JPH01228554A - Platinum group metal supporting mordenite and manufacture thereof - Google Patents

Abstract

PURPOSE:To increase inversion rate and selectivity, particularly at the time of isomerizing the paraffin having 4-6 carbon atoms in the presence of hydrogen, by depositing platinum group metal and rare earth oxide on mordenite to form a platinum group metal-supporting mordenite. CONSTITUTION:The mordenite impregnated with metal salt of the platinum group by ion-exchange of rare earth ions is baked in an oxygen atmosphere at a temperature of not more than 1000 deg.C to convert the rare earth ions into the rare earth oxide and, alternatively, the mordenite impregnated with rare earth ions by ion-exchange is baked in an oxygen atmosphere at a temperature of not more than 1000 deg.C to convert rare earth ions into rare earth oxide and this baked product is then impregnated with the salt of the platinum group. The platinum group metal is thereafter reduced, thereby depositing the platinum group metal on the mordenite together with the rare earth oxide to form a platinum group metal-supporting mordenite.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to platinum group metal-supported mordenite and a method for producing the same. The mordenite can be used as a dewaxing catalyst, a hydrocracking catalyst, a hydrorefining catalyst, a CO oxidation catalyst,
It can be effectively used in a wide range of fields such as hydrocarbon oxidation catalysts, reforming catalysts, naphthene isomerization catalysts, and paraffin isomerization catalysts. It has particularly excellent performance as a paraffin isomerization catalyst.

[Conventional technology]

PT group/H type mordenite in which platinum group metal is supported on mordenite in which the exchangeable cations present in mordenite are replaced with hydrogen ions (U.S. Pat.
No. 939 specification) Alternatively, after supporting a platinum group metal on mordenite substituted with ammonium ions, the temperature is 50°C.
There is pt group/H type mordenite (US Pat. No. 31,342.114), which has almost all ammonium ions removed by firing at 0° C. or higher.

[Problem to be solved by the invention]

However, in none of these methods is the reaction activity controlled, and high reactivity cannot be obtained unless the reaction conditions are made harsher. The inventors of the present invention have arrived at the present invention as a result of intensive research aimed at obtaining platinum group metal-supported mordenite having catalytic properties not previously available.

[Means to solve the problem]

That is, the gist of the present invention is as follows: (1) A platinum group metal supported mordenite, characterized in that a rare earth oxide is supported together with a platinum group metal. (Hereinafter, also referred to as the substance of the present invention) (2) (a) Mordenite containing a platinum group metal salt containing rare earth ions by ion exchange is calcined at 1000°C or less in an oxygen atmosphere to convert the rare earth ions into rare earth oxides. (b) Mordenite containing rare earth ions by ion exchange is fired at 1000°C or less in an oxygen atmosphere to convert the rare earth ions into rare earth oxides, and then a platinum group metal salt is added to the fired product. and (c) then reducing a platinum group metal salt. (3) (a) Mix mordenite supported on a platinum group metal and a rare earth oxide and sinter at 200 to 1000°C in an oxygen atmosphere, or (b) Mix mordenite and a rare earth oxide and heat the mixture in an oxygen atmosphere. A method for producing platinum group metal-supported mordenite, which comprises: firing at 200 to 1000°C, impregnating the fired product with a platinum group metal salt, and (c) then reducing the platinum group metal salt. (4) (a) Mix platinum group metal-supported mordenite and rare earth salt and sinter at 1000°C or less in an oxygen atmosphere to convert the rare earth salt to rare earth oxide, or (b) Mordenite and rare earth oxide (c) After converting the rare earth salt into rare earth oxide by baking at 1000° C. or lower in an oxygen atmosphere, the baked product is impregnated with a platinum group metal salt. A method for producing platinum group metal-supported mordenite characterized by reducing salt. It is in. The substance of the present invention> When mordenite is expressed as a molar ratio of oxides, it is M27゜0・A
I 203 ・(9,5-20.5) S i O2
(Here, M is an alkali metal, an alkaline earth metal, H, NH4, a nitrogen-containing organic compound, etc., and n is the valence of M). The material of the present invention is composed of this mordenite, a rare earth oxide, and a platinum group metal, but it is not a simple mixture of these, but a mordenite in which the latter two are supported. In the case of H type, it is excellent as a catalyst for various reactions, especially paraffin isomerization, and in the case of Na type, it is used as a reforming catalyst for paraffin reforming.
Decomposition activity is moderately suppressed and high liquid yield is obtained. The rare earths include scandium, i-sotrium,
Lanthanum 1 Cerium, praseodymium, neodymium, promethium, samarium, europium. Gadolinium, terbium, dysprosium, holmium, erbium, thulium, terbium, lutetium, etc. can be used. In particular, when cerium is used, its activity as a catalyst for paraffin isomerization is high. The number of rare earth oxides to be supported may be one or two.
More than one species can also be used. When the substance of the present invention is used as a catalyst for isomerization of paraffin, etc., the amount of supported rare earth oxide is as follows: mordenite
~20.5) S i 02 ) Rare earth ions no, o+: +42 to 1.27 gram atoms per mole,
In particular, a proportion of 0.021 to 0.85 gram atoms is desirable. When the amount of rare earth oxide is less than 0.0042 gram atom, the catalyst activity is low, and when it is more than 1.27 gram atom, the effect is small compared to the supported amount. Further, as the platinum group metal, any of platinum, rhodium, palladium, ruthenium, osmium, and iridium can be used. Particularly preferred as a catalyst component is platinum. There is no particular limit to the amount of platinum group metal supported, but when the substance of the present invention is used as a catalyst for isomerization of paraffin, it is 0.1 to 3 Ovt%, preferably 0.3 Ovt%, based on mordenite. It may be set to 1.5 νt%. This is because if the content of the platinum group metal is less than 0.1 wL%, the catalytic activity is too low, and if it exceeds 3.0vL%, the effect is small compared to the supported amount. Production method> In the production method of the substance of the present invention, when mordenite is used as a starting material, the mordenite may be either natural or synthetic, and it is clear from the descriptions in (2), (3), and (4) above. Basically, it consists of the following four steps. (a) Addition port for platinum group metal salts (c) Reduction of platinum group metal salts (c) Addition of rare earth substances (2) Naturally, the treatment at the firing port must be performed after the treatment in (a), and the treatment in (2) must be performed after the treatment in (c). Furthermore, since the second treatment is usually carried out in an oxidizing atmosphere, the mouth treatment should be performed after the second treatment. The processing in step (a) may be performed before or after steps (c) and (2), or between (1) and (2). (Supporting Platinum Group Metal) Supporting of platinum group metal, which consists of the above-mentioned treatments (a) and (a), may be carried out by a conventionally well-known method. That is, first, mordenite or rare earth ion I
If mordenite is impregnated with an aqueous solution of one or more platinum group metal salts by impregnation treatment, extraction treatment, ion exchange treatment, or the like. Among them, ion exchange treatment or mordenite containing the metal is particularly preferred. As the ion exchange method, ion exchange treatment using a compound in which the metal is present as a cation, such as a metal complex such as ammonia, alkylamine, hydroxylamine, hydrazine, etc., is preferable. In this way, the platinum group salt D'
After drying the f-7 product, it is heat-treated in the presence of a reducing agent such as ammonia, hydrogen, etc., preferably hydrogen, to reduce the platinum group metal to its metallic form. (Supporting Rare Earth Oxide) A rare earth oxide is supported on mordenite or platinum group-containing mordenite by the treatments /X and 2 above. The present invention provides the following two methods. l. Ion exchange calcination method First, the material to be treated (mordenite or platinum group metal salt-containing mordenite) is heated to a compound in which a rare earth element exists as a cation in an aqueous solution, such as a nitrate. By contacting with an aqueous solution of chloride, acetate, oxalate, carbonate, etc., part or all of the exchangeable cations in the object to be treated are exchanged into rare earth ions. When scales are used as a catalyst for paraffin isomerization, etc., as described above, the amount of exchange is changed to mordenite (former scale M2/, 0-Al□03 ・ (9,5 to 20.5
) S i 02 ) 0.0042 to 1.27 g atoms in terms of rare earth element per 1 mole, especially 0.02
The proportion may be 1 to 0.85 gram atoms. As described above, after this ion exchange treatment, a treatment for impregnating a platinum group metal can be performed before the next firing. The ion-exchanged product is dried and then fired at 1000° C. or lower in an oxygen atmosphere to convert the rare earth ions into oxides and support them on mordenite. This oxygen atmosphere does not need to be high in oxygen content; air is sufficient. Naturally, this calcination must be carried out at a temperature high enough to convert the rare earth ions into oxides, and the calcination temperature is selected from the range of 400 to 1000°C (within this temperature range, it is necessary to simultaneously convert the rare earth ions into mordenite). responsibilities are also fulfilled). The reason why the upper limit of the firing temperature is set to 1000° C. is that if this temperature is exceeded, the crystal structure of mordenite will be destroyed. The reason why the upper limit of the firing temperature is set at 1000° C. in all the manufacturing methods of the present invention is for the same reason. Through this firing process, the areas where rare earth ions were present become H
Becomes a mold. This is presumed to be due to decomposition of the OH groups coordinated to the rare earth ions to generate hydrogen ions. Conversion of rare earth ions to their oxides is confirmed by X-ray diffraction. That is, the 2θ-6,5" and 13.9° peaks characteristic of mordenite disappear when rare earth ions are exchanged, but when rare earth ions are converted to oxides, these two peaks reappear. However, due to the above conversion, Items whose colors are expressed can be easily confirmed by the change in color.For example, cerium oxide is pale yellow, neodymium oxide is blue, and europium oxide is pale pink.Mordenite containing platinum group metal salts When firing,
Although it can be fired as is, natural clays (e.g. kaolin, halloysite, montmorillonite, etc.) and/or inorganic oxides (e.g. silica; binary gels such as silica-alumina, silica-zirconia, silica-magnesia, aluminum phosphate); Ternary gel such as silica-magnesia-alumina; alumina, titania, zirconia, etc.)
It is also possible to granulate the granules using, for example, sintering. 1i. Mixing firing method First, mordenite or platinum group metal salt-containing mordenite and a rare earth oxide and/or rare earth salt are mixed. This mixing method includes dry mixing method, as long as it is mixed uniformly.
Either wet mixing method may be used. Rare earth salts are nitrates, halides, and acetates. Oxalates, carbonates, oxohalides, thiosulfates, selenate, hydroxides, chromates, phosphates, borates, silicates, cyanides, formates. Ethyl sulfate, dimethyl phosphate, malonate. One kind of glycolate, sebacate, cacodylate, etc. may be used, or two or more kinds thereof can be used. After this mixing, a treatment for impregnating a platinum group metal salt can be performed before the next firing. Next, it is fired at 1000° C. or lower in an oxygen atmosphere. This atmosphere is 1. As in the ion exchange calcination method, it is not necessary to use a material with a high oxygen content, and air is sufficient. When using rare earth oxides, the firing temperature is 200
~1000°C. If the temperature is lower than 200°C, the rare earth oxide remains simply mixed with mordenite and is not supported, so that a highly active catalyst cannot be obtained. This change in state can be confirmed by a change in the intensity of peaks such as 20=6.5° and 13.9' in the X-ray diffraction chart. When using rare earth salts, the temperature must naturally be high enough to convert the rare earth salts into oxides, and the firing temperature is between 200 and 100 ℃.
It is selected from a range of 0° C. (as is clear from the above explanation, in this temperature range, the rare earth oxide is supported on mordenite). When firing a mixture containing a platinum group metal salt, i,
As in the case of the ion exchange calcination method, the granules can be fired as they are, or they can be granulated using a binder and then fired.

[Effects of the Invention] The platinum group metal-supported mordenite supporting the rare earth oxide of the present invention can be used as a dewaxing catalyst and a hydrogenolysis catalyst. It is useful as a hydrorefining catalyst, a CO oxidation catalyst, a hydrocarbon oxidation catalyst, a reforming catalyst, a naphthene isomerization catalyst, a paraffin isomerization catalyst, and the like. In particular, when this is used to isomerize paraffins having 4 to 6 carbon atoms in the presence of hydrogen, high conversion and/or selectivity can be achieved under relatively mild conditions. Therefore, the mordenite supporting rare earth oxides and platinum group metals according to the present invention can be widely used as a catalyst in the petroleum industry including petroleum refining, and the chemical industry with H effect. Moreover, the above-mentioned platinum group-supported mordenite can be easily and industrially produced by any of the production methods of the present invention.

【Example】

EXAMPLES In order to explain the present invention more specifically, Examples are shown below, but the present invention is not limited to the following Examples. Example 1 30 g of synthetic Na-type mordenite (S i 02 /A
After dispersing 12O3 molar ratio -14.9) in 300 ml of ammonium chloride aqueous solution with a concentration of 2.0 mol/1,
Ammonium ion exchange was performed by stirring at 0° C. for 3 hours. This operation was repeated twice. The contents were then separated by suction filtration and washed repeatedly until no chloride ions were detected. The residual N am of the obtained NH4 type mordenite was determined by atomic absorption spectrometry and was found to be less than 0.1 νL%. An X-ray diffraction chart of this NH4 type mordenite is shown in FIG. This NH4 type mordenite was dispersed in 10,100 O of an aqueous solution of cerous nitrate with a concentration of 0.1 mol/I, and then stirred at 80° C. for 5 hours to perform cerium ion exchange. The amount of ion exchange is determined by ED of the cerous nitrate aqueous solution before and after ion exchange.
Calculated by TA titration. 8.0νL in terms of CeO2 96
Met. An X-ray diffraction chart of the obtained CeNH4 type mordenite is shown in FIG. 50 (
The cerium ion was converted into an oxide by firing in air at 1° C. for 2 hours. The fired product contains the generated CeO2
Therefore, the color was pale yellow. The X-ray diffraction chart is shown in FIG. j Platinum (platinum reagent: Pt (NH3) 4 Cl2) of 5 wt % of polished CeO2-supported H-supported small mordenite (CeO2-supported H-supported small mordenite)
was ion-exchanged using the ion-exchange method. After ion exchange,
After repeated washing until no chloride ions were detected, it was dried in a hot air dryer at 110°C overnight. The obtained CeO2-supported Pt-H type mordenite was pressure-molded, then crushed, sieved to collect 16 to 32 mesh pieces, and calcined in air at 509°C for 2 hours. Subsequently, the mixture was filled into a quartz reaction tube and subjected to hydrogen reduction at 300° C. for 3 hours. Example 2 Synthetic Na! 4! ! Mordenite 30g (S i 02
/Al2O3 molar ratio -14.9) was dispersed in 300 ml of ammonium chloride aqueous solution having a concentration of 2.0 mol/l, and then stirred at 60°C for 3 hours to perform ammonium ion exchange. This operation was repeated twice. The contents were then separated by suction filtration and washed repeatedly until no chloride ions were detected. The residual Na m of the obtained NH4 type mordenite was measured by atomic absorption spectrometry and was found to be 0. lvt%. This NH4 type mordenite was dispersed in 1000 ml of an aqueous lanthanum nitrate solution having a concentration of 0.1 mol/l, and then stirred at 80° C. for 5 hours to perform lanthanum ion exchange. The amount of ion exchange was calculated by titrating the lanthanum nitrate aqueous solution before and after ion exchange with EDTA. 9.0ν in terms of La2O3
It was L%. The obtained LaNH4 type mordenite (
Lanthanum ions were converted into oxides by firing in air at 50° C. for 2 hours. 0.5νL% (La203-supported H-type mordenite)
platinum (platinum reagent: Pt (for type mordenite))
NH3)4Cl2) was ion-exchanged by an ion exchange method. After ion exchange, washing was repeated until chloride ions were no longer detected, and then dried in a hot air dryer at 110° C. all day and night. The obtained La20. After pressure forming the supported Pt-H type mordenite, it is crushed and sieved to form I
A portion of C~32Cl powder was collected and calcined in air at 500°C for 2 hours. Next, fill the quartz reaction tube,
Hydrogen reduction was performed at 00°C for 3 hours. Example 3 30 g of synthetic Na-type mordenite (S i 02 /A
After dispersing 12O3 molar ratio -14.9) in 300 ml of ammonium chloride aqueous solution with a concentration of 2.0 mol/l, 6
Ammonium ion exchange was performed by stirring at 0° C. for 3 hours. This operation was repeated twice. The contents were then separated by suction filtration and washed repeatedly until no chloride ions were detected. The amount of residual Na in the obtained NH4 type mordenite was measured by atomic absorption spectrometry and was found to be O.1w.
It was less than t%. This NH4 type mordenite was dissolved in 1000 m of an aqueous cerous nitrate solution with a concentration of 0.1 mol/1.
After dispersing the mixture in 1 liter of water, the mixture was stirred at 80° C. for 5 hours to perform cerium ion exchange. The amount of ion exchange was calculated by titrating the cerous nitrate aqueous solution before and after ion exchange with EDTA. It was 7.9 wt% in terms of CeO2. Obtained CeN
Platinum (platinum reagent: Pt(NH
l) 4C12) was ion-exchanged by an ion-exchange method. After ion exchange, washing was repeated until chloride ions were no longer detected, and then dried in a hot air dryer at 110°C overnight. The obtained pt·CeNH4 type mordenite was pressure-molded, then crushed, sieved to collect 16 to 32 mesh pieces, and calcined in air at 500°C for 2 hours. The obtained fired product was filled into a quartz reaction tube and heated to 300°C.
Hydrogen reduction was carried out for 3 hours. Comparative Example 1 30g of synthetic Na-type mordenite (S i 02 /A
After dispersing 12O, molar ratio -14.9) in 300 ml of ammonium chloride aqueous solution with a concentration of 2.0 mol/l, 6
Ammonium ion exchange was performed by stirring at 0°C for 3 hours. This operation was repeated twice. The contents were then separated by suction filtration and washed repeatedly until no chloride ions were detected. The residual NaQ of the obtained NH4 type mordenite was measured by atomic absorption spectrometry and was found to be 0.
．． It was less than 1 wt%. 0.5vt96 (relative to NH4 type mordenite) of platinum (platinum reagent 2Pt (NH3) 4C12) was added to the obtained NH4 type mordenite.
was ion-exchanged using the ion-exchange method. After ion exchange,
After repeated washing until no chloride ions were detected, it was dried in a hot air dryer at 110° C. all day and night. After pressure-molding the obtained pt/H type mordenite, it is crushed,
Sieve and collect 16 to 32 mesh pieces,
It was baked in air at 00°C for 2 hours. Subsequently, the mixture was filled into a quartz reaction tube and subjected to hydrogen reduction at 300° C. for 3 hours. Example 4 Crystallization slurry (solid content concentration: 12.9
wt%) looog was suction filtered using a porcelain Buchner funnel. After the filtration was completed, it was washed with 400 ml of warm water. Humidity is added to the cake layer formed in this way while being sucked into the cake layer.
2300 ml of 0.8N hydrochloric acid at 5°C was poured into the solution for about 10 minutes. It was thoroughly washed with water and washed with hydrochloric acid and dried. When the composition of the obtained crystal was measured by chemical analysis, it was found that Si
o2/A 1203 molar ratio is 25.3 and Na2
The Q content was less than 0.05 wt%, which is below the detection limit. The obtained H-type dealuminated mordenite was heated at 700°C.
It was baked in air for 1 hour. Platinum (platinum reagent: Pt(NH3)
)4C1□) was ion-exchanged by an ion exchange method. After ion exchange, washing was repeated until chloride ions were no longer detected, and then dried in a hot air dryer at 110° C. all day and night. The obtained Pt-H type dealuminated mordenite log and 21 g of CeO were thoroughly mixed, pressure-molded, crushed, sieved to collect 16 to 32 mesh pieces, and calcined in air at 500°C for 2 hours. . X-ray diffraction charts of the material before and after firing are shown in FIGS. 4 and 5, respectively. Subsequently, the mixture was filled into a quartz reaction tube and subjected to hydrogen reduction at 300° C. for 3 hours. Example 5 S i O2/Al2 synthesized by hydrothermal synthesis
1000 g of a crystallization slurry consisting of Na-type mordenite crystals with an O3 molar ratio of -14.9 and a crystallization mother liquor (solid content I degree: 12.9 vt%) was suction-filtered using a porcelain Buchner funnel. After the filtration was completed, it was washed with 400 ml of warm water. Approximately 10 ml of 0.8N hydrochloric acid at a temperature of 35°C was poured into the cake layer thus formed while suctioning.
The liquid was passed for a minute. It was thoroughly washed with hydrochloric acid and immersed in water, and then dried. When the composition of the obtained crystal was determined by chemical analysis, the SiO□/A 1203 molar ratio was 25.3, and the Na 20 -containing ML was 0.05νt below the detection limit.
% or less. The obtained H-type membrane aluminum mordenite was fired in air at 700° C. for 1 hour. This H
0.5wt0δ (relative to the H-type membrane aluminum mordenite) of platinum (platinum reagent: P t (NH3) 4 Cl2) was ion-exchanged to the type membrane aluminum mordenite by an ion exchange method. After ion exchange, washing was repeated until no chloride ions were detected, and then 110
It was dried in a hot air dryer at ℃ overnight. The obtained Pt-H
The mold membrane aluminum mordenite log and 1.5 g of lanthanum nitrate hexahydrate were thoroughly mixed, pressure molded, crushed, and sieved to collect a portion of 16 to 32 mm.
It was baked in air at 0° C. for 3 hours. Subsequently, the mixture was filled into a quartz reaction tube and subjected to hydrogen reduction at 300° C. for 3 hours. Comparative Example 2 A pt-containing H-type dealuminated mordenite was prepared in the same manner as in Example 3, except that it was fired and reduced without mixing CeO2. Usage Examples Using the products prepared in Examples 1.2.3 and 4 and Comparative Examples 1 and 2 as catalysts, reaction temperature 230°C reaction pressure atmospheric pressure hydrogen/n-hexane vol ratio 2.5 weight hourly space velocity th-' The isomerization reaction of n-hexane was carried out under the following conditions, and the performance of the catalyst was evaluated. The conversion rate of 11-hexane and the selectivity of its skeletal isomer after 5 hours of passing n-hexane through the oil are shown in the table below. Note) n-Cb: n-hexane + C,: ・1゛1 isomer of n-hexane

[Brief explanation of the drawing]

Figures 1.2 and 3 show NH4 in Example 1, respectively.
1 is an X-ray diffraction chart of type mordenite, CeNH4 type mordenite, and a fired product thereof. 4 and 5 are X-ray diffraction charts 1- of the mixture of Pt/H type film aluminum mordenite and CeO2 before and after firing in Example 4, respectively. Special;;′ [Applicant: Tosoh Corporation

Claims (4)

[Claims] (1) A platinum group metal-supported mordenite characterized by supporting a rare earth oxide together with a platinum group metal. (2) (a) Platinum group metal salt-containing mordenite containing rare earth ions by ion exchange is placed in an oxygen atmosphere for 1 hour.
(b) Mordenite containing rare earth ions by ion exchange is fired at 1000°C or less in an oxygen atmosphere to convert rare earth ions into rare earth oxides. A method for producing platinum group metal-supported mordenite, which comprises converting the fired product into a platinum group metal salt, and (c) then reducing the platinum group metal salt. (3) (a) Mix mordenite containing a platinum group metal salt and a rare earth oxide and sinter at 200 to 1000°C in an oxygen atmosphere, or (b) Mix mordenite and a rare earth oxide and heat the mixture in an oxygen atmosphere. 1. A method for producing platinum group metal-supported mordenite, which comprises: firing at 200 to 1000°C, impregnating the fired product with a platinum group metal salt, and (c) then reducing the platinum group metal salt. (4) (a) Mix mordenite supported on platinum group metal and rare earth salt, and convert the rare earth salt into rare earth oxide by baking at 1000°C or less in an oxygen atmosphere, or (b) Mordenite and rare earth oxide. (c) After converting the rare earth salt into rare earth oxide by baking at 1000° C. or lower in an oxygen atmosphere, the baked product is impregnated with a platinum group metal salt. A method for producing platinum group metal-supported mordenite characterized by reducing salt.