainable from naphtha or light benzine thermal cracking plants.
For this purpose, 600 ml of the catalyst prepared according to the above instructions were filled into a vertical steel tube with a length of 180 cm and an internal diameter of 2.5 cm. The tube had a cooling jacket, which was charged with cooling water at 20C. There was free outflow from the bottom of the tube into a separator. Two connection pieces were fitted at the upper end of the tube, for metering the stream of propylene and the hydrogen for hydrogenation. 12 kg of the liquid stream of propylene per hour were metered in continuously via one connection piece, hydrogen, from a steel cylinder, was added via the second connection piece and a pressure such that the hydrogenated product was obtained free from acetylenic compounds was maintained in the reaction tube and the separator. The hydro-genated product was collected in the lower separator and continuously removed therefrom via a let-down valve,so that a constant liquid level was always maintained in the vessel. Samples were taken at regular intervals and these were examined by gas chromatography to determine their composition. After 1,000 hours in operation, the reactor pressure which was necessary for complete removal of the acetylenic impurities and which was adjusted by means of the amount of hydrogen fed in was 12 bars absolute.
The composition of the hydrogenated product after 1,000 hours in operation is indicated in column 2 of Table I. It can be seen that the acetylenic impurities methylacetylene and propadiene are hydrogenated to propylene with high selectivity and that only 0.15% by weight of dimers are formed.
Le A 17 320 S(~
Table I
Components in ~
by weight 1 2 3 propane 3.3 4.1 4.3 propylene 93.5 95.75 95.21 methylacetylene 1.8 0.003 O. 003 propadiene 1. 4 0.003 0.00 dimers - O.15 0.45 polymers - _ o.o4 Exam~le 2 (for comparison) a) Preparation of the catalYst An aluminium oxide support with a BET surface area of 350 m2/g, a bulk density of 827 g~l and an absorbency of 44.2 ml of H20/100 g of support was used. A catalyst 15 was prepared from this support following the instructions of Example 1 precisely. In contrast to Example 1, one litre of the abovementioned support was impregnated with 365 ml of an aqueous NaOH solution which contained 1. 2 g, correspond-ing to 0.03 gram equivalent, of NaOH, corresponding to the change in the absorbency. The support impregnated in this way and dried according to Example 1 was impregnated, corresponding to its absorbency, with an aqueous solution of sodium tetrachloropalladate containing 2 g, corresponding to O .037 g equivalent, of Pd and further processed in 25 accordance with Example 1. The finished support con-tained, as described in Example 1, 2 g of Pd per litre of support ( ~v 0.24% by weight).
b) Use -The catalyst was employed in the same~apparatus and 30 with the same stream of propylene as in Example 1 for the hydrogenation of acetylenic impurities. In this case, after 1,000 hours in operation the pressure required for complete hydrogenation was 13 bars. The composition of the hydrogenation product after this period in operation is 35 indicated in column 3 of Table I. It can be seen that the activity and selectivity of the catalyst are similar to those of the catalyst described in Example 1. However, the formation of dimers, in an amount of 0. 45% by weight, is three times as high as in Example 1 and, additionally, Le A 17 320 ll~ZS(~6 polymers are formed in an amount of 0.04% by weight.
Example 3 The catalyst of Example 1 was employed in the same apparatus as in Example 1 for the hydrogenation of a buta-diene-rich C4 fraction,such as is obtained from the thermal crac~ing of naphtha or light benzine. The composition of this fraction is indicated in column 1 of Table II.
The object of the hydrogenation was selectively to hydrogen-ate the butadiene in this stream to n-butene. For this purpose, 4 kg/hour of the liquid C4 fraction having the composition indicated in column 1 of Table II were metered into the hydrogenation apparatus described in Example 1.
In order to dilute the feed product, 8 kg/hour of the hydro-genated product from the seParator were fed as a recycle stream, together with the C4 fraction, to the top of the reaction tube. The pressure of the reaction system was again adjusted, via the amount of hydrogen metered in, so that it was sufficiently high to achieve complete removal of butadiene. After 1,000 hours in operation, the pres-sure required for this was 15 bars absolute. The compo-sition thus achie~ed for the hydrogenated product can be seen from column 2 of Table II. The butadiene was hydrogenated to butene with high selectivity. Dimer formation was only 0.03% by weight.
25 Table II
Components in % 1 2 3 by weight n + i-butane 5.4 6.1 10.5 n + i-butene 49.24 93.77 89.37 1,3-butadiene 44.~ 0.1 0.1 vinylacetylene 0.87 ethylacetylene 0.19 dimers _ 0 03 0 03 Example 4 (for comparison) a) Preparation of the catalyst Using the aluminium oxide support from ~xample 1, with a BET surface area of 4 m2/g, a catalyst was prepared as follows without pretreatment of the support with a base:
1 1 of the support was impregnated with 325 ml of Le A 17 320 S~6 an aqueous solution of sodium tetrachloropalladate contain-ing ~ g of Pd. After a waiting period of 15 minutes, the catalyst was reduced with an aqueous solution of hydra-zine, washed with water and dried, as described in Example 1. The catalyst prepared in this way contained 6 g of palladium/l of support ( ~v 0.51% by weight).
b) Use The catalyst was employed in exactly the same manner as described in Example 3 for the hydrogenation of the C4 fractions indicated in that example.
After 1,000 hours in operation, the pressure had to be adjusted to 22 bars absolute in order to achieve removal of the butadiene, a hydrogenated product having the compo-sition according to column 3 of Table II being obtained.
It can be seen that this catalyst, which was pre-pared according to the prior art without pretreatment of the support with a base and which contains considerably more palladium than the catalyst described in Example 3 or Example 1 is discernibly less active and lessselective, which can be concluded, in particular, from the fact that the hydrogenation pressure required is considerably higher and that the over-hydrogenation of the butadiene to butane was considerably more extensive than in Example 3.
Exam~le 5 a) Preparation of the catalvst One litre of an aluminium oxide support consisting of spheres with a diameter of 2.4 - 4.0 mm and having a BET
surface area of 74 m2/g, an absorbency of 54 ml of H20 per 100 g of support and a bulk density of 717 g/l was impreg-nated with 387 ml of an aqueous NaOH solution which con-tained 6.0 g, corresponding to 0.15 gram equivalent, of NaOH. The solution was completely absorbed by the support within 2 minutes. The moist support was poured into a vertical glass tube with a capacity of about 2 1 and then treated from bottom to top with warm air at 105 -120C at a rate of 20 m3/hour. Drying of the support was carried out to constant weight and this was the case after 30 mi~utes. After cooling to room temperature, the residual moisture content of the dried support was Le A 1? 320 0.25~ by weight, corresponding to about 0.47~ of the absorbency.
Corresponding to its absorbency, the pretreated, dry support was impregnated with an aqueous solution of sodium tetrachloropalladate containing 5 g of Pd, corres-ponding to 0.094 gram equivalent, and left to stand for 15 minutes. The catalyst was then washed in a running stream of distilled water until no further sodium and chloride ions were detectable in the wash water; this was the case after 12 hours.
Subsequent drying was effected in a stream of warm air, as described above for drying of the support. The catalyst prepared in this way contained, calculated as the metal, 5 g of Pd per litre of support (~J O.691% by weight).
b) Use The catalyst was employed in the same apparatus as in Example 1 for the hydrogenation of pyrolysis benzine such as is obtained from the thermal cracking of naphtha or light benzine. The composition of this product is indicated in column 1 of Table III. The object of this hydrogenation was to lower the diene content of the pyrolysis benzine to such an extent that a hydrogenation product was obtained which was stable to ageing and which met the specifications for use as carburettor fuel. For this purpose, 3 kg/
hour of the pyrolysis benzine having the composition indi-cated in column 1 of Table III were me'ered into the hydrogenation apparatus described in Example 1. The pressure of the reaction system was adjusted to 28 bars via the amount of hydrogen metered in. The cooling ~ac~et of the reactor tube was charged with cooling water at 55C.
The hydrogenation product was continuously withdrawn from the lower separator.
The composition of the hydrogenation product after 1,000 hours in operation is indicated in column 2 of Table III. It can be seen that a virtually diene-free product which is stable to ageing was obtained and that no new formation of existent gum took place.
Le A 17 ~20 ~1 ~50$~
Table III
bromine number, g of Br/100 g 68 22 diene content, % by weight 17 0.5 5 existent gum, mg/100 ml 2 2 potential gum, mg/100 ml6,000 3 induction period,minutes<60 ~360 Le A 17 320
~ he present invention relates to a novel, highly active noble metal supported catalyst and its preparation and use for the hydrogenation of hydrocarbons.
The petrochemical base products ethylene, propylene, butadiene, isoprene, benzene, toluene and many others are nowadays obtained world-wide by thermal or catalytic crack-ing of natural gases or petroleum fractions. The cracking processes, however, produce, in addition to the desired hydrocarbons, more or less large amounts of more highly unsaturated hydrocarbons, so that purification steps -usually of a hydrogenating type - generally have to be employed These hydrogenating purification processes for unsaturated hydrocarbons are therefore of great economic sigrlficance throughout the petrochemical industry and the processes are chosen on the one hand according to select-ivity, activity, price and the life of the catalysts used and, on the other hand, according to the expenditure on investment costs, on personnel and auxiliary energy sources for operation of the processes. Hydrogenation pro-cesses for unsaturated hydrocarbons operate in the gasphase or the liquid phase, the gas phase essentially being restricted to the low-boiling C2- and C3-hydrocarbons, since ir, the case of the higher-boiling hydrocarbons temperatures which are high and unfavourable for the reac-tion have to be employed to keep these substances in thegas phase.
For this type of hydrogenation of unsaturated con-stituents in hydrocarbon fractions, nickel, cobalt or tungsten catalysts or corresponding mixed catalysts on inert supports are used. Furthermore, because of their high selectivity a~d because of the advantageous tempera-ture and pressure conditions which they make possible, noble metal catalysts of group VIII of the periodic table, cuch as are described in Chemical Engineering Progress, ~me69, No. 5 (1973) pages 65-~8, are particularly advan-tageously employed ~atalysts used are, for example, according to German Patent Specification 1,518,827, Le A 17 320 tl~A,50~i palladium-on-lithium aluminium spinel with internal surface areas of up to 100 m2/g or also, according to U.S. Patent Specification 3,842,137, palladium on aluminium oxide supports with a surface area of about 90 m2/g. DT-OS
(German Published Specification) 2,059,978 describes how a palladium catalyst for the hydrogenation of hydrocarbons is obtained by steam and high temperature pretreatment of an alumina support with a surface area of more than 120 m2/g and subsequent impregnation of the support with a salt of the noble metal An improvement in the characteristics of noble ~.etal catalysts of this type can also be achieved by the addition of promoters. Thus, according to DT-OS
(German Published Specification) 2,546,513 rare earths are mixed into a catalyst in which palladium is used as the active material and alumina/SiO2 with an internal surface area of more than 200 m2/g is used as the support. DT-OS (~erman Published Specification) 3,947,510 describes a process according to which a diolefineis hydrogenated to an olefineon a palladium supported catalyst with the addition of an aqueous solution of a zinc salt to the diolefineto be hydrogenated.
A highly active hydrogenation catalyst which con-tains a noble metal of group VIII of the periodic table on aluminium o~ide as the support has now been found, which is obtainable by impregnating an aluminium oxide support material with an internal surface area (BET) of less than 80 m2/g,in accordance with its absorbency, to saturation with an aqueous solution containing an inorganic base, drying the material in a stream of warm air to a residual moisture content of less than 2~ by weight and impregnating it in a manner which is in itself known with a noble metal salt solution, 0.1 - 50 gram equivalents of inorganic base being employed per gram equivalent of noble metal for impregnation, and subjecting the catalyst thus obtained to ~5 optional reduction, washing with water and drying.
In general, the support used to prepare the cata-lysts according to the invention is an aluminium oxide with a BET surface area of less than ~0 m2/g, preferably less than 20 m2/g and very particularly preferentially less than Le A 17 320 114250~
,,, 10 m2/g. ~upport materials of this type in general have an absorbency of 20 - 60 ml of water per 100 g of support.
They are usually in the form of spheres, extrudates or tablets with a diameter of 2 - 8 mm.
Inorganic bases which can be used are, in general, sodium hydroxide, potassium hydroxide and lithium hydroxide, as well as the corresponding carbonates and bicarbonates.
The apprGpriate procedure for the pretreatment of the aluminium oxide support with an aqueous solution of an inorganic base is first to determine the absorbency of the support for water and then to carry out the impregnation with the amount of base solution which corresponds to the maximum absorbency, so that saturation is just achieved.
This method has the advantage that the amount to be applied can be accurately determined. The concentr~tion of the base solution is appropriately determined by the amount of inorganic base to be applied and this, in turn, is calcul-ated from the amount of noble metal to be applied, 0.1 - 50 and preferably 0.1 - 20 gram equivalents of base being employed per gram equivalent of noble metal. Very preferentially, the ratio of 0.1 - 5 gram equivalents of base per gram equivalent of noble metal is chosen.
Drying of the support in a stream of warm air is effected by conventional meth~ods in fixed beds through ~5 which the stream of warm air is passed. Drying to a residual moisture content of less than 2% by weight is carried out to constant weight and is an essential step in obtaining the hydrogenation catalyst according to the invention. The stream of warm air is appropriately at a temperature of 80-150C. In general, residual moist-ure contents of less than 2% by weight and preferentially of less than 1% by weight are obtained. These absolute residual moisture contents correspond to values of less than 10~, preferably less than 4% and particularly preferentially ~5 less than 1% of the absorbency of the support.
Noble metals which can be used for the process according to the invention are the corresponding elements of group VIII of the periodic table, for example palladium, platinum, rhodium and iridium. Palladium and platinum Le A 17 320 S~
are preferably used as the catalytically active constituent.
Palladium is very particularly suitable. The noble metal is applied in the form of a solution of a commercially available salt to the pretreated support.
Advantageously, the method used to apply the noble metal salt is that already described, according to which the amount of liquid containing the noble metal in the form of a commercially available salt is so measured that it corres-ponds to the absorbency of the base-treated support to saturation. Other methods of application, such as spray-coating or covering with a layer of the noble metal salt solution are also possible. The concentration of the metal salt solution is so adjusted that the finished catalyst contains up to 10 g and preferably up to 5 g of noble metal per litre of support.
The noble metal used is preferably palladium, in general in the form of the salt Na2[PdC14], or also in the form of another salt. In general, the impregnation by the noble metal has taken place after a waiting period of about 30 minutes and the catalyst can then, depending on the intended use form, be employed direct or reduced accord-ing to known methods with hydrazine, formaldehyde or hydrogen, washed with water and dried.
The catalysts according to the invention are suit-able for the hydrogenation of unsaturated constituents inmixtures of hydrocarbons o~ all types. The invention accordingly also relates to the use of the new catalysts for the hydrogenation of unsaturated hydrocarbons contain-ing from 3 to 10 carbon atoms. Preferably, they are used for the hydrogenation of acetylenes, diolefines and olefines in hydrocarbons of the C3- to C10-boiling range or in mixtures of hydrocarbons containing 3 to 10 carbon atoms.
They are suitable ~or hydrogenation reactions in the liquid or trickle phase. Due to the low noble metal content and also due to the simple mode of preparation, which necessitates neither expensive treatment of the support nor doping with promoters which are expensive or difficult to apply, particularly inexpensive catalysts are provided.
Coupled with this, the activity and selectivity of the Le A 17 320 sa-~
catalysts according to the invention are exceptionally high, so that high product throughputs with low catalyst and reactor volumes are achieved. In industrial opera-tion, the activity of the catalysts prepared according to the invention remains virtually constant over an operating period of several thousand hours. If necessary, after an extremely long period in operation, the activity can be restored by simply heating in air to 500C, in a manner which is in itself known, so that the catalyst is again usable The high degree of flexibility of the catalysts according to the invention in use is to be singled out:
not only can unsaturated hydrocarbons with 3 - 10 carbon atoms be hydrogenated but it is also possible selectively to hydrogenate acetylenic impurities in the indicated C3-to C10-boiling range without changing the diolefinic and olefinic hydrocarbons, for example to hydrogenate methyl-acetylene and propadiene to propylene. Furthermore, acetylenic and diolefinic hydrocarbons can also be hydro-genated selectively without hydrogenation of the olefinic constituents taking place. For example, vinylacetylene, ethylacetylene and 1,3-butadiene, as the unsaturated con-stituents of, for example, a C4 fraction obtained from the thermal cracking of naphtha or light benzine, can be so hydrogenated that vinylacetylene and ethylacetylene are converted quantitatively to n- and i-butane and the 1,3-butadiene is converted virtually completely selectively to n- and i-butene. If necessary, it is also possible to hydrogenate all of the acetylenic, diolefinic and olefinic components to the corresponding paraffins.
A further advantage, which is not to be under-estimated, of the catalysts according to the invention is the very small amounts in which they form higher-boiling by-products, which, in the case of similar hydrogenation processes, are known to those skilled in the art by the term "Green Oil1' and, because of the large amounts in which they are formed, frequently necessitate a so-called oil wash of the hydrogenated product in these processes.
Thus, the formation of Green Oil not only lowers the yield of the desired productsbut also makes the process involved Le A 17 320 and expensive.
The examples which follow are intended to illustrate the catalyst according to the invention and its use in more detail.
Example 1 a) Preparation of the catalvst:
One litre of an aluminium oxide support, consisting of 3 mm e~trudates with a BET surface area of 4 m2/g, an absorbency of 28 ml of H20 per 100 g of support and a bulk density of 1,161 g/l, was impregnated with 325 ml of an aqueous NaOH solution which contained 1.2 g, corresponding to 0.03 gram equivalent, of NaOH. The solution was com-pletely absorbed by the support within 2 minutes. The moist support was poured into a vertical glass tube with a capacity of about 2 1 and then treated from bottom to top with warm air at 105 to 120C at a rate of 20 m3/hour.
Drying of the support was carried out to constant weight, which was the case after 30 minutes. After cooling to room temperature, the residual moisture content of the dried support was 0.11% by weight, corresponding to about 0.39%
of the absorbency.
The pretreated, dry support was impregnated, in accordance with its absorbency, with an aqueous solution of sodium tetrachloropalladate containing 2 g of Pd, corresponding to 0.037 gram equivalent, and left to stand for 15 minutes. In order to reduce the palladium, the support was covered, in a glass beaker, with 400 ml of a 10% aqueous solution of hydrazine hydrate. The cata-lyst was then washed in a running stream of distilled water until no further sodium and chloride ions and no further hydrazine were detectable in the wash water; this was the case after 10 hours. Subsequent drying was carried out in a stream of warm air, as described above for drying of the support. The catalyst prepared in this way contained 2 g of Pd per litre of support (~
0.172~ by weight).
b) Use:
The catalyst was employed for the selective hydro-genation of acetylenic impurities in a stream of propylene Le A 17 320 S(~6 having the composition indicated in column 1 of Table I, such as is obtainable from naphtha or light benzine thermal cracking plants.
For this purpose, 600 ml of the catalyst prepared according to the above instructions were filled into a vertical steel tube with a length of 180 cm and an internal diameter of 2.5 cm. The tube had a cooling jacket, which was charged with cooling water at 20C. There was free outflow from the bottom of the tube into a separator. Two connection pieces were fitted at the upper end of the tube, for metering the stream of propylene and the hydrogen for hydrogenation. 12 kg of the liquid stream of propylene per hour were metered in continuously via one connection piece, hydrogen, from a steel cylinder, was added via the second connection piece and a pressure such that the hydrogenated product was obtained free from acetylenic compounds was maintained in the reaction tube and the separator. The hydro-genated product was collected in the lower separator and continuously removed therefrom via a let-down valve,so that a constant liquid level was always maintained in the vessel. Samples were taken at regular intervals and these were examined by gas chromatography to determine their composition. After 1,000 hours in operation, the reactor pressure which was necessary for complete removal of the acetylenic impurities and which was adjusted by means of the amount of hydrogen fed in was 12 bars absolute.
The composition of the hydrogenated product after 1,000 hours in operation is indicated in column 2 of Table I. It can be seen that the acetylenic impurities methylacetylene and propadiene are hydrogenated to propylene with high selectivity and that only 0.15% by weight of dimers are formed.
Le A 17 320 S(~
Table I
Components in ~
by weight 1 2 3 propane 3.3 4.1 4.3 propylene 93.5 95.75 95.21 methylacetylene 1.8 0.003 O. 003 propadiene 1. 4 0.003 0.00 dimers - O.15 0.45 polymers - _ o.o4 Exam~le 2 (for comparison) a) Preparation of the catalYst An aluminium oxide support with a BET surface area of 350 m2/g, a bulk density of 827 g~l and an absorbency of 44.2 ml of H20/100 g of support was used. A catalyst 15 was prepared from this support following the instructions of Example 1 precisely. In contrast to Example 1, one litre of the abovementioned support was impregnated with 365 ml of an aqueous NaOH solution which contained 1. 2 g, correspond-ing to 0.03 gram equivalent, of NaOH, corresponding to the change in the absorbency. The support impregnated in this way and dried according to Example 1 was impregnated, corresponding to its absorbency, with an aqueous solution of sodium tetrachloropalladate containing 2 g, corresponding to O .037 g equivalent, of Pd and further processed in 25 accordance with Example 1. The finished support con-tained, as described in Example 1, 2 g of Pd per litre of support ( ~v 0.24% by weight).
b) Use -The catalyst was employed in the same~apparatus and 30 with the same stream of propylene as in Example 1 for the hydrogenation of acetylenic impurities. In this case, after 1,000 hours in operation the pressure required for complete hydrogenation was 13 bars. The composition of the hydrogenation product after this period in operation is 35 indicated in column 3 of Table I. It can be seen that the activity and selectivity of the catalyst are similar to those of the catalyst described in Example 1. However, the formation of dimers, in an amount of 0. 45% by weight, is three times as high as in Example 1 and, additionally, Le A 17 320 ll~ZS(~6 polymers are formed in an amount of 0.04% by weight.
Example 3 The catalyst of Example 1 was employed in the same apparatus as in Example 1 for the hydrogenation of a buta-diene-rich C4 fraction,such as is obtained from the thermal crac~ing of naphtha or light benzine. The composition of this fraction is indicated in column 1 of Table II.
The object of the hydrogenation was selectively to hydrogen-ate the butadiene in this stream to n-butene. For this purpose, 4 kg/hour of the liquid C4 fraction having the composition indicated in column 1 of Table II were metered into the hydrogenation apparatus described in Example 1.
In order to dilute the feed product, 8 kg/hour of the hydro-genated product from the seParator were fed as a recycle stream, together with the C4 fraction, to the top of the reaction tube. The pressure of the reaction system was again adjusted, via the amount of hydrogen metered in, so that it was sufficiently high to achieve complete removal of butadiene. After 1,000 hours in operation, the pres-sure required for this was 15 bars absolute. The compo-sition thus achie~ed for the hydrogenated product can be seen from column 2 of Table II. The butadiene was hydrogenated to butene with high selectivity. Dimer formation was only 0.03% by weight.
25 Table II
Components in % 1 2 3 by weight n + i-butane 5.4 6.1 10.5 n + i-butene 49.24 93.77 89.37 1,3-butadiene 44.~ 0.1 0.1 vinylacetylene 0.87 ethylacetylene 0.19 dimers _ 0 03 0 03 Example 4 (for comparison) a) Preparation of the catalyst Using the aluminium oxide support from ~xample 1, with a BET surface area of 4 m2/g, a catalyst was prepared as follows without pretreatment of the support with a base:
1 1 of the support was impregnated with 325 ml of Le A 17 320 S~6 an aqueous solution of sodium tetrachloropalladate contain-ing ~ g of Pd. After a waiting period of 15 minutes, the catalyst was reduced with an aqueous solution of hydra-zine, washed with water and dried, as described in Example 1. The catalyst prepared in this way contained 6 g of palladium/l of support ( ~v 0.51% by weight).
b) Use The catalyst was employed in exactly the same manner as described in Example 3 for the hydrogenation of the C4 fractions indicated in that example.
After 1,000 hours in operation, the pressure had to be adjusted to 22 bars absolute in order to achieve removal of the butadiene, a hydrogenated product having the compo-sition according to column 3 of Table II being obtained.
It can be seen that this catalyst, which was pre-pared according to the prior art without pretreatment of the support with a base and which contains considerably more palladium than the catalyst described in Example 3 or Example 1 is discernibly less active and lessselective, which can be concluded, in particular, from the fact that the hydrogenation pressure required is considerably higher and that the over-hydrogenation of the butadiene to butane was considerably more extensive than in Example 3.
Exam~le 5 a) Preparation of the catalvst One litre of an aluminium oxide support consisting of spheres with a diameter of 2.4 - 4.0 mm and having a BET
surface area of 74 m2/g, an absorbency of 54 ml of H20 per 100 g of support and a bulk density of 717 g/l was impreg-nated with 387 ml of an aqueous NaOH solution which con-tained 6.0 g, corresponding to 0.15 gram equivalent, of NaOH. The solution was completely absorbed by the support within 2 minutes. The moist support was poured into a vertical glass tube with a capacity of about 2 1 and then treated from bottom to top with warm air at 105 -120C at a rate of 20 m3/hour. Drying of the support was carried out to constant weight and this was the case after 30 mi~utes. After cooling to room temperature, the residual moisture content of the dried support was Le A 1? 320 0.25~ by weight, corresponding to about 0.47~ of the absorbency.
Corresponding to its absorbency, the pretreated, dry support was impregnated with an aqueous solution of sodium tetrachloropalladate containing 5 g of Pd, corres-ponding to 0.094 gram equivalent, and left to stand for 15 minutes. The catalyst was then washed in a running stream of distilled water until no further sodium and chloride ions were detectable in the wash water; this was the case after 12 hours.
Subsequent drying was effected in a stream of warm air, as described above for drying of the support. The catalyst prepared in this way contained, calculated as the metal, 5 g of Pd per litre of support (~J O.691% by weight).
b) Use The catalyst was employed in the same apparatus as in Example 1 for the hydrogenation of pyrolysis benzine such as is obtained from the thermal cracking of naphtha or light benzine. The composition of this product is indicated in column 1 of Table III. The object of this hydrogenation was to lower the diene content of the pyrolysis benzine to such an extent that a hydrogenation product was obtained which was stable to ageing and which met the specifications for use as carburettor fuel. For this purpose, 3 kg/
hour of the pyrolysis benzine having the composition indi-cated in column 1 of Table III were me'ered into the hydrogenation apparatus described in Example 1. The pressure of the reaction system was adjusted to 28 bars via the amount of hydrogen metered in. The cooling ~ac~et of the reactor tube was charged with cooling water at 55C.
The hydrogenation product was continuously withdrawn from the lower separator.
The composition of the hydrogenation product after 1,000 hours in operation is indicated in column 2 of Table III. It can be seen that a virtually diene-free product which is stable to ageing was obtained and that no new formation of existent gum took place.
Le A 17 ~20 ~1 ~50$~
Table III
bromine number, g of Br/100 g 68 22 diene content, % by weight 17 0.5 5 existent gum, mg/100 ml 2 2 potential gum, mg/100 ml6,000 3 induction period,minutes<60 ~360 Le A 17 320
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Hydrogenation catalyst containing a noble metal of group VIII of the periodic table on aluminium oxide as the support, obtained by impregnating an aluminium oxide support material with an internal surface area (BET) of less than 80 m2/g, in accordance with its absorbency, to saturation with an aqueous solution con-taining an inorganic base, drying the material in a stream of warm air to a residual moisture content of less than 2% by weight and impregnating it with a noble metal salt solution 0.1 - 50 gram equivalents of inorganic base being employed per gram equivalent of noble metal for impregnation, and subjecting the catalyst thus obtained to washing with water and drying.
2. A catalyst according to Claim 1, obtained by impregnating an aluminium oxide support material with an internal surface area (BET) of less than 80 m2/g, in accordance with its absorbency, to saturation with an aqueous solution containing an inorganic base, drying the material in a stream of warm air to a residual moisture content of less than 2% by weight and impregnating it with a noble metal salt solution, 0.1 - 50 gram equivalents of inorganic base being employed per gram equivalent of noble metal for impregnation, and subjecting the catalyst thus obtained to reduction, washing with water, and drying.
3. Process for the preparation of a catalyst containing a noble metal of group VIII of the periodic table on aluminium oxide as the support, wherein an aluminium oxide support material with an internal surface area (BET) of less than 80 m2/g is impregnated, in accordance with its absorbency, to saturation with an aqueous solution containing an inorganic base, dried in a stream of warm air to a residual moisture content of less than 2% by weight and impregnated with a noble metal solution, 0.1 - 50 gram equivalents of inorganic base being employed per gram equivalent of noble metal for impregnation, and in that the catalyst thus obtained is washed and dried.
4. A process according to Claim 3, wherein the process includes a reduction step applied after the impregnation of the support with the noble metal solution.
5. A process for the hydrogenation of unsaturated hydro-carbons containing 3 to 10 carbon atoms wherein a supported cata-lyst as defined in Claim 1 is used.
6. A process for the selective hydrogenation of acetylenes, olefins, and diolefines which are contained in hydrocarbons of the class having a C3 to C10 boiling range, or which are contained in mixtures of hydrocarbons having 3 to 10 carbon atoms, wherein a supported catalyst as defined in Claim 1 is used.
7. A catalyst according to Claim 1 wherein the noble metal of Group VIII of the periodic table is palladium.
8. A catalyst according to Claim 1 wherein the aqueous solution of an inorganic base is an aqueous solution of sodium hydroxide.
9. A process according to Claim 3 wherein the noble metal of Group VIII of the periodic table is palladium.
10. A process according to claim 3 wherein the aqueous solution of an inorganic base is an aqueous solution of sodium hydroxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19782849026 DE2849026A1 (en) | 1978-11-11 | 1978-11-11 | HYDRATION CATALYST |
| DEP2849026.8 | 1978-11-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1142506A true CA1142506A (en) | 1983-03-08 |
Family
ID=6054443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000334271A Expired CA1142506A (en) | 1978-11-11 | 1979-08-22 | Hydrogenation catalyst |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0013286B1 (en) |
| JP (1) | JPS5564840A (en) |
| AT (1) | ATE343T1 (en) |
| CA (1) | CA1142506A (en) |
| DE (2) | DE2849026A1 (en) |
| ES (1) | ES483530A1 (en) |
| ZA (1) | ZA794456B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3312252A1 (en) * | 1983-04-05 | 1984-10-11 | EC Erdölchemie GmbH, 5000 Köln | HYDRATION CATALYST, METHOD FOR PRODUCING IT AND ITS USE |
| JPS62197153A (en) * | 1986-02-25 | 1987-08-31 | Nippon Oil Co Ltd | Preparation of heavy oil hydrogenating catalyst |
| DE3538129A1 (en) * | 1985-10-26 | 1987-04-30 | Bayer Ag | CARRIER CATALYSTS AND HYDRATION METHOD USING THESE CARRIER CATALYSTS |
| CN1097480C (en) * | 1999-06-25 | 2003-01-01 | 中国石油化工集团公司 | Catalyst for selective hydrogenation of acetylene hydrocarbon |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1283737A (en) * | 1968-09-04 | 1972-08-02 | Nat Distillers Chem Corp | Method of catalyst preparation |
| DE2025411A1 (en) * | 1970-05-25 | 1971-12-09 |
-
1978
- 1978-11-11 DE DE19782849026 patent/DE2849026A1/en not_active Withdrawn
-
1979
- 1979-08-13 DE DE7979102929T patent/DE2961252D1/en not_active Expired
- 1979-08-13 AT AT79102929T patent/ATE343T1/en not_active IP Right Cessation
- 1979-08-13 EP EP79102929A patent/EP0013286B1/en not_active Expired
- 1979-08-21 ES ES483530A patent/ES483530A1/en not_active Expired
- 1979-08-22 CA CA000334271A patent/CA1142506A/en not_active Expired
- 1979-08-22 JP JP10613079A patent/JPS5564840A/en active Granted
- 1979-08-23 ZA ZA00794456A patent/ZA794456B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5564840A (en) | 1980-05-15 |
| DE2849026A1 (en) | 1980-05-22 |
| DE2961252D1 (en) | 1982-01-14 |
| JPS625012B2 (en) | 1987-02-03 |
| ATE343T1 (en) | 1981-11-15 |
| EP0013286A1 (en) | 1980-07-23 |
| ES483530A1 (en) | 1980-05-16 |
| EP0013286B1 (en) | 1981-11-04 |
| ZA794456B (en) | 1980-09-24 |
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