JPH0416236A - Preparation of metal-supporting carrier - Google Patents

Abstract

PURPOSE:To obtain a carrier especially enhanced in its adsorbing capacity of a sulfur compound by heat-treating clay mineral within a specific temp. range at first to change the structure thereof and exchanging the magnesium ion of the clay mineral with a transition metal ion. CONSTITUTION:When double chain structure type clay mineral is heat-treated at 400-800 deg.C at first, the water present in the tunnels of the structure of this clay mineral is removed and, next, the bonding force of octahedral Mg-O of the MgO layer constituting a crystal is lowered and a magnesium ion becomes easy to elute in water. Herein, the clay mineral is immersed in an aqueous solution containing a transition metal ion such as Co<2+> or Ni<2+> to easily exchange the magnesium ion with the transition metal ion. Therefore, a carrier capable of adsorbing a sulfur compound by the formation of a complex of the transition metal ion and sulfur is obtained.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a clay mineral metal-supported support having a double-chain structure, which contains a large amount of transition metals such as copper, cobalt, iron, and nickel in its structure. . Furthermore, in detail, the adsorption capacity of the clay mineral carrier for sulfur-based compounds is significantly improved, and it is also provided with a function as a catalyst. Furthermore, in order to further enhance the catalytic function, it is necessary to support different types of catalytic metals on the carrier. The present invention relates to a method for producing a metal-supported carrier in which iron or copper is easily and inexpensively introduced into the multi-chain clay mineral.

[Conventional technology]

Multi-chain clay minerals have traditionally had excellent adsorption ability for gases and liquids, and have been used as catalysts for chemical reactions and purification adsorbents.

For example, sepiolite was used as a chemical reaction catalyst by supporting metals by the method disclosed in ``Catalyst for Hydrogenation of Hydrocarbons'' (Japanese Patent Laid-Open No. 53-34691).

In this method, the structure of a sepiolite carrier that has been dried at a low temperature is broken down with a strong acid at a low temperature, and ions of lanthanide, iron, etc. used as a catalyst are supported on the sepiolite carrier.

However, in the second method, the amount of metal ions supported is small and sufficient catalytic activity cannot be obtained. Furthermore, when attempting to cause various catalytic reactions by using sepiolite as a carrier to support various catalytic metals other than those mentioned above, it has been difficult to support other catalytic metals on sepiolite. This is because the disclosed method lacks metals such as lanthanide and iron, which serve as cores when supporting different types of catalyst metals. Additionally, there was a risk that the crystal structure of the multi-chain clay mineral would be destroyed by the strong acid. Furthermore, since strong acids are used, it is necessary to invest in manufacturing equipment and environmental purification, resulting in high manufacturing costs.

[Purpose of the invention]

As shown above, in the conventional method, the amount of transition metal supported was small, and the catalyst activity, in particular, could not exhibit sufficient performance against sulfur compounds.

In view of the shortcomings of conventional manufacturing methods, the present inventors have conducted extensive research to develop a manufacturing method for a multi-chain clay mineral metal support that has particularly improved adsorption performance for sulfur-based compounds. As a result, it was discovered that this could be achieved by a heat treatment method.

[Structure of the invention]

In the method for producing a double-chain structure mineral metal support of the present invention, the structure of a double-chain structure clay mineral is changed, and magnesium ions in the structure of the clay mineral are ion-exchanged with other transition metal ions. In the method for producing a chain structure type clay mineral metal support, the clay mineral is heated at a temperature of 400°C or higher to 800°C.
It is characterized in that the structure of the clay mineral is changed by heat treatment at the following temperature.

[Action of the invention]

Multi-chain clay minerals change from crystalline structure to amorphous structure due to heat. This structural change occurs from 400℃ to 800℃
It happens in First, the water in the tunnels in the structure of the clay mineral escapes. Next, the binding force of Mg-0 in the octahedron of the Mg0=layer that constitutes the crystal decreases, and magnesium ions become easily eluted in water. Here, Co”
When this is immersed in an aqueous solution containing transition metal ions such as Ni"Fe'+ and Cu2", it is possible to easily ion-exchange the magnesium ions with reduced binding strength with a large amount of transition metal ions.

The multi-chain clay mineral metal support supporting transition metal ions in this manner adsorbs sulfur compounds through a complex formation reaction between the transition metal ions supported in its structure and sulfur. Furthermore, ammonia and amine compounds can be adsorbed by reaction with hydroxyl groups present on the surface of the clay mineral. The adsorbed compound further reacts and changes due to the catalytic action of the supported metal. For example, hydrocarbon,
Nitrogen oxides and sulfur oxides are decomposed by this reaction.

Further, the supported metal becomes the core when supporting a new catalyst metal on a double-chain structure type clay mineral. It is difficult to support such a catalytic metal in the absence of a supported metal serving as a core.

〔Effect of the invention〕

According to the present invention, a metal-supported carrier having sufficient adsorption performance and catalytic activity for both nitrogen compounds and sulfur compounds can be easily produced in large quantities. Furthermore, when trying to impart a new catalytic ability by supporting a new catalytic metal, the supported metal becomes a core for supporting the new catalytic metal and can easily support the new catalytic metal. In addition, since strong acids and strong bases are not used, manufacturing costs can be reduced with less investment in manufacturing equipment and environmental purification.

[Other inventions]

The heat treatment temperature of the present invention is preferably 400°C to 800°C. If the temperature is lower than 400°C, the structure of the clay mineral cannot be sufficiently changed. At temperatures exceeding 800°C, the structure of the clay mineral changes to a stable enstatite crystal structure,
There is no way to sufficiently support the metal. Further, in the present invention, when dispersing the clay mineral in water, the amount of water is 1
It is preferable that the amount is 0 times by weight or more. If the amount is less than this, the clay mineral will be poorly dispersed and it will be difficult to support the metal uniformly. In the present invention, transition metals are preferred as the metals to be supported on the double-chain structure type clay mineral in view of the need to adsorb sulfur compounds. Among them, cobalt, nickel, iron and copper are particularly suitable in view of availability and price. When these metal salts are added to the dispersion, the amount added is suitably 5 parts by weight to 70 parts by weight. If the amount added is less than this, the amount of metal supported will be reduced, there will be almost no reaction with sulfur compounds, and the effectiveness as a sulfur compound adsorbent will be significantly reduced. Further, even if the amount added is increased from this value, the amount of metal supported will not increase. Preferably it is 30 to 60 parts by weight. The salts of these metals can be added by any commonly used addition method, such as directly adding the salt itself or adding Gorera salt as an aqueous solution. As a method for extracting the metal-supported carrier of the present invention, any commonly used method such as washing with water, filtration, drying, etc. may be used.

Further, as the double-chain structure type clay mineral of the present invention, sepiolite, palygorskite, and attapulgite can be used. Its structure is sepiolite (S i 1
2) (Mgs) 030 (
OH)4 (082)・8H20, attapulgite and palygorskite (MgAf)5 (S
1Af)s 02G(OH)2 ・8H20.

There are no particular limitations on the shape or size of the clay mineral used in the present invention.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to examples, but the present invention is not limited to these examples in any way unless it exceeds the gist thereof.

(Example 1) Sepiolite from Turkey was used as the double-chain structure type clay mineral.

The second sepiolite was placed in an alumina crucible and heat treated in a Nichrome furnace at a temperature ranging from 400°C to 800°C for 4.5 hours.

30g of sepiolite heat-treated at a predetermined temperature was collected,
The mixture was placed in a household mixer, 900 cc of ion-exchanged water was added, and the mixture was operated for 10 minutes to fully disperse sepiolite in the ion-exchanged water. After that, chloride steel (CuC1*-2
Hz O) from 5 to 7 per 100 parts by weight of sepiolite.
After adding 0 parts by weight, the mixer was operated again for 5 minutes to uniformly dissolve and mix the copper chloride. A mixed suspension consisting of a copper chloride solution and sepiolite was stirred for 30 minutes using a disper to cause the copper ions to react sufficiently with the sepiolite.

After the reaction, suction filtration was repeated several times to thoroughly wash and remove chlorine ions and the like. Thereafter, it was dried at 100° C. for 15 hours to prepare the metal-supported carrier of this example.

As described above, the amount of supported metal in the prepared metal supported support was examined by atomic absorption spectroscopy.

Furthermore, an adsorption test for hydrogen sulfide (N2S), which is a sulfur compound, was conducted using the metal support prepared as described above.

In the gas adsorption test, the metal-supported carrier prepared as described above was placed in a gas-impermeable odor bag with a capacity of 101 kg at 1° Og, and after sealing the odor bag, hydrogen sulfide with a concentration of 110,000 pp was added at 101 g.
I put it in. Thereafter, the gas concentration in the gas-impermeable odor bag was measured using a milk-type gas detection tube. The amount of gas adsorption was determined from the concentration when the gas concentration in the gas-impermeable odor bag stopped changing. The results are shown in Table 1 ThA-1 to ThA-10.

In addition, as a comparative example, we used Turkish sepiolite that was not heat-treated and dried at 100°C as it was.
NαR-1), a carrier-free reagent copper chloride itself (
N11R-2) and Turkish sepiolite at 200℃
Metal support carriers (R-3, R-4, R-7) produced by heat treating at 1350°C and 900°C and adding 60 and 45 parts by weight of chlorinated steel to 100 parts by weight of sepiolite.
Furthermore, Turkish sepiolite was heat treated at 650°C, and copper chloride was added to 4 and 2 parts by weight per 100 parts by weight of sepiolite.
Metal-supported carriers prepared by adding parts by weight (R-5, R-6
) was determined. The results of the second test are shown in Table 1.

The hydrogen sulfide gas adsorption capacity of this example was 2 to 1O times that of the sepiolite carrier, and 100 to 500 times that of chloride steel itself.

In addition, Comparative Examples R-3 to R-7 in which the heat treatment temperature or amount of supported metal was inappropriate showed almost the same performance as the support itself or the chloride steel itself (Table 1, Table 2 (Example 3) 650°C Cobalt chloride (
The metal support of this example was prepared in the same manner as in Example 1, except that 601 L parts of Co C1 * 6 Hz O) were added (NIC).

Further, as a comparative example, a metal-supported carrier was prepared by heat-treating at 650° C. and adding 5 parts by weight or less of cobalt chloride to sepiolite (=&R-10).

The hydrogen sulfide gas adsorption capacity of these carriers was measured and shown in Table 2. The carrier of this example was not treated with a supported metal salt.

(Example 2) Using Turkish sepiolite heat-treated at 650°C for 4.5 hours, nickel chloride (NiCz
2-6H20) per 100 parts by weight of sepiolite.
The metal-loaded carrier of this example was prepared in the same manner as in Example 1, except that 0 was added in some portions (Seed B).

In addition, as a comparative example, a metal supporting carrier was prepared by heat-treating at 900'C and adding 70 parts by weight of nickel chloride to 100 parts by weight of sepiolite.
The amount of hydrogen sulfide gas adsorbed was tested in the same manner as 1J1. The results are shown in Table 2. This table shows the results of a similar test on the reagent nickel chloride itself (&R-9
) was also shown. The hydrogen sulfide gas adsorption ability of this example was approximately 50 times that of a comparative example that was subjected to inappropriate heat treatment, and approximately 500 times as excellent as that of nickel chloride itself.

The adsorption capacity was approximately 6 times higher than that of the comparative example, which had an inappropriate amount of adsorption.

(Example 4) Ferrous chloride (Fe
Except for adding 60 parts by weight of C#2 ・nHz O),
The metal support of this example was prepared in the same manner as in Example 1.

The adsorption amount of hydrogen sulfide gas on the second carrier was determined in the same manner as in Example 1 and is shown in Table 2 N (LD).

The metal-supported carrier of this example exhibited performance that was about 15 times as excellent as that of the sepiolite carrier itself of Comparative Example R-1, and about 790 times as excellent as that of the copper chloride reagent of Comparative Example R-2.

Claims (1)

[Claims] In a method for producing a multi-chain structure type clay mineral metal-supporting support, the structure of the multi-chain structure type clay mineral is changed and magnesium ions in the structure of the clay mineral are ion-exchanged with other transition metal ions. A method for producing a double-chain structure type clay mineral metal-supporting carrier, characterized in that the structure of the clay mineral is changed by heat treatment at a temperature of 800° C. or higher.