CN112940795A - Iron-based desulfurizer for blast furnace gas and preparation method thereof - Google Patents

Abstract

The invention discloses an iron-based desulfurizer for blast furnace gas, which comprises the following main raw materials: 30-50wt% of ferrous sulfate, 20-30wt% of calcium hydroxide, 10-40wt% of carbide slag, 5-15wt% of fly ash and 5-15wt% of sawdust. The solid reacts in the kneading and forming process to generate a desulfurizer precursor, and then the desulfurizer precursor is naturally oxidized into a finished desulfurizer product. The desulfurizer prepared by the method has high sulfur capacity, working sulfur capacity of 35-45wt%, saturated sulfur capacity of 60-70wt%, simple preparation process, no waste water and waste residue in the production process, low production cost and suitability for large-scale production.

Description

Iron-based desulfurizer for blast furnace gas and preparation method thereof

Technical Field

The invention relates to the technical field of gas purification, in particular to an iron-based desulfurizer for blast furnace gas and a preparation method thereof.

Background

The blast furnace gas generally contains a large amount of COS and H₂And (4) S gas. The blast furnace gas is directly combusted or used as chemical raw material gas, sulfide in the blast furnace gas can poison subsequent catalysts, and simultaneously, a large amount of SO can be generated by combustion₂The subsequent treatment cost is very high for the standard discharge.

Before the blast furnace gas is combusted or used as a chemical raw material gas, a desulfurization process is additionally arranged, so that the purification cost can be obviously reduced, and equipment and subsequent catalysts are protected. At present, the desulfurization of blast furnace gas generally adopts organic sulfur hydrolytic agent to convert COS into H₂S, then using a desulfurizing agent to react H₂And (4) S absorption. Blast furnace gas de-H₂S generally adopts an active carbon desulfurizer or an iron oxide desulfurizer, and the active carbon desulfurizer has higher price and is not suitable for a production process with large gas quantity of blast furnace gas and huge desulfurizer consumption; the common ferric oxide desulfurizer has low sulfur capacity, generates waste water and waste residue in the production process, and is not suitable for large-scale production and use. Currently, the production and use of iron oxide desulfurizers are severely limited.

Disclosure of Invention

Aiming at the problems in the related art, the invention provides an iron-based desulfurizer for blast furnace gas and a preparation method thereof, which solve the problems of low sulfur capacity, high production cost and waste water and waste residue discharge in the production process of the existing desulfurizer.

In order to achieve the technical purpose, the technical scheme of the invention is as follows:

an iron-based desulfurizer for blast furnace gas comprises the following main raw materials: 30-50wt% of ferrous sulfate, 20-30wt% of calcium hydroxide, 10-40wt% of carbide slag, 5-15wt% of fly ash and 5-15wt% of sawdust.

Further, the raw material of the desulfurizing agent also comprises ammonium bicarbonate solid.

A preparation method of an iron-based desulfurizer for blast furnace gas comprises the following steps:

s1, mixing ferrous sulfate solid, calcium hydroxide powder, carbide slag, fly ash and sawdust according to the mass ratio: (25-50): (20-30): (10-40): (5-15): (5-15), adding the mixture into a reaction tank, and uniformly mixing to obtain a solid mixture a;

s2, dissolving ammonium bicarbonate solid in water to prepare an ammonium bicarbonate solution b with the concentration of 1-5%;

s3, injecting a ammonium bicarbonate solution b into a reaction tank of the solid mixture a, mixing and stirring the solid while injecting the ammonium bicarbonate solution until the solid matter becomes a mud state, continuously mixing and stirring for 2-3 hours, then stopping stirring, and aging for 12-24 hours to obtain a solid mud state matter c;

s4, extruding the aged solid mud-like object c into strips by using a hydraulic press to form a desulfurizer precursor d;

s5, directly drying the desulfurizer precursor d in the sun, and naturally oxidizing for 24-36 hours to obtain a finished desulfurizer product e.

The invention has the beneficial effects that: the main raw material of the iron-based desulfurizer is solid waste, waste is changed into valuable, no waste water and waste residue are discharged in the production process, and the prepared desulfurizer has high working sulfur capacity, low price and simple production process and is suitable for large-scale production.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.

FIG. 1 is a diagram of a sulfur capacity detecting apparatus for an iron-based desulfurizing agent for blast furnace gas according to the present invention.

In the figure:

1、H₂s, storing a gas cylinder; 2. a flow meter; 3. water vapourA saturator; 4. a reactor; 5. a first constant-temperature water bath device; 6. a second constant-temperature water bath device; 7. and a buffer tank.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.

An iron-based desulfurizer for blast furnace gas comprises the following main raw materials: 45wt% of ferrous sulfate, 20wt% of calcium hydroxide, 20wt% of carbide slag, 10wt% of fly ash and 5wt% of sawdust.

In this example, the desulfurizing agent feedstock also included 1kg of ammonium bicarbonate solids.

In this example, the ferrous sulfate is derived from titanium dioxide byproduct waste.

In the embodiment, the carbide slag is derived from waste slag generated by hydrolysis of carbide.

The preparation method of the iron-based desulfurizer for blast furnace gas is characterized by comprising the following steps:

s1, mixing ferrous sulfate solid, calcium hydroxide powder, carbide slag, fly ash and sawdust according to a mass ratio of 45: 20: 20: 10: 5, adding the mixture into a reaction tank, and uniformly mixing to obtain a solid mixture a;

s2, dissolving 1kg of ammonium bicarbonate solid in 20kg of water to prepare an ammonium bicarbonate solution b with the concentration of 5%;

s3, injecting a ammonium bicarbonate solution b into a reaction tank of the solid mixture a, mixing and stirring the solid while injecting the ammonium bicarbonate solution until the solid matter becomes a mud state, adding 6kg of the solution b in total, continuing mixing and stirring for 3 hours, stopping stirring, and aging for 24 hours to obtain a solid mud-like substance c;

s4, extruding the aged solid mud-like object c into strips by using a hydraulic press to form a desulfurizer precursor d;

s5, directly drying the desulfurizer precursor d in the sun, and naturally oxidizing for 36 hours to obtain a finished desulfurizer product e.

In this example, the obtained desulfurization agent product e was charged into the fixed bed reactor 4, and its sulfur capacity was measured. Wherein the sulfur capacity is detected according to the sulfur capacity test method of HG/T4354-2012 normal-temperature iron oxide, the detection temperature is 30 ℃, and the airspeed is 500-1000h^-1，H₂S concentration 3000-₂The concentration is 0.2-0.3%.

In this embodiment, the working sulfur capacity of the obtained desulfurizer product e can reach 35-45wt%, and the saturated sulfur capacity can reach 60-70 wt%.

In summary, the invention combines the current blast furnace gas desulfurization process flow in the steel industry to develop a high-efficiency iron-based desulfurizer, which is suitable for the desulfurization of blast furnace gas and other gas components in complex environments, has low production cost and no waste water and waste residue, and is suitable for large-scale production and use.

The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (3)

1. An iron-based desulfurizer for blast furnace gas is characterized by comprising the following main raw materials: 30-50wt% of ferrous sulfate, 20-30wt% of calcium hydroxide, 10-40wt% of carbide slag, 5-15wt% of fly ash and 5-15wt% of sawdust.

2. The iron-based desulfurizing agent for blast furnace gas according to claim 1, wherein said desulfurizing agent raw material further comprises ammonium bicarbonate solids.

3. The preparation method of the iron-based desulfurizer for blast furnace gas is characterized by comprising the following steps:

s1, mixing ferrous sulfate solid, calcium hydroxide powder, carbide slag, fly ash and sawdust according to the mass ratio: (25-50): (20-30): (10-40): (5-15): (5-15), adding the mixture into a reaction tank, and uniformly mixing to obtain a solid mixture a;

s2, dissolving ammonium bicarbonate solid in water to prepare an ammonium bicarbonate solution b with the concentration of 1-5%;

s3, injecting a ammonium bicarbonate solution b into a reaction tank of the solid mixture a, mixing and stirring the solid while injecting the ammonium bicarbonate solution until the solid matter becomes a mud state, continuously mixing and stirring for 2-3 hours, then stopping stirring, and aging for 12-24 hours to obtain a solid mud state matter c;

s4, extruding the aged solid mud-like object c into strips by using a hydraulic press to form a desulfurizer precursor d;

s5, directly drying the desulfurizer precursor d in the sun, and naturally oxidizing for 24-36 hours to obtain a finished desulfurizer product e.

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