JPS6118433A - Catalyst for synthesizing hydrocarbon - Google Patents

Abstract

PURPOSE:To increase the catalytic activity for reducing carbon monoxide with hydrogen by depositing cobalt or cobalt and lanthanum on a carrier consisting of zeolite to mold the catalyst for synthesizing hydrocarbons. CONSTITUTION:A catalyst for synthesizing hydrocarbons is molded by depositing cobalt or cobalt and lanthanum on a carrier consisting of zeolite which is hydrated inosilicate minerals of porous magnesium. As the shape of the carrier, a granular body, a platelike body, a pelletized body and a honeycombed body or the like are used. As the method for depositing cobalt and lanthanum on the zeolite carrier, for example, the zeolite carrier is immersed into an aq. soln. of metallic salts of catalytic components such as cobalt nitrate, lanthanum nitrate, cobalt chloride and lanthanum chloride and the drying plus calcining thereof are performed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a catalyst for hydrocarbon synthesis, which is used when synthesizing hydrocarbons such as butane by hydrogen reduction of -oxidation return element.

[Conventional technology]

The above-mentioned hydrocarbon synthesis catalyst conventionally used on an industrial scale is called Fischer-Drohr'7S/bisynthesis catalyst. Catalysts are used in which nickel, cobalt, iron, etc. are supported on carriers such as silica, alumina, and diatomaceous earth.

However, even such conventional catalysts cannot be said to have satisfactory activity. Furthermore, when diatomaceous earth is used as a carrier in the conventional catalyst described above, the method for preparing the catalyst is difficult and the reproducibility of the catalyst activity is low. That is, a precipitation method is used as a method for preparing a catalyst using diatomaceous earth as a carrier.

In this method, the catalyst components are prepared as an aqueous solution in the form of nitrates, sulfates, etc., diatomaceous earth is added to the solution, and the aqueous solution of kernels is then made basic to precipitate the catalyst components on the surface of the diatomaceous earth. however.

The method for preparing a catalyst by such a precipitation method is difficult to prepare, such as the conditions during precipitation, and the reproducibility of the catalyst activity is low.

゛Again. When silica or alumina is used as a support in such conventional catalysts, thorium oxide ('l'hO,'') is used as a promoter in order to increase the activity and selectivity to hydrocarbons.

However, thorium contained in such promoters exists only in rare quantities as a resource. moreover.

Since this thorium is a nuclear fuel material, an "internationally controlled substance use permit" or a "nuclear fuel material use permit" is required to use it.

It must be kept to a minimum.

[Problem that the invention seeks to solve]

The present invention has excellent activity without using thorium,
The present invention also provides a catalyst for hydrocarbon synthesis that is easy to prepare.

[Means for solving problems]

The present invention is a catalyst for hydrocarbon synthesis, using sepiolite as a carrier and supporting cobalt or cobalt and lanthanum on the carrier to synthesize hydrocarbons by reducing oxidized carbon with hydrogen. .

Sepiolite is a porous magnesium hydrated inosilicate mineral, naturally occurring as a secondary mineral in limestone, and its composite material can also be synthesized from magnesium salts and silicate compounds. I can do it. In the present invention,
The above sepiolite.

Both natural products and synthetic products can be used.

The shape of the carrier is 1 grain, plate, pellet,
Examples include honeycomb-shaped bodies, and there are no particular limitations. At that time 1
As a method for producing a granular carrier, it is preferable to dry sepiolite at a temperature of 100 to 160° C. to remove attached moisture, and then crush the sepiolite into a single granule. In addition, the particle size is preferably in the range of 1 to i o op in order to improve moldability.

In addition, as a method for manufacturing carriers such as plate-shaped bodies and pellet-shaped bodies, one granular sepiolite is mixed with polyvinyl alcohol
The slurry is kneaded with a thickening material such as an aqueous solution to form a soufflee, and the slurry is formed into a plate shape, pellet shape, etc., and then heated to evaporate and burn out the thickening material. Further, the slurry of sepiolite described above may be coated on the surface of a honeycomb-shaped substrate made of cordierite, alumina, etc., and then heated to form a honeycomb-shaped carrier. Further, the specific surface area of the carrier is 50 to 100
A range of om/g is desirable. When the specific surface area is outside this range, it is difficult to exhibit excellent activity.

The above sepiolite carrier is coated with cobalt (Co) which is a catalytic component.
), lanthanum (La) is supported in the same manner as in the case of supporting ordinary catalyst components.2 For example, cobalt nitrate, lanthanum nitrate, cobalt chloride, lanthanum chloride, sulfuric acid <y), e [The above sepiolite is immersed in an aqueous solution of a metal salt of a catalyst component such as lanthanum, dried, and calcined. As a result of the above-mentioned calcination, the metal salts become respective catalytic components. This supported catalyst component is composed of conortane or coba/1/) tranthanum, and lampt4
It is often in the lanthanum oxide state. In addition, Koba lv
) and lanthanum 9 Examples 1 For example, in the method of immersing the carrier in an aqueous solution of the metal salt of the catalyst component described above, two types of aqueous solutions may be used for each.
An aqueous solution containing a mixture of both metal salts may be used to simultaneously support the metal salts.

In addition, when supporting, the point at which the catalyst component is supported on the carrier is 1 to 20% by weight when only cobalt is supported, and 0.05 to 6% by weight when supporting lanthanum. It is desirable to set it as weight%. If the supported amount is less than the above range, sufficient catalytic activity may not be obtained, but the above-mentioned l'i properties may not be obtained, and the cost will be high. In the case of carrying both a co-metal and a lanthanum, the ratio of lanthanum to the co-metal is preferably 5 to 50% by weight. However, if the above ratio is less than 5% by weight, there is a possibility that the catalyst activity will not be improved by supporting lanthanum. Furthermore, if the ratio is greater than 50%, the selectivity of C6 or higher will be poor, making it difficult to produce C3 or higher hydrocarbons with high efficiency.

The catalyst according to the present invention is in the form of two particles or a pellet.

It does not matter the shape or structure, such as a honeycomb-like body. Also.

The catalyst has a reaction temperature of 10% as in the case of the conventional catalyst.
0-300℃ 1 reaction pressure 1-20 atm, space velocity 200
It is desirable to use it for ~2000 hr-.

〔Effect of the invention〕

The catalyst according to the present invention can perform hydrogen reduction at a rate of 11 L of -carbon oxide, and can produce hydrocarbons of 01 or higher, such as methane and phethane, with good yield.

In particular, liquid hydrogen ash of 06 or higher can be produced with good yield. Moreover, this effect is superior to that of a catalyst using thorium. In addition, since thorium is not used, it is not subject to the above-mentioned legal regulations, and an inexpensive catalyst can be provided. Also, since the catalyst according to the present invention uses sepiolite as a carrier, The method for preparing the catalyst is simple and simple, and the reproducibility of the catalyst activity (conversion rate 1 selectivity) is also excellent.

However, the catalyst that supports cobalt 1vF and lanthanum as catalyst components has superior activity in terms of selectivity, with a Co conversion rate of 106 or higher, compared to the catalyst that supports only cobalt (see Examples). .

〔Example〕

Two aspects of the present invention will be described in detail below.

Example 1゜ Sepiolite according to the invention is used as a carrier.

A Co catalyst supporting CO was prepared. That is.

The pellet-shaped sepiolite carrier was immersed for 15 minutes in an aqueous solution consisting of 42% Coba nitrate/7% (the same weight ratio below) and 58% water, and the mother liquor was thoroughly removed.

It was dried at 110°C for 10 hours, and then fired at 400°C for 6 hours. Thereby, a pellet-shaped catalyst (catalyst seat 1 shown in Table 1) having a diameter of 2 to 3 φ according to the present invention and supporting 4% of Go was prepared.

Note that the sepiolite carrier has a pore volume of 0.487c.
7f(/, specific surface area 100 doors/(1, average pore radius 0
．． 01μ (measured by mercury porosimetry).

In addition, for comparison, a catalyst using diatomaceous earth as a carrier [(catalyst volume 8
1) was prepared as follows. That is.

First, 200 g of cobalt nitrate was dissolved and boiled in 500 CO of water. In addition, powdered diatoms as a carrier ±6
Add 0g to 200cc of water and boil.

Next, the above-mentioned boiling liquid containing cobalt nitrate was added to this. Next, a solution prepared by dissolving 150 f of potassium carbonate in 500 cc of water was gradually added to the vigorously stirred solution containing cobalt nitrate, diatomaceous earth, etc.

After boiling with stirring for about 10 minutes, the solution was filtered, and the mill residue was washed with ion-exchanged water until potassium ions disappeared. Next, the remainder of the five units was dried at 2110° C. for 20 hours and formed into a pellet-like body with a diameter of 2 to 3 flφ to prepare a catalyst in which 67% of Coo was supported on diatomaceous earth.

Next, the catalytic activity of the above two types of catalysts was evaluated. To evaluate the catalytic activity, a stainless steel reaction tube with an inner diameter of 18 flφ was filled with 20 ml of the above catalyst.
Hydrogen reduction at 0°C for 1 hour, then 9 reaction temperature 220°C9
Reaction pressure 5 kg/d < gauge), contact time 68.1 h
hydrogen (■2)/-carbon oxide (C
O) Mo μ ratio B A mixed gas of B was introduced into the reaction tube, and the conversion rate of -carbon oxide and the amount of hydrocarbons in the reaction product were measured. Here, the term "carbon oxide conversion rate" refers to the rate (%) of carbon monoxide converted into other substances.

Also, the hydrogen ash in this converted reaction product.

C2°C expressed as the elementary amount in one molecule of hydrocarbon
3. Regarding C,, C5, etc., # is shown in the gas chromatogram.
), Co, and Cot. The above C7 means methane, 102 means ethane, ethylene, CG means propane, propylene+04 means butane, butylene 105 means pentane, etc. Note that hydrocarbons of C6 or higher were measured all at once.

The results of these measurements are shown in Table 1. In the same table.

The generation ratio (selectivity %) of the above C1 to C4 and C5 or higher hydrogen ashing is shown.

As is known from Table 1, 9 CO of the catalyst according to the present invention
It can be seen that the conversion rate of is higher than that of the comparative catalyst. Furthermore, it can be seen that the catalyst according to the present invention has a higher selectivity of 06 or more and has excellent activity compared to the comparative catalyst.

Table 1 Example 2゜9 Co according to the present invention using heptabiolite as a carrier
-La catalyst was prepared and the catalytic activity was measured.

That is, sepiolite carrier 9 was prepared under the same conditions as in Example 1, except that 4% of 3a and 1% of La were supported using an aqueous solution of Coba/L' nitrate and an aqueous solution of lanthanum nitrate.

A pellet-shaped catalyst according to the present invention (catalyst rod 2 in Table 2)
was prepared.

For comparison, a comparative catalyst was prepared in the same manner as the comparative catalyst of Example 1, using diatomaceous earth as a carrier and using a mixed solution of cobatium nitrate and lanthanum nitrate to support 0067% and ][, a12%. (Catalyst &82) was prepared.

Next, the activity of the catalyst described above was evaluated in the same manner as in Example 1. The measurement results are shown in Table 2.

As shown in Table 2, the catalyst according to the present invention is:
It can be seen that the CO conversion rate is superior to that of the comparative catalyst. In addition, regarding the 1 selectivity, it can be seen that the catalyst of the present invention has an excellent activity in that the 9 selectivity for C6 or more is higher than that of the comparative catalyst.

Table 2

Claims (1)

[Claims] A hydrocarbon synthesis catalyst for synthesizing hydrocarbons by reducing carbon monoxide with hydrogen, which comprises sepiolite as a carrier and cobalt or cobalt and lanthanum supported on the carrier.