JPH0290946A - Catalyst consisting of hectorite-like substance containing nickel and manufacture thereof - Google Patents

Abstract

PURPOSE:To obtain highly active and industrial catalysts by specifying the properties of catalysts consisting of hectorite-like substance containing nickel and controlling the contents of Ni/Si and Li/Si to a specified ratio. CONSTITUTION:The subject catalyst consists of hectorite-like substance which contains nickel, and has a specific area of about 10 to 1,000m<2>/g, a pore volume of about 0.1 to 1cm<2>/g and an average pore diameter of about 10 to 100Angstrom . In addition, the ratio of nickel to silicon expressed by Ni/Si is about 0.05 to 2 and that of lithium to silicon by Li/Si is about 0.01 to 3. The catalyst obtained as described above contains an inorganic substance which substitutes magnesium in the octahedron structure of hectorite with nickel and forms pillars between the layers. Consequently, the catalyst has outstanding properties and is used for industrial applications.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a catalyst made of a hectorite-like substance containing nickel and a method for producing the same.

According to McEwan, the model chemical formula for hectorite is (
1) Expressed by the formula (Montmorllonlte
mlnerals by D, M, C, MacEwan
, The X-rayldentflcatlon
and crystal 5 structures o
fclay m1nerals edited by
G. Brown.

Mlneralogical 5oc1ety, Lo
ndon, 1972. pp 143-207).

(S1s) [Mg! ,,a3LI9. AV co Oai
+(OH)j (1)↓ Mo6.67 Here, M◆ is a monovalent exchangeable cation present between the layers. Hectorite belongs to the 3-octahedral smectite group.
Silicon is located in the tetrahedral layer, and magnesium and lithium are located in the octahedral layer, and it is generally believed that the amount of lithium in the octahedral layer corresponds to the layer charge. Hectorite is a type of smectite that has a unique property of forming complexes with inorganic or organic substances because the layer charge of hectorite is smaller than that of mica. Attempts have been made to utilize this property to create a zeolite-like porous body by placing inorganic pillars between the layers and use it as a catalyst, catalyst carrier, adsorbent, etc.

For example, using montmorillonite, a type of naturally occurring di-octahedral smectite, aluminum hydroxide is introduced between its layers by ion exchange, and then heated in an electric furnace to form porous aluminum hydroxide into alumina pillars. A method for manufacturing the clay body is known (Shoji Yamanaka, Clay Science, 21, 78-82, 1981). In this case, a reaction time of about one week is required to add an aqueous sodium hydroxide solution to an aqueous aluminum salt solution to synthesize an aluminum hydroxide oligomer. In addition, a large excess amount of aluminum hydroxide is required to cause the montmorillonite and aluminum hydroxide to react well, and the reaction time is also long. Moreover, it has the disadvantage that it is quite difficult to remove a large excess of aluminum hydroxide and by-product solutes after the reaction is completed. Furthermore, since the montmorillonite used exists as one of the constituent substances in bentonite, quartz 1. Because it contains impurities such as cristobalite and calcite, it is necessary to extract, separate and purify only montmorillonite in advance. Normally, pure montmorillonite products are produced by extraction from a dilute aqueous bentonite dispersion solution of about 1 to 2%, which requires refining costs such as dry quality, and is commercially available at an extremely high price.

Moreover, since it is a natural product, its material properties such as chemical composition, structure, defects, and impurities vary greatly, so when producing a catalyst by compounding it, it is difficult to control its properties, and impurities such as iron that can poison the catalyst Taking this into account, it lacks suitability for use as a catalyst or catalyst carrier.

On the other hand, there have been reports of using synthetic smectite as a raw material in order to avoid the influence of impurities and make it easier to control properties, but as with the case of natural smectite, it takes a long time to produce a porous body. It has the disadvantage that it is often difficult to complex with aluminum hydroxide than natural smectite. For example, the specific surface area of an aluminum crosslinked synthetic fluorinated hectorite catalyst obtained by the reaction of synthetic fluorinated hectorite and aluminum hydroxide is given as 73 m2/g (K, Urabe.

H, 5akural and Y, Izuml, J
,Chem,Soc,,Chem.

Commun, 1986.1074-107G).

Since the specific surface area of the aluminum cross-linked montmorillonite catalyst synthesized in the same manner is 228 m
have reported.

The purpose of the present invention is to provide a catalyst as a precisely designed material that is industrially satisfactory and does not have the disadvantages seen in catalysts obtained from natural smectite or synthetic smectite as raw materials, and a method for producing the same. It is.

As a result of many years of intensive research into catalysts with excellent properties and methods for producing the same, the inventors of the present invention have come up with the invention of a novel catalyst made of a nickel-containing hectorite-like substance and a method for producing the same.

That is, this invention has a specific surface area of about 100 to about 1000 m
2/g and its pore volume is about 0.1 to about 1 cm
3/g, an average pore diameter of about 10 to about 10 OA, a ratio of nickel to silicon in Nl/Sl of about 0.05 to about 2, and a ratio of lithium to silicon of about 0.01. The present invention comprises a catalyst made of a nickel-containing hectorite-like material, characterized in that it has a nickel-containing hectorite-like substance of 0.3 to about 0.3, and a method for producing the same.

The catalyst made of a nickel-containing hectorite-like substance of the present invention has a basic structure of nickel-containing hectorite in which part or all of the magnesium in the hectorite structure is replaced with nickel in the hectorite of formula (1). Conceivable. When dehydrated, smectite usually shrinks between its layers and becomes a mica-like structure without pores, but the catalyst made of the nickel-containing hectorite-like material of the present invention can achieve the claimed values by heating and dehydrating. Since it has pores with a satisfactory specific surface area, total pore volume, or average pore diameter, it is thought that it contains an inorganic substance that functions as a pillar between the layers, and was probably introduced between the layers during synthesis. It can be inferred that

The catalyst made of the nickel-containing hectorite-like material of the present invention can be produced even when the value of silicon is 8, and the value of nickel is between 6 and 16, which would prevent it from entering the octahedral structure. Nickel is thought to exist between layers. In addition, the present invention can be achieved by substituting part of divalent metals such as magnesium, cobalt, zinc, and copper that can enter the octahedral structure with nickel, and the amount of nickel satisfies the claimed value. Good, but preferably old/5l
A value between =0.1 and 1 is desirable.

Next, a method for achieving the present invention will be described below. The method for producing a catalyst made of a nickel-containing hectorite-like material according to the present invention comprises the following steps.

Firstly, silicon, nickel, and lithium that satisfy the values indicated in the claims, as well as divalent metals such as magnesium, cobalt, zinc, copper, iron, manganese, lead, and cadmium, alkali metals, and alkalis. A slurry is prepared by adding earth metals, fluorine, etc., secondly, the slurry is subjected to a hydrothermal reaction at 100 to 350°C, thirdly, this hydrothermal reaction product is filtered and dried at 300°C or less, Fourthly, the product of the present invention can be obtained by crushing, sizing, or granulating.

In the first step, when preparing the slurry, noble metals such as aluminum, titanium, zirconium, tin, indium, gallium, or gold, silver, platinum, and palladium, which cannot enter the hectorite silicate structure, are added to prepare the product of the present invention. You can also get it.

Since these metals have difficulty entering the hectorite silicate structure, they are thought to exist in the interlayers between silicates. As the silicon used for the slurry, water-soluble materials such as sodium silicate, water glass, and silicic acid solution are used. Divalent metals such as nickel and magnesium, alkali metals, alkaline earth metals, noble metals, trivalent metals such as aluminum, tetravalent metals such as titanium, chlorides, fluorides, hydroxides, nitrates, sulfates, phosphates, Used in the form of perchlorate, etc. As the fluorine, hydrofluoric acid, sodium fluoride, etc. are used.

The product of the present invention can be obtained if silicon, nickel, and lithium in the slurry satisfy the values specified in the claims.
Other divalent metals such as magnesium, alkali metals,
The present invention can be achieved even when alkaline earth metals, noble metals, trivalent metals such as aluminum, tetravalent metals such as titanium, and fluorine coexist.

In order to avoid the influence of secondary salts generated from the raw material reagents used, the slurry is usually prepared by preparing a composite precipitate of silicon, nickel and other metals necessary to achieve the present invention, and after removing the secondary salts, water is added to the slurry. Vine is prepared by adding solutions such as lithium oxide, sodium hydroxide and fluoric acid.

In the second step, the slurry obtained in the first step is transferred to an autoclave and subjected to a hydrothermal reaction at 100 to 350° C., thereby producing a nickel-containing hectorite-like substance, thereby achieving the present invention.

In the third step, the hydrothermal reaction product obtained in the second step is filtered and dried at 300° C. or lower. Although it is not necessary to wash the product by washing with water during filtration, washing is absolutely prohibited. When drying, it is okay to make the conditions gentler so that the moisture content is suitable for granulation and carry it to the next step. It is also a good idea to strengthen the drying conditions to form a hard solid material before carrying it to the next step. After filtering the hydrothermal reactant, ion exchange can be performed at any stage. Ion exchange can be carried out as long as it is a cation, such as alkali metal ions, alkaline earth metal ions, transition metal ions, rare earth metal ions, trivalent metal ions such as aluminum, alkyl quaternary ammonium ions, alkyl tertiary ammonium ions, It can be selected from alkyl secondary ammonium ions, alkyl primary ammonium ions, etc.

In the fourth step, the dried product obtained in the third step is pulverized and sized to a particle size that can be used as a catalyst to obtain the product of the present invention. Alternatively, the product of the present invention can be obtained by completely crushing the powder into a powder, adding moisture to the powder, and granulating it.

It is also possible to mix an organic substance such as a thermoplastic resin or a thermosetting resin with the powder before granulation and use it as a binder. Examples of thermoplastic resins include vinyl chloride resin, vinyl acetate resin, ethylene-vinyl acetate resin and saponified products thereof,
Examples include polystyrene resin, thermoplastic polyurethane resin, polyethylene resin, polypropylene resin, ABS resin, acrylic resin, polyamide resin, acetal resin, polycarbonate resin, and cellulose plastic. As a thermosetting resin, phenol formaldehyde It
Examples include fat, urea+i fat, and melamine resin. Inorganic binders can also be used during granulation, such as sodium silicate, aluminum silicate, silica powder, aluminum phosphate, kaolin, bentonite,
Apatalgite, talc, pyrophyllite, acid clay, etc. can be used. Furthermore, it is also possible to directly granulate the product obtained in the third step by adjusting the water content. Even if it is granulated as it is, a product with mechanical strength sufficient to be used as a catalyst can be obtained, but in order to further increase the strength, it may be granulated under pressure of 1000 kg/cm2 or less. The product of the present invention can also be obtained by firing at a temperature of 100 to 1000°C after granulation.

The catalyst made of a nickel-containing hectorite-like substance obtained by carrying out the present invention is determined by X-ray diffraction, differential thermal analysis, infrared absorption spectrum, chemical analysis, specific surface area, pore volume, average pore diameter, catalytic activity, etc. can be evaluated. The catalyst made of the nickel-containing hectorite-like substance of the present invention has a diffraction angle (2θ
) appears at about 61' for (35,06) of the (nk) reflection, indicating that it contains 3-octahedral smectite.

The X-ray diffraction pattern is very similar to that of hectorite, but is often broader overall. The specific surface area is about 100 to about 1000 m2/gs, the total pore volume is about 0.1 to about 1 cm"/g, and the average pore diameter is about 10 to about 10 OA, and it contains nickel in its structure. It is extremely useful as a catalyst.The catalyst made of the nickel-containing hectorite-like substance of the present invention can be used in oxidation reactions, reduction reactions, decomposition reactions, synthesis reactions, isomerization reactions, dehydration reactions, etc., and is useful. .

Next, an example will be given and explained.

Example 1 14 g of magnesium chloride-grade reagent (purity 98%) and chloride were added to 300 ml of a silicic acid solution prepared from 43 g of No. 3 water glass (S102 28%, Na2O 9%, 2 molar ratio 3.22) and 10 ml of 16N nitric acid. Dissolve 18 g of nickel (II) hexahydrate special grade reagent (98% purity) and add the resulting silicic acid-nickel salt-magnesium salt solution to 200 ml of 2N sodium hydroxide solution for 3 minutes with stirring. Drip. Immediately, the obtained reaction composite oxide was filtered and thoroughly washed with water, followed by an aqueous solution 15 in which 0.73 g of lithium hydroxide hydrate special grade reagent (purity 98%) was dissolved.
Add m1 to make a slurry and transfer it to an autoclave.
15.9 kg/cm2. React at 200°C for 2 hours. After cooling, the reaction product was taken out and dried at 80°C to obtain a product of the present invention. The chemical composition obtained by chemical analysis is Sl:
NI:Mg:Ll:Na=1:0.43:0. H:0
．． It was 09:0.20.

The X-ray diffraction pattern shows an overall broad pattern similar to hectorite, and the d value of (35, OB) is 1.
It was 522A. Specific surface area of sample 153 m2/g1
Total pore volume 0.11 cm3/g and average pore diameter 29
．． It was 3A.

The product of the present invention was pulverized into 16-32 mesh particles and used as a catalyst to carry out the dehydration reaction of 2-propanol in a normal pressure flow system, W/F = 3.6gh/mol, 2-
Proper tool partial pressure 8 kPa (carrier is helium)
The reaction temperature was 350° C., and the reaction product was quantitatively analyzed using a gas chromatograph. The products are diisopropyl ether and propylene, and the total conversion is 34%.
Met. Selectivity to diisopropyl ether is 92
The mo was 1%.

Example 2 The same procedure as in Example 1 was carried out using the following amounts of raw materials.

No. 3 water glass 43 g Nickel (II) chloride hexahydrate special grade reagent 32 g Lithium hydroxide hydrate special grade reagent 0.6 g The chemical composition of the obtained product of the present invention is S do old: LI: Na = 1 =0°88:0
．． 10:0.18. The X-ray diffraction pattern was similar to that of hectorite, but broader overall, and the d value for (35,08) was 1.524 A. Specific surface area 19 [i m2/g, total pore volume 0.12
cm3/g and average pore diameter of 24.5 A.

2 under the same conditions as Example 1 using the product of the present invention as a catalyst.
- Dehydration reaction of propatool was carried out. Diisopropylnitertofuropylene was obtained as a product, and the total conversion was 46%. The selectivity to diisopropyl ether was 79 mo1%.

Example 3 The same procedure as in Example 1 was carried out except that the amount of raw materials charged was as follows.

No. 3 water glass 43 g Nickel (II) chloride hexahydrate special grade reagent 32 g Lithium hydroxide hydrate special grade X O, Ggl 0% hydrofluoric acid solution 15 ml The chemical composition of the obtained product of the present invention is Sl :Old:Li:Na:p= 1:0.8G
:0. OE! :0.15:0.38. The X-ray diffraction pattern was similar to hectorite, with overall broader peaks. The d value of (35, OG) is 1.52
It was 2A. Specific surface area 323 m2/g1 Total pore volume 0.21 cm3/g and average pore diameter ze, oA
Met.

A dehydration reaction of 2-propanol was carried out under exactly the same conditions as in Example 1 using the product of the present invention as a catalyst.

Diisopropyl ether and propylene were obtained as products, and the total conversion was 60%. The selectivity to diisopropyl ether was 95 mo1%.

Claims (1)

[Claims] 1) The specific surface area is about 100 to about 1000 m^2/g, and the pore volume is about 0.1 to about 1 cm^3/g,
The average pore diameter is about 10 to about 100 Å, and the Ni/Si
The ratio of nickel to silicon expressed as approximately 0.0
A catalyst comprising a nickel-containing hectorite-like material, characterized in that the ratio of lithium to silicon expressed as Li/Si is from about 0.01 to about 0.3. 2) Prepare slurry by adding divalent metals such as magnesium, cobalt, zinc, copper, iron, manganese, lead, cadmium, alkali metals, alkaline earth metals, fluorine, etc. to silicon, nickel, and lithium as necessary. Claims characterized in that the slurry is subjected to a hydrothermal reaction at 100 to 350°C, the obtained hydrothermal reaction product is filtered, dried at 300°C or less, and pulverized, sized, or granulated. 1st
A method for producing a catalyst comprising a nickel-containing hectorite-like substance as described in 1. 3) The method according to claim 2, characterized in that aluminum, titanium, zirconium, tin, indium, and gallium are added when preparing the slurry. 4) The method according to claim 2, characterized in that a noble metal such as gold, silver, platinum, or palladium is added when preparing the slurry. 5) After filtration of the hydrothermal reactant, ion exchange is performed with trivalent metal ions such as alkali metal ions, alkaline earth metal ions, transition metal ions, rare earth metal ions, and aluminum. Method described. 6) After filtration of the hydrothermal reactant, ion exchange with alkyl quaternary ammonium ion, alkyl tertiary ammonium ion, alkyl secondary ammonium ion, alkyl primary ammonium ion, etc. and baking at 100 to 1000°C. The method according to claim 2, characterized in that: 7) The method according to claim 2, wherein after pulverization, a thermoplastic resin and a thermosetting resin are mixed and granulated. 8) After crushing, sodium silicate, aluminum silicate, silica powder, aluminum phosphate, kaolin, bentonite, apatalgite, talc, pyrophyllite,
The method according to claim 2, characterized in that the granulation is carried out by mixing an inorganic substance such as acid clay. 9) The method according to claim 2, characterized in that during granulation, pressure is applied at a pressure of 1000 kg/cm^2 or less. 10) The method according to claim 8, characterized in that during granulation, pressure is applied at a pressure of 1000 kg/cm^2 or less. 11) The method according to claim 2, which comprises firing at 100 to 1000°C after granulation or granulation. 12) The method according to claim 7, which comprises firing at 100 to 1000°C after granulation. 13) The method according to claim 8, which comprises firing at 100 to 1000°C after granulation.