JPS60166033A - Desulfurizing agent - Google Patents

Abstract

PURPOSE:To obtain a desulfurizing agent by which a sulfide contained in a reducing gas is removed effectively and which can be regenerated and used repeatedly by using manganese nodule. CONSTITUTION:A manganese nodule is used as a desulfurizing agent having excellent adsorption performance and regeneration efficiency. The manganese nodule is porous generally and an amorphous transition-metal oxide (hydroxide) and its essential component is Mn and Fe, and as a trace element, Ni, Co, Cu and Ti, etc. are contained by about 0.1-1.0% respectively. In the manganese nodule as desulfurizing agent in this method, the total of Mn and Fe is contained >=50% expressed in terms of MnO2 and Fe2O3. Since the adsorption capacity is increased and also the manganese nodule can be regenerated for a short time in comparison with conventional iron ore, manganese nodule is the desulfurizing agent having excellent adsorption performance and regeneration efficiency.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a desulfurization agent, and particularly to a desulfurization agent that can efficiently remove sulfides contained in reducing gas and can be repeatedly recycled and used.

High crude oil prices and heavier imported crude oil have darkened the outlook for Japan's energy and chemical raw materials.

As a response to this problem, the use of carbon monoxide (CO) and hydrogen (H2) obtained by gasifying the residue obtained by distilling light components from crude oil, so-called distillation residue, or coal, as a raw material, is being considered. In other words, there is a method of directly using Co and H! as fuel, a method of synthesizing this gas into liquefied fuel, and a method of converting it to ethylene, propylene, acetic acid, etc. that were conventionally obtained from petroleum (naphtha). Alternative energy policies are being launched.

Sulfur compounds in heavy oil and coal are converted into sulfides, mainly H,8 (about 10% is 00B) during gasification reactions,
It mixes into reducing gases such as co and H. In the case of fuel, sulfur oxides are a source of air pollution, and in the case of synthetic raw materials, catalysts are poisoned, so various purification methods have been proposed and some are currently in use.

One of them is the wet method, which is a process that chemically absorbs and removes hydrogen sulfide. This method requires cooling the gas in order to absorb hydrogen sulfide into the solution, which poses problems such as energy loss, regeneration of the absorption liquid, and wastewater treatment.

Another method is a so-called dry method in which K is adsorbed using an adsorbent (for example, iron oxide, molybdenum oxide, etc. are known), desorbed as an oxide with oxygen, and the adsorbent is regenerated and used repeatedly. A law is proposed. .

The present invention relates to a sulfur compound adsorbent applied to this dry method.

Iron oxide has been well known as a desulfurization agent. Iron ore itself has desulfurization performance as iron oxide, but H, S
The adsorption amount of +0OEI is small, it takes a long time for adsorption and regeneration, and it has the disadvantage that it becomes powder due to repeated adsorption and regeneration.

In view of the current situation, the inventors of the present invention have made earnest efforts to develop an adsorbent that (1) has a large adsorption capacity, (2) can be regenerated in a simple manner in just two hours, and can be used repeatedly. The present invention was achieved by discovering that manganese nodules are a substance that satisfies the above objectives.

Manganese nodules are generally porous, almost amorphous transition metal oxides (hydroxides) whose main components are Mn and IF.
e and υ as a trace component.

Co, Ou, TI, etc. are contained in a of about 1 to 1.0% each. In the manganese nodule as a desulfurization agent in the present invention, Mn and 'Pe are MnO2 and P'92
The total is 50% or more when converted to 0.03.

Hereinafter, the adsorbent of the present invention will be explained according to Examples.

Example 1 The sample was prepared by crushing the manganese nodules shown in the table below.
The particles that had been sized with mesh to 24 mesh buttons were used.

Chemical composition of manganese nodules (wt%) A quartz tube with an inner diameter of 15 fins was used as the reaction tube, and 20 samples were filled inside.
N2 days 0.3%, H as gas to be treated from the upper part of the reaction tube
210%, 0025%.

Synthesis gas consisting of 13% CO, 2% H2O, and 59.7% N was fed at a flow rate of 601 Jt/H. The reaction temperature is 4
The removal rate of hydrogen sulfide was measured at 00°C. The removal rate is the rate of decrease in hydrogen sulfide concentration at the inlet and outlet of the adsorbent packed bed. For comparison, iron ore was also measured.

As a result, the amount of hydrogen sulfide adsorbed until the hydrogen sulfide removal rate reached 80% was 15.7 mmot% (56 mmot) for iron ore and manganese nodule, respectively.

Furthermore, Fig. 1 shows the change over time in the hydrogen sulfide removal rate. 1st
From the figure, the time for which the H2S removal rate can be maintained at 90% or more is 88 minutes for iron ore (B), compared to 88 minutes for manganese nodile).
It turned out that the time was 138 minutes, a huge improvement.

Example 2 Immediately after the absorption operation according to Example 1 was completed and the N2 gas was turned off, the remaining N! While a carrier gas consisting of The output SO and concentration of the packed bed were measured, and the amount of desorption was calculated.

This result is excessive as shown in Figure 2, and the amount of sulfur desorbed is 149 m for each of iron ore and manganese nodules.
mot, 21.2 mmot, and it was found that the time required for desorption was approximately the same. In this way, the sulfur content was desorbed and the adsorbent was regenerated.

As shown in the examples above, manganese nodules have increased adsorption capacity and can be regenerated in approximately the same time compared to conventional iron ore, proving that it is a desulfurization agent with good adsorption performance and regeneration efficiency. It was done.

[Brief explanation of the drawing]

FIG. 1 and FIG. 2 are diagrams showing the performance test results of the desulfurizing agent of the present invention. Sub-agents 1) Meifuku agent Ryo Hagiwara -

Claims (1)

[Claims] A desulfurizing agent for removing sulfides in reducing gases consisting of manganese nodules.