CN114367182A - Low-hydrogen low-pressure sulfur-resistant deoxidation process for tail gas of submerged arc furnace - Google Patents

Low-hydrogen low-pressure sulfur-resistant deoxidation process for tail gas of submerged arc furnace Download PDF

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CN114367182A
CN114367182A CN202210050786.2A CN202210050786A CN114367182A CN 114367182 A CN114367182 A CN 114367182A CN 202210050786 A CN202210050786 A CN 202210050786A CN 114367182 A CN114367182 A CN 114367182A
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tail gas
submerged arc
low
arc furnace
deoxidation
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CN114367182B (en
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张艺馨
方芳
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Hubei Hegu Environmental Protection Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/104—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/408—Cyanides, e.g. hydrogen cyanide (HCH)

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Abstract

The invention provides a low-hydrogen low-pressure sulfur-resistant deoxidation process for tail gas of a submerged arc furnace, which comprises the following steps of: leading the tail gas of the submerged arc furnace into a purification tower filled with an oil removal agent for oil removal; introducing the tail gas of the submerged arc furnace after oil removal into a heat exchanger for heating; then, a vulcanizing agent is supplemented into the tail gas of the submerged arc furnace; and introducing the submerged arc furnace tail gas supplemented with the vulcanizing agent into a deoxidizing furnace filled with a deoxidizing agent for deoxidizing. The invention relates to a low-hydrogen low-pressure sulfur-resistant deoxidation process for tail gas of a submerged arc furnace to remove O2High efficiency, O in the inlet gas2When the content is less than or equal to 15000ppm, the deoxidation rate is more than 95 percent; the deoxidation process of the invention has strong toxicity resistance, can resist sulfur and remove O2The effect is not affected by aromatic hydrocarbon such as toluene and aliphatic hydrocarbon such as ethylene(ii) a In the high-efficiency removal of O2Simultaneously, HCN can be removed together, and a certain amount of organic sulfur can be converted; the deoxidation process has strong adaptability, and can effectively remove O in the feed gas under the conditions of low hydrogen even no hydrogen, low pressure and normal pressure2。

Description

Low-hydrogen low-pressure sulfur-resistant deoxidation process for tail gas of submerged arc furnace
Technical Field
The invention relates to the technical field of submerged arc furnace tail gas treatment, in particular to a low-hydrogen low-pressure sulfur-resistant deoxidation process for submerged arc furnace tail gas.
Background
The tail gas of the submerged arc furnace comprises lead and zinc smelting in non-ferrous smelting, black smelting and inorganic non-metal smeltingThe furnace tail gas, blast furnace gas, converter gas, ferroalloy furnace tail gas, calcium carbide furnace gas, yellow phosphorus tail gas and the like have the main components of CO with the content of over 50 percent, can be used as a valuable raw material of a carbonization chemical industry after being purified, and are used for producing chemical products with higher added values. However, the tail gas of the submerged arc furnace contains a lot of impurities, the main component of the tail gas is CO, and the tail gas also contains other impurities, such as inorganic sulfur (H)2S), aromatic hydrocarbons such as organic sulfur (COS), HCN, and toluene, aliphatic hydrocarbons such as ethylene, and dust, which provide new challenges to the efficient use of converter tail gas.
Comprehensive treatment and deep utilization of the tail gas of the submerged arc furnace are the direction of encouraging development of the country and tend to be great. The first prerequisite is the deep purification of the ore-smelting furnace tail gas, the existing method for removing sulfur in a targeted manner, and the O content of the ore-smelting furnace tail gas2One of the technical bottlenecks in comprehensive utilization of the tail gas of the submerged arc furnace, such as combined tempering and the like, is O in the tail gas of the submerged arc furnace2And (4) removing. The tail gas of the submerged arc furnace such as converter tail gas, metallurgical tail gas and the like is utilized to produce chemical products, and the oxygen content has serious adverse effect on subsequent processes and must be removed in advance. At present, the commonly used gas purification deoxidizers mainly comprise 3 methods of catalytic deoxidation, chemical absorption deoxidation, carbon combustion deoxidation and the like. The traditional deoxidation catalyst comprises three main types of copper, nickel, precious metal and the like, which need to be desulfurized firstly, and easily causes the problems of long process flow, large equipment investment, easy poisoning of the catalyst, short service life and the like in the comprehensive utilization project of the tail gas of the submerged arc furnace such as toughening co-production and the like. Although the traditional sulfur-resistant deoxidation process can resist sulfur, the deoxidation effect is not ideal under the conditions of low pressure and low hydrogen.
Based on the defects of the prior deoxidation of the tail gas of the ore-smelting furnace, the improvement is needed.
Disclosure of Invention
In view of the above, the invention provides a low-hydrogen low-pressure sulfur-resistant deoxidation process for submerged arc furnace tail gas, so as to solve the technical problems in the prior art.
In a first aspect, the invention provides a low-hydrogen low-pressure sulfur-tolerant deoxidation process for tail gas of a submerged arc furnace, which comprises the following steps:
leading the tail gas of the submerged arc furnace into a purification tower filled with an oil removal agent for oil removal;
introducing the tail gas of the submerged arc furnace after oil removal into a heat exchanger and heating to 150-350 ℃;
then, a vulcanizing agent is supplemented into the ore smelting furnace tail gas, and the sulfur content in the ore smelting furnace tail gas is controlled to be more than or equal to 20 multiplied by 10-6；
And introducing the submerged arc furnace tail gas supplemented with the vulcanizing agent into a deoxidizing furnace filled with a deoxidizing agent, and deoxidizing at 200-400 ℃.
Preferably, in the low-hydrogen low-pressure sulfur-tolerant deoxidation process of the submerged arc furnace tail gas, the degreasing agent is an HGT-12 type degreasing agent.
Preferably, the low-hydrogen low-pressure sulfur-tolerant deoxidation process is carried out on the submerged arc furnace tail gas, and the deoxidizer is an HGT-601 type deoxidizer.
Preferably, the submerged arc furnace tail gas low-hydrogen low-pressure sulfur-tolerant deoxidation process comprises a vulcanizing agent comprising dimethyl disulfide or carbon disulfide.
Preferably, the low-hydrogen low-pressure sulfur-tolerant deoxidation process for the submerged arc furnace tail gas further comprises before introducing the submerged arc furnace tail gas into a purification tower filled with an oil removal agent: and introducing the tail gas of the submerged arc furnace into a gas-liquid separator to separate condensed water and organic matters from the tail gas of the submerged arc furnace.
Preferably, the low-hydrogen low-pressure sulfur-tolerant deoxidation process of the submerged arc furnace tail gas comprises the step of introducing the deoxidized submerged arc furnace tail gas into a heat exchanger to be cooled to less than 40 ℃ after introducing the deoxidized submerged arc furnace tail gas into a deoxidizing furnace filled with a deoxidizing agent to be deoxidized.
Preferably, in the low-hydrogen low-pressure sulfur-tolerant deoxidation process for the submerged arc furnace tail gas, the temperature of the gas inlet of the deoxidation furnace is 150-350 ℃.
Preferably, in the low-hydrogen low-pressure sulfur-tolerant deoxidation process for the submerged arc furnace tail gas, the pressure in the deoxidation furnace is 0.1-0.6 MPa.
Preferably, in the low-hydrogen low-pressure sulfur-tolerant deoxidation process for the submerged arc furnace tail gas, the space velocity of the deoxidation furnace inlet submerged arc furnace tail gas is 1400-1500 h-1。
Compared with the prior art, the low-hydrogen low-pressure sulfur-resistant deoxidation process for the tail gas of the submerged arc furnace has the following beneficial effects:
according to the low-hydrogen low-pressure sulfur-resistant deoxidation process for the tail gas of the submerged arc furnace, the tail gas of the submerged arc furnace enters a purification tower, free oil is removed through a deoiling agent, then heat exchange is carried out through a heat exchanger to reach 150-250 ℃, a vulcanizing agent is supplemented into the tail gas of the submerged arc furnace, the tail gas is introduced into a deoxidation furnace to remove oxygen and HCN, and finally the temperature is reduced to be less than 40 ℃ through the heat exchanger; the invention relates to a low-hydrogen low-pressure sulfur-resistant deoxidation process for tail gas of a submerged arc furnace to remove O2High efficiency, O in the inlet gas2When the content is less than or equal to 15000ppm, the deoxidation rate is more than 95 percent; the deoxidation process of the invention has strong toxicity resistance, can resist sulfur and remove O2The effect is not affected by aromatic hydrocarbons such as toluene and aliphatic hydrocarbons such as ethylene; in the high-efficiency removal of O2Simultaneously, HCN can be removed together, and a certain amount of organic sulfur can be converted; the deoxidation process has strong adaptability, and can effectively remove O in the feed gas under the conditions of low hydrogen even no hydrogen, low pressure and normal pressure2(ii) a The deoxidation process has the advantages of short flow, no complex process and simple flow; the deoxidation process of the invention uses less equipment, has no special equipment and has small investment in the whole process.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a flow chart of the low-hydrogen low-pressure sulfur-tolerant deoxidation process of the tail gas of the submerged arc furnace.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with 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, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The embodiment of the application provides a low-hydrogen low-pressure sulfur-resistant deoxidation process for tail gas of a submerged arc furnace, which comprises the following steps:
s1, introducing the tail gas of the submerged arc furnace into a purification tower filled with an oil removal agent for oil removal;
s2, introducing the tail gas of the submerged arc furnace after oil removal into a heat exchanger, and heating to 150-350 ℃;
s3, adding vulcanizing agent into the ore smelting furnace tail gas, and controlling the sulfur content in the ore smelting furnace tail gas to be more than or equal to 20 multiplied by 10-6；
And S4, introducing the submerged arc furnace tail gas supplemented with the vulcanizing agent into a deoxidizing furnace filled with a deoxidizing agent, and deoxidizing at 200-400 ℃.
In the low-hydrogen low-pressure sulfur-tolerant deoxidation process of the submerged arc furnace tail gas in the embodiment of the application, the main components of the submerged arc furnace tail gas are shown in table 1 below.
TABLE 1 mine Heat furnace Tail gas principal Components
Composition of Volume content (%)
CO 50～65
H2 0.1～1
CO2 10～20
O2 0.1～0.5
N2 20～30
CH4 0～0.5
Saturated water Balance of
Specifically, the tail gas of the submerged arc furnace also contains H2S, HCN, aromatic hydrocarbons such as toluene, and aliphatic hydrocarbons such as ethylene, and the like, as shown in Table 2 below.
TABLE 2 contents of impurities in tail gas of submerged arc furnace
Composition of Volume content (10)-6)
Benzene and its derivatives 0～5
Toluene ～5
Xylene 0～3
Ethylbenzene production 0～2
Naphthalene 0～1
Oxygen gas 0～5000
Ethylene 0～150
Acetylene 0～8
Ethane (III) 0～1
Methane 0～5000
HCN 0～5
H2S 0～3
In some embodiments, the oil removal agent is an HGT-12 type oil removal agent.
In some embodiments, the deoxygenating agent is an HGT-601 type deoxygenating agent.
Specifically, in the above examples, the HGT-12 type oil remover and the HGT-601 type deoxidizer are those produced by Hubei cereal Co.
In some embodiments, the vulcanizing agent comprises dimethyl disulfide or carbon disulfide.
In some embodiments, before passing the mine hot furnace tail gas to the purification tower filled with the oil removal agent, the method further comprises: and introducing the tail gas of the submerged arc furnace into a gas-liquid separator to separate condensed water and organic matters from the tail gas of the submerged arc furnace.
In some embodiments, after the submerged arc furnace tail gas is introduced into the deoxidizing furnace filled with the deoxidizing agent for deoxidizing, the method further comprises the step of introducing the deoxidized submerged arc furnace tail gas into the heat exchanger for cooling to be less than 40 ℃.
In some embodiments, the temperature of the inlet of the deoxygenator furnace is 150-350 ℃.
In the above embodiment, the deoxidizer has a certain temperature rise during the deoxidation reaction, and the temperature rise plus the inlet temperature (i.e. the temperature of the gas inlet) of the deoxidation furnace is about 200 to 400 ℃.
In some embodiments, the pressure in the deoxidizing furnace is between 0.1 and 0.6 MPa.
Specifically, the low-hydrogen low-pressure sulfur-resistant deoxidation process for the submerged arc furnace tail gas specifically comprises the following steps: after the tail gas of the submerged arc furnace is pressurized by a compressor, the tail gas is introduced into a gas-liquid separator to separate condensed water and organic matters, then the tail gas enters a purification tower to be subjected to oil removal to remove free oil, then the heat is exchanged to 150-250 ℃ by a heat exchanger, a vulcanizing agent is supplemented into the tail gas of the submerged arc furnace by a metering pump, the tail gas is introduced into a deoxidizing furnace to remove oxygen and HCN, and finally the tail gas is cooled to be less than 40 ℃ by the heat exchanger and then is sent to the next working section. Fig. 1 shows a flow chart of the low-hydrogen low-pressure sulfur-resistant deoxidation process for the submerged arc furnace tail gas, wherein in fig. 1, a vulcanizing agent is carbon disulfide, and the vulcanizing agent is added into the submerged arc furnace tail gas through a metering pump.
The low-hydrogen low-pressure sulfur-resistant deoxidation process for the tail gas of the submerged arc furnace has the following specific advantages:
1. de-O2The efficiency is high: in the inlet air O2When the content is less than or equal to 15000ppm, the deoxidation rate is more than 95 percent;
2. strong toxicity resistance, sulfur resistance and O removal2The effect is not affected by aromatic hydrocarbons such as toluene and aliphatic hydrocarbons such as ethylene; in the high-efficiency removal of O2Simultaneously, HCN can be removed together, and a certain amount of organic sulfur can be converted;
3. the adaptability is strong: the O in the raw material gas can be effectively removed under the conditions of low hydrogen even no hydrogen and low pressure to normal pressure2；
4. The process is short: the whole process consists of 5 conventional steps, no complex process is needed, and the flow is simple;
5. the investment is small: the equipment is less, no special equipment is provided, and the investment of the whole process is small;
6. the service life is long: the service life of the deoxidizer is more than 2 years, and the expected value is 3-5 years.
The following further describes the low-hydrogen low-pressure sulfur-tolerant deoxidation process of the submerged arc furnace tail gas by using specific examples.
Example 1
The embodiment provides a low-hydrogen low-pressure sulfur-resistant deoxidation process for tail gas of a heating furnace, which comprises the following steps of:
s1, setting the flow rate at 45000Nm3After the tail gas of the submerged arc furnace is pressurized by a compressor, introducing the tail gas into a gas-liquid separator to separate condensed water and organic matters;
s2, removing oil from the tail gas of the submerged arc furnace by two purification towers which can run in series and in parallel and are filled with HGT-12 type oil removal agents, wherein the oil removal amount of each purification tower is 30m3Total of 60m3；
S3, introducing the tail gas of the submerged arc furnace after oil removal into a heat exchanger, and heating to 150-250 ℃;
s4, supplementing carbon disulfide to the ore smelting furnace tail gas after temperature rise through a metering pump at the speed of 2kg/h, and controlling the sulfur content in the ore smelting furnace tail gas to be more than or equal to 20 multiplied by 10-6；
S5, introducing the submerged arc furnace tail gas supplemented with the vulcanizing agent into a deoxidizing furnace filled with HGT-601 type deoxidizing agent, and leading O in the feed gas to be catalyzed by the deoxidizing agent2Completely removing and simultaneously removing HCN; wherein the loading amount of the deoxidizer is 30m3；
S6, cooling the tail gas of the submerged arc furnace after passing through the deoxidizing furnace to be less than 40 ℃ through a heat exchanger, and then sending the tail gas to the next working section;
wherein, the components of the submerged arc furnace tail gas used in the step S1 are shown in tables 1-2.
Example 2
The embodiment provides a low-hydrogen low-pressure sulfur-resistant deoxidation process for tail gas of a heating furnace, which comprises the following steps of:
s1, setting the flow rate as 40000Nm3Pressurizing the metallurgical furnace tail gas by a compressor, and introducing gasThe liquid separator separates condensed water and organic matters;
s2, removing oil from the tail gas of the metallurgical furnace in a purification tower filled with HGT-12 type oil removing agent, wherein the oil removing agent is filled in the purification tower at an amount of 54m3；
S3, introducing the deoiled metallurgical furnace tail gas into a heat exchanger, and heating to 260 ℃;
s4, supplementing dimethyl disulfide to the tail gas of the submerged arc furnace after temperature rise at the rate of 1.6kg/h through a metering pump, and controlling the sulfur content in the tail gas of the submerged arc furnace to be more than or equal to 20 multiplied by 10-6；
S5, introducing the metallurgical furnace tail gas supplemented with the vulcanizing agent into a deoxidizing furnace filled with an HGT-601 type deoxidizing agent, and leading O in the raw material gas to be catalyzed by the deoxidizing agent2Completely removing; wherein the loading amount of the deoxidizer is 27m3；
S6, cooling the tail gas of the submerged arc furnace after passing through the deoxidizing furnace to be less than 40 ℃ through a heat exchanger, and then sending the tail gas to the next working section;
the composition of the metallurgical furnace off-gas used in step S1 is shown in table 3 below.
TABLE 3 metallurgical furnace Tail gas composition
Composition of Volume content (%)
CO 67％
H2 5.8％
CO2 16.8％
O2 0.6％
N2 6％
CH4 0.1％
Benzene and its derivatives 0.8×10-6
H2S 10×10-6
COS 70×10-6
Saturated water Balance of
The deoxidation results in test examples 1-2 are shown in Table 4 below.
TABLE 4 deoxidation results in examples 1 to 2
Figure BDA0003474210250000071
Figure BDA0003474210250000081
The deoxidation furnace inlet temperature, the deoxidation furnace inlet tail gas space velocity, and the deoxidation furnace inlet O in Table 42Volume content, deoxidation furnace outlet O2The volume content, the volume content of HCN at the inlet of the deoxidizing furnace and the volume content of HCN at the outlet of the deoxidizing furnace are all actual measured values.
As can be seen from Table 4 above, the low-hydrogen low-pressure sulfur-tolerant deoxidation process, O, of the hot furnace tail gas of the present application2The removal efficiency can reach 99.6-99.9%, and the removal efficiency of HCN can reach 93.3%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. The low-hydrogen low-pressure sulfur-resistant deoxidation process for the tail gas of the submerged arc furnace is characterized by comprising the following steps of:
leading the tail gas of the submerged arc furnace into a purification tower filled with an oil removal agent for oil removal;
introducing the tail gas of the submerged arc furnace after oil removal into a heat exchanger and heating to 150-350 ℃;
then, a vulcanizing agent is supplemented into the ore smelting furnace tail gas, and the sulfur content in the ore smelting furnace tail gas is controlled to be more than or equal to 20 multiplied by 10-6；
And introducing the submerged arc furnace tail gas supplemented with the vulcanizing agent into a deoxidizing furnace filled with a deoxidizing agent, and deoxidizing at 200-400 ℃.
2. The low-hydrogen low-pressure sulfur-tolerant deoxidation process of submerged arc furnace tail gas as claimed in claim 1, wherein said degreasing agent is HGT-12 type degreasing agent.
3. The low-hydrogen low-pressure sulfur-tolerant deoxidizing process of submerged arc furnace tail gas as claimed in claim 1, wherein said deoxidizing agent is an HGT-601 type deoxidizing agent.
4. The submerged arc furnace tail gas low-hydrogen low-pressure sulfur-tolerant deoxygenation process of claim 1, wherein said sulfiding agent comprises dimethyl disulfide or carbon disulfide.
5. The low-hydrogen low-pressure sulfur-tolerant deoxidation process for submerged arc furnace tail gas as claimed in claim 1, wherein before introducing the submerged arc furnace tail gas into the purification tower filled with oil removal agent, the process further comprises: and introducing the tail gas of the submerged arc furnace into a gas-liquid separator to separate condensed water and organic matters from the tail gas of the submerged arc furnace.
6. The low-hydrogen low-pressure sulfur-tolerant deoxidation process for submerged arc furnace tail gas as claimed in claim 1, wherein the step of introducing the submerged arc furnace tail gas into the deoxidation furnace filled with the deoxidizer for deoxidation further comprises introducing the deoxidized submerged arc furnace tail gas into the heat exchanger for cooling to less than 40 ℃.
7. The low-hydrogen low-pressure sulfur-tolerant deoxidation process for submerged arc furnace tail gas as claimed in claim 1, wherein the temperature of the deoxidation furnace inlet is 150-350 ℃.
8. The low-hydrogen low-pressure sulfur-tolerant deoxidation process for submerged arc furnace tail gas as claimed in claim 1, wherein the pressure in the deoxidation furnace is 0.1-0.6 Mpa.
9. The low-hydrogen low-pressure sulfur-tolerant deoxidation process for submerged arc furnace tail gas as claimed in claim 1, wherein the space velocity of the deoxidation furnace inlet submerged arc furnace tail gas is 1400-1500 h-1。
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