CN112892202A - Sulfur-containing gas desulfurization device system and method - Google Patents

Sulfur-containing gas desulfurization device system and method Download PDF

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CN112892202A
CN112892202A CN202110093711.8A CN202110093711A CN112892202A CN 112892202 A CN112892202 A CN 112892202A CN 202110093711 A CN202110093711 A CN 202110093711A CN 112892202 A CN112892202 A CN 112892202A
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sulfur
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CN112892202B (en
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穆廷桢
邢建民
杨茂华
苗得露
赵胥浩
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Institute of Process Engineering of CAS
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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
    • B01D53/84—Biological 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • 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
    • B01D53/48—Sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/306—Organic sulfur compounds, e.g. mercaptans
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention provides a sulfur-containing gas desulfurization device system and a sulfur-containing gas desulfurization method. The device system enables organic sulfur in sulfur-containing gas to react with sulfur particles through the arrangement of the tail gas removing device and the anaerobic conversion device to generate sulfides, the sulfides are mixed with the effluent of the deep absorption tower and enter the biological regeneration tower, and HS is oxidized by sulfur oxidizing microorganisms under the condition of oxygen enrichment‑Oxidizing to generate elemental sulfur and recovering. Compared with the traditional method, the invention effectively reduces the inhibition of organic sulfur on the biological desulfurization process and strengthens the desulfurization of HS by the desulfurization bacteria by adding the organic sulfur conversion process‑Absorption and HS‑Selection of oxidative pathwaysReduce S in the process2O3 2‑And SO4 2‑The formation improves the generation rate of elemental sulfur, and has good economic benefit and application prospect.

Description

Sulfur-containing gas desulfurization device system and method
Technical Field
The invention belongs to the technical field of environmental engineering, relates to a desulphurization device system, and particularly relates to a desulphurization device system and a desulphurization method for sulfur-containing gas.
Background
The natural gas and the methane are subjected to desulfurization treatment, so that not only can clean fuel gas be obtained, but also sulfur can be recovered, and therefore, the method has two purposes and is an important technical means for changing waste into valuable. However, natural gas and biogas often contain a large amount of sulfur-containing compounds, such as hydrogen sulfide, mercaptans, and sulfides. The sulfur-containing compound has certain toxicity and corrosiveness and is relatively harmful to the environment; in addition, in the biological desulfurization process, organic sulfur in the sulfur-containing compounds can generate certain inhibition effect on the activity of microbial cells, so that the desulfurization effect is greatly influenced.
CN 110240961A discloses a halophilic and alkalophilic biological desulfurization treatment process and a treatment device, wherein the device comprises a biological purification tower, a deep adsorption tower, a biological regeneration tower and a sulfur collection tower. The process comprises the following steps: absorbing H in biogas by using absorption liquid containing sulfur-oxidizing microorganisms2S, then stirring the liquid phase in an anaerobic environment to strengthen the sulfur-oxidizing microorganism to HS-Absorption of (2); HS by using sulfur oxidizing microorganism under oxygen-enriched condition-Oxidizing to generate elemental sulfur and recovering. The treatment process effectively weakens the chemical oxidation process existing in the biological desulfurization process of the biogas and reduces S in the treatment process2O3 2-And SO4 2-The formation of (2) improves the generation rate of elemental sulfur. However, the sulfur-containing gas does not simply contain H2S, and also contains organic sulfur inevitably.
The organic sulfur in the sulfur-containing gas includes methyl mercaptan, ethyl mercaptan, propyl mercaptan, carbon disulfide, dimethyl sulfide, dimethyl disulfide or dimethyl trisulfide, which are mostly liquid at room temperature and almost all have unpleasant odor, but the toxicity of the organic sulfur is higher than that of H in natural gas and biogas2S is low.
When treating sulfur-containing gases by biological methods, H2S is firstly absorbed by alkali liquor, and organic sulfur in the gas is absorbed into the alkali liquor, and a series of reactions further occur in the bioreactor. Taking methyl mercaptan in organic purity as an example, methyl mercaptan has strong nucleophilicity and can spontaneously generate a series of chemical reactions to form a plurality of polysulfide compounds, reaction products mainly comprise sulfide, polysulfide, DMDS, DMTS and the like, and a few trace amount of long-chain dimethyl polysulfide can be formed, so that the recycling of sulfur in sulfur-containing gas is influenced.
Polysulphides and polysulfanes from methanethiol and S8Chemical reactions occur to form, and then chemical reactions occur between the polysulfanes to form metastable intermediates that rapidly decompose into stable di-or tri-sulfide species.
Under halophilic and basophilic conditions, the organic sulfur in the bioreactor is mainly composed of dimethyl disulfide and dimethyl trisulfide. In the biological desulfurization process, the common organic sulfur reaction is as follows:
①CH3SH+OH-→CH3S-+H2O
②2CH3SH+0.5O2→CH3S2CH3+H2O
③
Figure BDA0002912235860000021
④
Figure BDA0002912235860000022
⑤
Figure BDA0002912235860000023
the thiol organic substance contains sulfur-based structure (-SH), which can destroy intramolecular disulfide bond, and RSH binds to sulfide oxidase FCC of sulfur oxidizing bacteria to change enzyme structure or active site of enzyme to reduce enzyme activity, thereby reducing enzyme activityThe oxidation activity of the cells is reduced, so that the chemical oxidation of sulfide in the culture solution is enhanced, and S is generated during the treatment2O3 2-And SO4 2-Increased yield of SO4 2-And S2O3 2-The accumulation of (2) causes the total mineralization of the system to be increased continuously, and the cells need to consume a large amount of energy to produce a large amount of compatible solute in order to cope with the continuously increased environmental osmotic pressure, thereby causing the activity and desulfurization performance of the cells to be reduced.
Thiols readily chemically react to form polythioethers, which are strongly hydrophobic and readily adsorb to sulfur particles, which results in reduced organosulfur inhibition. Meanwhile, under the anaerobic state, the biological sulfur and organic sulfur react to generate sulfide, so that the inhibition on cells is reduced. In addition, studies have also found that the inhibitory effect of mercaptans on cells can be removed from the bioreactor media by stripping and chemical reaction with biological sulfur particles.
Therefore, if the absorption process, the anaerobic enhanced treatment, the organic sulfur stripping and other processes are added on the basis of the traditional process, the inhibition of organic sulfur on the biological desulfurization process can be effectively reduced, and the HS of the desulfurization bacteria can be enhanced-Absorption and HS-Selection of oxidation pathways that reduce S in biological desulfurization2O3 2-And SO4 2-The formation of the sulfur-containing compound improves the generation rate of elemental sulfur, can also reduce the requirement on the pH value of the alkali liquor, and improves the economy of the biological desulfurization process.
Disclosure of Invention
The invention aims to provide a sulfur-containing gas desulfurization device system and a method, wherein the sulfur-containing gas desulfurization device can treat organic sulfur in sulfur-containing gas, can effectively reduce the inhibition of the organic sulfur on a biological desulfurization process, and can strengthen the HS (high-speed sulfur) of desulfurization bacteria-Absorption and HS-The selection of oxidation route realizes S in the process of treating the gas containing organic sulfur2O3 2-And SO4 2-The reduction of the amount of formation, the increase of the production rate of elemental sulphur, the reduction of the need for lye for pH adjustment, haveGood economic benefit and application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a sulfur-containing gas desulfurization apparatus system, which includes a biological purification apparatus, a deep adsorption apparatus, a tail gas removal apparatus, an anaerobic conversion apparatus, a biological regeneration apparatus, and a sulfur collection apparatus.
And a liquid outlet of the biological purification device is connected with a liquid inlet of the deep adsorption device.
And a liquid outlet of the tail gas removing device is connected with a liquid inlet of the anaerobic conversion device.
And the liquid outlet of the deep adsorption device and the liquid outlet of the anaerobic conversion device are respectively and independently connected with the liquid inlet of the biological regeneration device.
And a liquid outlet of the biological regeneration device is respectively and independently connected with a liquid inlet of the biological purification device, the tail gas removal device and the sulfur collection device.
The sulfur collecting device is used for separating elemental sulfur, and clear liquid obtained by separation flows back to the biological regeneration device.
The gas outlet of the biological purification device and the gas outlet of the deep adsorption device are respectively and independently connected with the gas inlet of the tail gas removal device; and a gas outlet of the tail gas removing device is provided with a gas backflow branch, and the gas backflow branch is respectively and independently connected with a gas inlet of the anaerobic conversion device and an aeration piece in the deep adsorption device.
The biological purification device of the invention includes but is not limited to a biological purification tower; the deep adsorption device includes but is not limited to a deep adsorption tower; the tail gas removal unit includes, but is not limited to, a tail gas removal column; the anaerobic conversion device includes, but is not limited to, an anaerobic conversion tower; the biological regeneration device comprises but is not limited to a biological regeneration tower, and conventional components such as an electrode plate, a pH meter and a thermometer are arranged in the biological regeneration tower, so that the control of oxidation-reduction potential, pH value and temperature in the biological regeneration process is facilitated.
The gas outlet of the biological purification device and the gas outlet of the deep adsorption device are respectively and independently connected with the gas inlet of the tail gas removal device, so that residual H in the tail gas is removed2S and further absorption of organic sulfur, organic sulfur and residual H in gas2And (4) completely removing S. A gas outlet of the tail gas removal device is provided with a gas backflow branch, and the gas backflow branch is respectively and independently connected with a gas inlet of the anaerobic conversion device and an aeration piece in the deep adsorption device; wherein the gas backflow branch is connected with the anaerobic conversion device to provide balanced pressure and stable anaerobic environment for the anaerobic conversion device, the gas backflow branch is connected with the aeration piece in the deep adsorption device to realize anaerobic stirring of the deep adsorption device, and the sulfur oxidizing microorganisms in the absorption liquid to HS are strengthened-Absorption of (2).
The discharged liquid at the liquid outlet of the biological regeneration device contains elemental sulfur, and the elemental sulfur can react with organic sulfur absorbed by the absorption liquid to generate sulfide, so that the adverse effect of the organic sulfur on biological desulfurization in the biological regeneration device is reduced.
The biological purification device is in an oxygen-enriched environment, so that HS is oxidized by sulfur-oxidizing microorganisms under the oxygen-enriched condition-Oxidized into elemental sulfur, and the elemental sulfur is recycled by utilizing a sulfur collecting device.
The invention effectively reduces the inhibition of organic sulfur to the biological desulfurization process and strengthens the desulfurization of HS by the desulfurization bacteria through the arrangement of the deep adsorption device, the tail gas removal device and the anaerobic conversion device-Absorption and HS-The selection of oxidation route greatly reduces S in the treatment process2O3 2-And SO4 2-The method improves the generation rate of elemental sulfur, reduces the requirement on liquid caustic soda for adjusting pH, and has good economic benefit and application prospect.
Preferably, an aeration device is arranged in the biological regeneration device and is used for providing oxygen-containing gas for the biological regeneration device.
HS absorbed by sulfur oxidizing microorganisms in the biological regeneration device in the presence of an oxygen-containing gas-Converted to elemental sulfur.
Preferably, the aeration device comprises an aeration pipe and/or an aeration disc.
Preferably, the aeration member comprises an aeration pipe and/or an aeration disc.
The aeration piece provided by the invention can stir liquid in the deep adsorption device under the condition of providing anaerobic atmosphere for the deep adsorption device, so that HS (high-speed hydrogen) caused by sulfur oxidizing microorganisms in the liquid is enhanced-The absorption effect of (1).
Preferably, a mechanical stirring device is arranged in the deep adsorption device.
The mechanical stirring device of the present invention includes, but is not limited to, a conventional stirring paddle. The invention can further strengthen the HS pair by sulfur oxidizing microorganisms in the liquid by arranging the mechanical stirring device-The absorption effect of (1).
In a second aspect, the present invention provides a sulfur-containing gas desulfurization method carried out in the sulfur-containing gas desulfurization apparatus system described in the first aspect.
Preferably, the method for desulfurizing sulfur-containing gas comprises the following steps:
(1) treating sulfur-containing gas by using a first absorption liquid to obtain a primary purified gas and a first sulfur-containing liquid;
(2) deeply adsorbing the first sulfur-containing liquid obtained in the step (1) to obtain a sulfur adsorption liquid and anaerobic treatment gas;
(3) treating the anaerobic treatment gas obtained in the step (2) by using a second absorption liquid to obtain a clean gas and a second sulfur-containing liquid;
(4) reacting organic sulfur in the second sulfur-containing liquid with sulfur particles under an anaerobic condition, and mixing the sulfur adsorption liquid obtained in the step (2) with the reacted second sulfur-containing liquid to obtain a mixed liquid;
(5) carrying out aeration treatment on the mixed solution obtained in the step (4) by using oxygen-containing gas to enable sulfur oxidizing microorganisms in the mixed solution to be in an oxidizing sulfur-producing state to obtain a reaction solution;
(6) dividing the reaction solution into a first reaction solution, a second reaction solution and a third reaction solution, wherein the first reaction solution is used as the first absorption solution in the step (1); the second reaction solution is used as the second absorption solution in the step (3); carrying out solid-liquid separation on the third reaction liquid, and recycling the obtained clear liquid in the step (5);
the first absorption liquid and the second absorption liquid are respectively and independently buffer solutions containing sulfur-oxidizing microorganisms;
and (4) recycling part of the clean gas obtained in the step (3) for deep adsorption in the step (2).
Step (1) of the sulfur-containing gas desulfurization method of the present invention is carried out in a biological purification apparatus; step (2) of the sulfur-containing gas desulfurization method of the present invention is carried out in a deep absorption apparatus; step (3) of the sulfur-containing gas desulfurization method of the present invention is carried out in a tail gas removal device; the reaction of step (4) of the sulfur-containing gas desulfurization method of the present invention is carried out in an anaerobic conversion apparatus; step (5) of the sulfur-containing gas desulfurization method of the present invention is carried out in a biological regeneration apparatus; the solid-liquid separation in step (6) of the sulfur-containing gas desulfurization method of the present invention is performed in a sulfur collection device.
The invention uses the first absorption liquid to absorb H in the sulfur-containing gas in the biological purification device2S and organic sulfur, to H2S and organic sulfur enter a liquid phase, and sulfur-containing gas is primarily purified.
After the first sulfur-containing liquid enters the deep adsorption device, the deep adsorption device keeps an anaerobic environment to the sulfur-containing liquid-The liquid phase of (A) is subjected to gas stirring to promote sulfur oxidizing microorganisms to carry out HS-Absorption of (2); at the same time, partial dissolved organic sulfur can be discharged through the stripping action, the inhibition effect on the biological regeneration device is reduced, and the anaerobic treatment gas extracted by the stripping action is reabsorbed in the tail gas removing device and is converted into sulfide in the anaerobic conversion device.
The primary purified gas generated by the biological purification device enters a tail gas removing device to ensure that organic sulfur and a small amount of H in the primary purified gas2S is completely removed fromThereby obtaining clean gas. Mixing the second sulfur-containing liquid after reaction in the anaerobic conversion device with the sulfur adsorption liquid obtained by the deep adsorption device, entering a biological regeneration device, carrying out oxygen-containing gas aeration treatment in the biological regeneration device, controlling the oxidation-reduction potential, the temperature and the pH value to enable sulfur-oxidizing microorganisms to be in an oxidation sulfur production state, concentrating the generated sulfur in the upper liquid through aeration to form a concentrated sulfur layer, obtaining reaction liquid and clear liquid, and recovering the reaction liquid.
Preferably, the sulfur oxidizing microorganisms in the buffer solution containing sulfur oxidizing microorganisms are sulfur oxidizing bacteria, preferably Vibrio thioalkali.
Preferably, the buffer solution containing sulfur-oxidizing microorganisms is Na2CO3And NaHCO3The buffer solution of (1).
Preferably, Na in the buffer solution containing the sulfur-oxidizing microorganisms+The concentration of (b) is 1 to 2mol/L, and may be, for example, 1mol/L, 1.2mol/L, 1.5mol/L, 1.8mol/L or 2mol/L, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the buffer solution containing the sulfur oxidizing microorganisms has a pH of 8 to 11, which may be, for example, 8, 8.5, 9, 9.5, 10, 10.5 or 11, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the first absorption liquid in the step (1) treats the sulfur-containing gas in a countercurrent manner.
Preferably, the second treatment liquid in step (3) is used for treating anaerobic treatment gas in a countercurrent mode.
Preferably, the sulfur-containing gas of step (1) comprises H2S and organic sulfur.
Preferably, the organic sulfur comprises methyl Mercaptan (MT), ethyl mercaptan (ET), propyl mercaptan (PT), carbon disulfide (CS)2) Any one or a combination of at least two of dimethyl sulfide (DMS), dimethyl disulfide (DMDS) or dimethyl trisulfide (DMTS); typical but non-limiting combinations include combinations of methyl mercaptan and ethyl mercaptan, combinations of ethyl mercaptan and propyl mercaptan, combinations of propyl mercaptan and carbon disulfide, carbon disulfide and dimethyl sulfideA combination of ethers, a combination of dimethyl sulfide and dimethyl disulfide, a combination of dimethyl disulfide and dimethyl trisulfide, a combination of methanethiol, carbon disulfide and dimethyl sulfide, a combination of ethanethiol, carbon disulfide and dimethyl disulfide, a combination of propanethiol, carbon disulfide and dimethyl trisulfide, or a combination of methanethiol, ethanethiol, propanethiol, carbon disulfide, dimethyl sulfide, dimethyl disulfide and dimethyl trisulfide.
The sulfur-containing gas desulfurization device and the method provided by the invention can treat the conventional organic sulfur in the field, and avoid the adverse effect of the conventional organic sulfur on biological desulfurization.
Preferably, the oxygen-containing gas in step (5) is oxygen and/or air, preferably air.
Preferably, the liquid-gas ratio of the first absorption liquid to the sulfur-containing gas in the step (1) is 1 (10-50), and may be, for example, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45 or 1:50, and the unit of the liquid-gas ratio is L/Nm3；
Preferably, the liquid-gas ratio of the second absorption liquid to the anaerobic treatment gas in the step (3) is 1 (10-50), and can be 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45 or 1:50, for example, the unit of the liquid-gas ratio is L/Nm3。
Preferably, the temperature of the treatment in step (1) is 20 to 40 ℃, for example 20 ℃, 25 ℃, 30 ℃, 35 ℃ or 40 ℃, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the temperature of the deep adsorption in step (2) is 20-40 ℃, for example, 20 ℃, 25 ℃, 30 ℃, 35 ℃ or 40 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the temperature of the treatment in step (3) is 20-40 ℃, for example 20 ℃, 25 ℃, 30 ℃, 35 ℃ or 40 ℃, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the reaction temperature in step (4) is 20-40 ℃, for example 20 ℃, 25 ℃, 30 ℃, 35 ℃ or 40 ℃, but not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
Preferably, the oxidation-reduction potential of the aeration treatment in step (5) is-400 mV to-300 mV, which may be, for example, -400mV, -390mV, -380mV, -370mV, -360mV, -350mV, -340mV, -330mV, -320mV, -310mV or-300 mV, but is not limited to the values recited, and other values not recited in the numerical ranges are equally applicable.
Preferably, the pH value in the aeration treatment process in the step (5) is 8-11, for example, 8, 8.5, 9, 9.5, 10, 10.5 or 11, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the temperature of the aeration treatment in step (5) is 20 to 40 ℃, for example, 20 ℃, 25 ℃, 30 ℃, 35 ℃ or 40 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the solid-liquid separation method in the step (6) is gravity settling.
As a preferable embodiment of the method for desulfurizing a sulfur-containing gas according to the second aspect of the present invention, the method for desulfurizing a sulfur-containing gas includes the steps of:
(1) using a first absorption liquid to perform countercurrent treatment on the sulfur-containing gas at the temperature of 20-40 ℃ to obtain a primary purified gas and a first sulfur-containing liquid; the sulfur-containing gas comprises H2S and organic sulfur; the liquid-gas ratio of the first absorption liquid to the sulfur-containing gas is 1 (10-50), and the unit of the liquid-gas ratio is L/Nm3；
(2) Deeply adsorbing the first sulfur-containing liquid obtained in the step (1) at the temperature of 20-40 ℃ to obtain a sulfur adsorption liquid and anaerobic treatment gas;
(3) carrying out countercurrent treatment on the anaerobic treatment gas obtained in the step (2) by using a second absorption liquid at the temperature of 20-40 ℃ to obtain a clean gas and a second sulfur-containing liquid; the liquid-gas ratio of the second absorption liquid to the anaerobic treatment gas is 1 (10-50), and the unit of the liquid-gas ratio is L/Nm3；
(4) Reacting organic sulfur in the second sulfur-containing liquid with sulfur particles at 20-40 ℃ under anaerobic conditions, and mixing the sulfur adsorption liquid obtained in the step (2) with the reacted second sulfur-containing liquid to obtain a mixed liquid;
(5) aerating the mixed liquor in the step (4) by using oxygen-containing gas at the temperature of 20-40 ℃ to enable sulfur oxidizing microorganisms in the mixed liquor to be in an oxidizing sulfur-producing state to obtain reaction liquid; the oxidation-reduction potential of the aeration treatment is-400 mV to-300 mV; the pH value in the aeration treatment process is 8-11;
(6) dividing the reaction solution into a first reaction solution, a second reaction solution and a third reaction solution, wherein the first reaction solution is used as the first absorption solution in the step (1); the second reaction solution is used as the second absorption solution in the step (3); carrying out solid-liquid separation on the third reaction liquid, and recycling the obtained clear liquid in the step (5);
the first absorption liquid and the second absorption liquid are respectively and independently buffer solutions containing sulfur-oxidizing microorganisms; the buffer solution containing sulfur-oxidizing microorganisms is Na2CO3And NaHCO3The buffer solution of (4); the pH value of the buffer solution containing the sulfur-oxidizing microorganisms is 8-11;
and (4) recycling part of the clean gas obtained in the step (3) for deep adsorption in the step (2).
Compared with the prior art, the invention has the following beneficial effects:
(1) the sulfur-containing gas desulfurization device system effectively reduces the inhibition of organic sulfur to the biological desulfurization process and strengthens the desulfurization of HS by the desulfurization bacteria through the arrangement of the deep adsorption device, the tail gas removal device and the anaerobic conversion device-Absorption and HS-The selection of oxidation route greatly reduces S in the treatment process2O3 2-And SO4 2-The formation improves the generation rate of the elemental sulfur, reduces the requirement on liquid caustic soda for adjusting the pH value and improves the generation rate of the elemental sulfur;
(2) the sulfur-containing gas desulfurization device system and the method provided by the invention effectively reduce the problem of organic sulfur inhibition in the biological desulfurization process of sulfur-containing gas, improve the generation rate of elemental sulfur, reduce the requirement on liquid caustic soda for adjusting pH, obviously improve the economy of the process, and have the advantages of high treatment efficiency, low energy consumption, low operation cost, high added value of products, easiness in industrial popularization and good application prospect.
Drawings
FIG. 1 is a schematic configuration diagram of a sulfur-containing gas desulfurization apparatus system provided in example 1;
FIG. 2 is a schematic configuration diagram of a sulfur-containing gas desulfurization apparatus system provided in comparative example 1;
FIG. 3 is a schematic configuration diagram of a sulfur-containing gas desulfurization apparatus system provided in comparative example 2;
FIG. 4 is a schematic configuration diagram of a sulfur-containing gas desulfurization apparatus system provided in comparative example 3;
FIG. 5 is a schematic view showing the constitution of a sulfur-containing gas desulfurization apparatus system provided in comparative example 4.
Wherein: 1, a biological purification tower; 2, a deep adsorption tower; 3, a tail gas removing tower; 4, an anaerobic conversion tower; 5, a biological regeneration tower; and 6, a sulfur collecting tower.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a sulfur-containing gas desulfurization device system, and the structural schematic diagram of the sulfur-containing gas desulfurization device system is shown in fig. 1, and the sulfur-containing gas desulfurization device system comprises a biological purification tower, a deep adsorption tower, a tail gas removal tower, an anaerobic conversion tower, a biological regeneration tower and a sulfur collection tower.
And a liquid outlet of the biological purification tower is connected with a liquid inlet of the deep adsorption tower.
And a liquid outlet of the tail gas removal tower is connected with a liquid inlet of the anaerobic conversion tower.
And the liquid outlet of the deep adsorption tower and the liquid outlet of the anaerobic conversion tower are respectively and independently connected with the liquid inlet of the biological regeneration tower.
And the liquid outlet of the biological regeneration tower is respectively and independently connected with the liquid inlets of the biological purification tower, the tail gas removal tower and the sulfur collection tower.
The sulfur collecting tower is used for separating elemental sulfur, and clear liquid obtained by separation flows back to the biological regeneration tower.
The gas outlet of the biological purification tower and the gas outlet of the deep adsorption tower are respectively and independently connected with the gas inlet of the tail gas removal tower; the gas outlet of the tail gas removal tower is provided with a gas reflux branch, the gas reflux branch is respectively and independently connected with a gas inlet of the anaerobic conversion tower and an aeration piece in the deep absorption tower, and the aeration piece is an aeration disc.
An aeration device is arranged in the biological regeneration tower and used for providing oxygen-containing gas for the biological regeneration tower, and the aeration device is an aeration disc.
Comparative example 1
This comparative example provides a sulfur-containing gas desulfurization plant system, the schematic structural diagram of which is shown in fig. 2, and which includes a biological purification tower, a biological regeneration tower, and a sulfur collection tower.
And the liquid outlet of the biological purification tower is connected with the liquid inlet of the biological regeneration tower.
And the liquid outlet of the biological regeneration tower is respectively and independently connected with the liquid inlets of the biological purification tower and the sulfur collection tower.
The sulfur collecting tower is used for separating elemental sulfur, and clear liquid obtained by separation flows back to the biological regeneration tower.
An aeration device is arranged in the biological regeneration tower and used for providing oxygen-containing gas for the biological regeneration tower, and the aeration device is an aeration disc.
Comparative example 2
This comparative example provides a sulfur-containing gas desulfurization apparatus system, the schematic structural diagram of which is shown in fig. 3, and which includes a biological purification tower, a tail gas removal tower, a biological regeneration tower, and a sulfur collection tower.
And the liquid outlet of the biological purification tower and the liquid outlet of the tail gas removal tower are respectively and independently connected with the liquid inlet of the biological regeneration tower.
And the liquid outlet of the biological regeneration tower is respectively and independently connected with the liquid inlets of the biological purification tower, the tail gas removal tower and the sulfur collection tower.
The sulfur collecting tower is used for separating elemental sulfur, and clear liquid obtained by separation flows back to the biological regeneration tower.
And a gas outlet of the biological purification tower is connected with a gas inlet of the tail gas removal tower.
An aeration device is arranged in the biological regeneration tower and used for providing oxygen-containing gas for the biological regeneration tower, and the aeration device is an aeration disc.
Comparative example 3
This comparative example provides a sulfur-containing gas desulfurization apparatus system, the schematic structural diagram of which is shown in fig. 4, and which includes a biological purification tower, a deep adsorption tower, a tail gas removal tower, a biological regeneration tower, and a sulfur collection tower.
And a liquid outlet of the biological purification tower is connected with a liquid inlet of the deep adsorption tower.
And the liquid outlet of the deep adsorption tower and the liquid outlet of the tail gas removal tower are respectively and independently connected with the liquid inlet of the biological regeneration tower.
And the liquid outlet of the biological regeneration tower is respectively and independently connected with the liquid inlets of the biological purification tower, the tail gas removal tower and the sulfur collection tower.
The sulfur collecting tower is used for separating elemental sulfur, and clear liquid obtained by separation flows back to the biological regeneration tower.
The gas outlet of the biological purification tower and the gas outlet of the deep adsorption tower are respectively and independently connected with the gas inlet of the tail gas removal tower; and a gas outlet of the tail gas removal tower is connected with an aeration piece in the deep adsorption tower, and the aeration piece is an aeration disc.
An aeration device is arranged in the biological regeneration tower and used for providing oxygen-containing gas for the biological regeneration tower, and the aeration device is an aeration disc.
Comparative example 4
The present comparative example provides a sulfur-containing gas desulfurization apparatus system, the schematic structural diagram of which is shown in fig. 5, and which includes a biological purification tower, a deep adsorption tower, a tail gas removal tower, an anaerobic conversion tower, a biological regeneration tower, and a sulfur collection tower.
And a liquid outlet of the biological purification tower is connected with a liquid inlet of the deep adsorption tower.
And a liquid outlet of the tail gas removal tower is connected with a liquid inlet of the anaerobic conversion tower.
And the liquid outlet of the deep adsorption tower and the liquid outlet of the anaerobic conversion tower are respectively and independently connected with the liquid inlet of the biological regeneration tower.
And the liquid outlet of the biological regeneration tower is respectively and independently connected with the liquid inlets of the biological purification tower, the tail gas removal tower and the sulfur collection tower.
The sulfur collecting tower is used for separating elemental sulfur, and clear liquid obtained by separation flows back to the biological regeneration tower.
The gas outlet of the biological purification tower and the gas outlet of the deep adsorption tower are respectively and independently connected with the gas inlet of the tail gas removal tower; the gas outlet of the tail gas removal tower is provided with a gas reflux branch, the gas reflux branch is respectively and independently connected with a gas inlet of the anaerobic conversion tower and an aeration piece in the deep absorption tower, and the aeration piece is an aeration disc.
An aeration device is arranged in the biological regeneration tower and used for providing oxygen-containing gas for the biological regeneration tower, and the aeration device is an aeration disc.
Application example 1
In this application example, the sulfur-containing gas desulfurization apparatus system provided in application example 1 was used to treat a sulfur-containing gas, which was a simulated sulfur-containing gas containing 60 vol% of N2And 40 vol% CO2As carrier gas, simulating H in sulfur-containing gas in steady state2The molar concentration of S is 90mmol/NL, the molar concentration of methyl mercaptan is 2mmol/NL, and the process for treating the sulfur-containing gas comprises the following steps:
(1) using first absorption liquid to perform countercurrent treatment on the sulfur-containing gas at the temperature of 30 ℃ to obtain primary purified gas and first sulfur-containing liquid; the liquid-gas ratio of the first absorption liquid to the sulfur-containing gas is 1:30, and the liquid isThe unit of gas ratio is L/Nm3；
(2) Deeply adsorbing the first sulfur-containing liquid obtained in the step (1) at the temperature of 30 ℃ to obtain a sulfur adsorption liquid and an anaerobic treatment gas;
(3) carrying out countercurrent treatment on the anaerobic treatment gas obtained in the step (2) by using a second absorption liquid at the temperature of 30 ℃ to obtain a clean gas and a second sulfur-containing liquid; the liquid-gas ratio of the second absorption liquid to the anaerobic treatment gas is 1:30, and the unit of the liquid-gas ratio is L/Nm3；
(4) Reacting organic sulfur in the second sulfur-containing liquid with sulfur particles at 30 ℃ under an anaerobic condition, and mixing the sulfur adsorption liquid obtained in the step (2) with the reacted second sulfur-containing liquid to obtain a mixed liquid;
(5) aerating the mixed liquor obtained in the step (4) by using oxygen-containing gas at the temperature of 30 ℃ to enable sulfur oxidizing microorganisms in the mixed liquor to be in an oxidizing sulfur production state to obtain reaction liquid; the oxidation-reduction potential of the aeration treatment is-350 mV; the pH value in the aeration treatment process is 9; the oxygen-containing gas is air;
(6) dividing the reaction solution into a first reaction solution, a second reaction solution and a third reaction solution, wherein the first reaction solution is used as the first absorption solution in the step (1); the second reaction solution is used as the second absorption solution in the step (3); carrying out solid-liquid separation on the third reaction liquid, and recycling the obtained clear liquid in the step (5);
the first absorption liquid and the second absorption liquid are respectively and independently buffer solutions containing sulfur-oxidizing microorganisms; the buffer solution containing sulfur-oxidizing microorganisms is Na2CO3And NaHCO3The buffer solution of (4); the pH value of the buffer solution containing the sulfur-oxidizing microorganisms is 9, and Na in the buffer solution+The concentration of (A) is 1.5 mol/L;
and (4) recycling part of the clean gas obtained in the step (3) for deep adsorption in the step (2).
Application example 2
The sulfur-containing gas desulfurization device system provided in application example 1 of this application example treats sulfur-containing gas, which is simulated sulfur-containing gas, and the composition of the simulated sulfur-containing gas is the same as that in application example 1, and the process of treating sulfur-containing gas includes the following steps:
(1) using a first absorption liquid to perform countercurrent treatment on the sulfur-containing gas at the temperature of 25 ℃ to obtain a primary purified gas and a first sulfur-containing liquid; the liquid-gas ratio of the first absorption liquid to the sulfur-containing gas is 1:20, and the unit of the liquid-gas ratio is L/Nm3；
(2) Deeply adsorbing the first sulfur-containing liquid obtained in the step (1) at 25 ℃ to obtain a sulfur adsorption liquid and an anaerobic treatment gas;
(3) carrying out countercurrent treatment on the anaerobic treatment gas obtained in the step (2) by using a second absorption liquid at the temperature of 25 ℃ to obtain a clean gas and a second sulfur-containing liquid; the liquid-gas ratio of the second absorption liquid to the anaerobic treatment gas is 1:20, and the unit of the liquid-gas ratio is L/Nm3；
(4) Reacting organic sulfur in the second sulfur-containing liquid with sulfur particles at 25 ℃ under an anaerobic condition, and mixing the sulfur adsorption liquid obtained in the step (2) with the reacted second sulfur-containing liquid to obtain a mixed liquid;
(5) aerating the mixed liquor obtained in the step (4) by using oxygen-containing gas at 25 ℃ to enable sulfur-oxidizing microorganisms in the mixed liquor to be in an oxidizing sulfur-producing state, so as to obtain reaction liquid; the oxidation-reduction potential of the aeration treatment is-360 mV; the pH value in the aeration treatment process is 9; the oxygen-containing gas is air;
(6) dividing the reaction solution into a first reaction solution, a second reaction solution and a third reaction solution, wherein the first reaction solution is used as the first absorption solution in the step (1); the second reaction solution is used as the second absorption solution in the step (3); carrying out solid-liquid separation on the third reaction liquid, and recycling the obtained clear liquid in the step (5);
the first absorption liquid and the second absorption liquid are respectively and independently buffer solutions containing sulfur-oxidizing microorganisms; the buffer solution containing sulfur-oxidizing microorganisms is Na2CO3And NaHCO3The buffer solution of (4); the pH value of the buffer solution containing the sulfur-oxidizing microorganisms is 9, and Na in the buffer solution+The concentration of (A) is 1.2 mol/L;
and (4) recycling part of the clean gas obtained in the step (3) for deep adsorption in the step (2).
Application example 3
The sulfur-containing gas desulfurization device system provided in application example 1 of this application example treats sulfur-containing gas, which is simulated sulfur-containing gas, and the composition of the simulated sulfur-containing gas is the same as that in application example 1, and the process of treating sulfur-containing gas includes the following steps:
(1) using first absorption liquid to perform countercurrent treatment on the sulfur-containing gas at the temperature of 35 ℃ to obtain primary purified gas and first sulfur-containing liquid; the liquid-gas ratio of the first absorption liquid to the sulfur-containing gas is 1:40, and the unit of the liquid-gas ratio is L/Nm3；
(2) Deeply adsorbing the first sulfur-containing liquid obtained in the step (1) at the temperature of 35 ℃ to obtain a sulfur adsorption liquid and an anaerobic treatment gas;
(3) carrying out countercurrent treatment on the anaerobic treatment gas obtained in the step (2) by using a second absorption liquid at the temperature of 35 ℃ to obtain a clean gas and a second sulfur-containing liquid; the liquid-gas ratio of the second absorption liquid to the anaerobic treatment gas is 1:40, and the unit of the liquid-gas ratio is L/Nm3；
(4) Reacting organic sulfur in the second sulfur-containing liquid with sulfur particles at 35 ℃ under an anaerobic condition, and mixing the sulfur adsorption liquid obtained in the step (2) with the reacted second sulfur-containing liquid to obtain a mixed liquid;
(5) aerating the mixed liquor obtained in the step (4) by using oxygen-containing gas at the temperature of 35 ℃ to enable sulfur oxidizing microorganisms in the mixed liquor to be in an oxidizing sulfur production state to obtain reaction liquid; the oxidation-reduction potential of the aeration treatment is-320 mV; the pH value in the aeration treatment process is 10; the oxygen-containing gas is oxygen;
(6) dividing the reaction solution into a first reaction solution, a second reaction solution and a third reaction solution, wherein the first reaction solution is used as the first absorption solution in the step (1); the second reaction solution is used as the second absorption solution in the step (3); carrying out solid-liquid separation on the third reaction liquid, and recycling the obtained clear liquid in the step (5);
the first absorption liquid and the second absorption liquid are respectively and independently buffer solutions containing sulfur-oxidizing microorganisms; the buffer solution containing sulfur-oxidizing microorganisms is Na2CO3And NaHCO3The buffer solution of (4); the pH value of the buffer solution containing the sulfur-oxidizing microorganisms is 10, and Na in the buffer solution+The concentration of (A) is 1.8 mol/L;
and (4) recycling part of the clean gas obtained in the step (3) for deep adsorption in the step (2).
Application example 4
The sulfur-containing gas desulfurization device system provided in application example 1 of this application example treats sulfur-containing gas, which is simulated sulfur-containing gas, and the composition of the simulated sulfur-containing gas is the same as that in application example 1, and the process of treating sulfur-containing gas includes the following steps:
(1) using first absorption liquid to perform countercurrent treatment on the sulfur-containing gas at 40 ℃ to obtain primary purified gas and first sulfur-containing liquid; the liquid-gas ratio of the first absorption liquid to the sulfur-containing gas is 1:50, and the unit of the liquid-gas ratio is L/Nm3；
(2) Deeply adsorbing the first sulfur-containing liquid obtained in the step (1) at 40 ℃ to obtain a sulfur adsorption liquid and an anaerobic treatment gas;
(3) carrying out countercurrent treatment on the anaerobic treatment gas obtained in the step (2) by using a second absorption liquid at 40 ℃ to obtain a clean gas and a second sulfur-containing liquid; the liquid-gas ratio of the second absorption liquid to the anaerobic treatment gas is 1:50, and the unit of the liquid-gas ratio is L/Nm3；
(4) Reacting organic sulfur in the second sulfur-containing liquid with sulfur particles at 40 ℃ under an anaerobic condition, and mixing the sulfur adsorption liquid obtained in the step (2) with the reacted second sulfur-containing liquid to obtain a mixed liquid;
(5) aerating the mixed liquor obtained in the step (4) by using oxygen-containing gas at 40 ℃ to enable sulfur oxidizing microorganisms in the mixed liquor to be in an oxidizing sulfur production state to obtain reaction liquid; the oxidation-reduction potential of the aeration treatment is-300 mV; the pH value in the aeration treatment process is 11; the oxygen-containing gas is air;
(6) dividing the reaction solution into a first reaction solution, a second reaction solution and a third reaction solution, wherein the first reaction solution is used as the first absorption solution in the step (1); the second reaction solution is used as the second absorption solution in the step (3); carrying out solid-liquid separation on the third reaction liquid, and recycling the obtained clear liquid in the step (5);
the first absorption liquid and the second absorption liquid are respectively and independently buffer solutions containing sulfur-oxidizing microorganisms; the buffer solution containing sulfur-oxidizing microorganisms is Na2CO3And NaHCO3The buffer solution of (4); the pH value of the buffer solution containing the sulfur-oxidizing microorganisms is 11, and Na in the buffer solution+The concentration of (A) is 2 mol/L;
and (4) recycling part of the clean gas obtained in the step (3) for deep adsorption in the step (2).
Application example 5
The sulfur-containing gas desulfurization device system provided in application example 1 of this application example treats sulfur-containing gas, which is simulated sulfur-containing gas, and the composition of the simulated sulfur-containing gas is the same as that in application example 1, and the process of treating sulfur-containing gas includes the following steps:
(1) using a first absorption liquid to perform countercurrent treatment on the sulfur-containing gas at the temperature of 20 ℃ to obtain a primary purified gas and a first sulfur-containing liquid; the liquid-gas ratio of the first absorption liquid to the sulfur-containing gas is 1:10, and the unit of the liquid-gas ratio is L/Nm3；
(2) Deeply adsorbing the first sulfur-containing liquid obtained in the step (1) at the temperature of 20 ℃ to obtain a sulfur adsorption liquid and an anaerobic treatment gas;
(3) carrying out countercurrent treatment on the anaerobic treatment gas obtained in the step (2) by using a second absorption liquid at the temperature of 20 ℃ to obtain a clean gas and a second sulfur-containing liquid; the liquid-gas ratio of the second absorption liquid to the anaerobic treatment gas is 1:10, and the unit of the liquid-gas ratio is L/Nm3；
(4) Reacting organic sulfur in the second sulfur-containing liquid with sulfur particles at 20 ℃ under an anaerobic condition, and mixing the sulfur adsorption liquid obtained in the step (2) with the reacted second sulfur-containing liquid to obtain a mixed liquid;
(5) aerating the mixed liquor obtained in the step (4) by using oxygen-containing gas at the temperature of 20 ℃ to enable sulfur oxidizing microorganisms in the mixed liquor to be in an oxidizing sulfur production state to obtain reaction liquid; the oxidation-reduction potential of the aeration treatment is-400 mV; the pH value in the aeration treatment process is 8; the oxygen-containing gas is air;
(6) dividing the reaction solution into a first reaction solution, a second reaction solution and a third reaction solution, wherein the first reaction solution is used as the first absorption solution in the step (1); the second reaction solution is used as the second absorption solution in the step (3); carrying out solid-liquid separation on the third reaction liquid, and recycling the obtained clear liquid in the step (5);
the first absorption liquid and the second absorption liquid are respectively and independently buffer solutions containing sulfur-oxidizing microorganisms; the buffer solution containing sulfur-oxidizing microorganisms is Na2CO3And NaHCO3The buffer solution of (4); the pH value of the buffer solution containing the sulfur-oxidizing microorganisms is 8, and Na in the buffer solution+The concentration of (A) is 1 mol/L;
and (4) recycling part of the clean gas obtained in the step (3) for deep adsorption in the step (2).
Comparative application example 1
The sulfur-containing gas desulfurization device system provided in comparative example 1 was applied to the sulfur-containing gas in this comparative application example, the sulfur-containing gas was a simulated sulfur-containing gas, the composition of the simulated sulfur-containing gas was the same as in application example 1, and the process of treating the sulfur-containing gas included the following steps:
(1) using first absorption liquid to perform countercurrent treatment on the sulfur-containing gas at the temperature of 30 ℃ to obtain primary purified gas and first sulfur-containing liquid; the liquid-gas ratio of the first absorption liquid to the sulfur-containing gas is 1:30, and the unit of the liquid-gas ratio is L/Nm3(ii) a The obtained primary purified gas is used as clean gas to be discharged;
(2) carrying out aeration treatment on the first sulfur-containing liquid in the step (1) by using oxygen-containing gas at the temperature of 30 ℃ to enable sulfur oxidizing microorganisms in the mixed liquid to be in an oxidizing sulfur-producing state to obtain reaction liquid; the oxidation-reduction potential of the aeration treatment is-350 mV; the pH value in the aeration treatment process is 9; the oxygen-containing gas is air;
(3) dividing the reaction solution into a first reaction solution and a third reaction solution, wherein the first reaction solution is used as the first absorption solution in the step (1); carrying out solid-liquid separation on the third reaction liquid, and recycling the obtained clear liquid for the step (2);
the first absorption liquid is a buffer solution containing sulfur-oxidizing microorganisms; the buffer solution containing sulfur-oxidizing microorganisms is Na2CO3And NaHCO3The buffer solution of (4); the pH value of the buffer solution containing the sulfur-oxidizing microorganisms is 9, and Na in the buffer solution+The concentration of (2) is 1.5 mol/L.
Comparative application example 2
The sulfur-containing gas desulfurization device system provided in comparative example 2 was applied to the sulfur-containing gas in this comparative application example, the sulfur-containing gas was a simulated sulfur-containing gas, the composition of the simulated sulfur-containing gas was the same as in application example 1, and the process of treating the sulfur-containing gas included the following steps:
(1) using first absorption liquid to perform countercurrent treatment on the sulfur-containing gas at the temperature of 30 ℃ to obtain primary purified gas and first sulfur-containing liquid; the liquid-gas ratio of the first absorption liquid to the sulfur-containing gas is 1:30, and the unit of the liquid-gas ratio is L/Nm3；
(2) Carrying out countercurrent treatment on the primary purified gas obtained in the step (1) by using a second absorption liquid at the temperature of 30 ℃ to obtain a clean gas and a second sulfur-containing liquid; the liquid-gas ratio of the second absorption liquid to the anaerobic treatment gas is 1:30, and the unit of the liquid-gas ratio is L/Nm3；
(3) Mixing the first sulfur-containing liquid and the second sulfur-containing liquid to obtain a mixed liquid;
(4) aerating the mixed liquor obtained in the step (3) by using oxygen-containing gas at the temperature of 30 ℃ to enable sulfur oxidizing microorganisms in the mixed liquor to be in an oxidizing sulfur production state to obtain reaction liquid; the oxidation-reduction potential of the aeration treatment is-350 mV; the pH value in the aeration treatment process is 9; the oxygen-containing gas is air;
(5) dividing the reaction solution into a first reaction solution, a second reaction solution and a third reaction solution, wherein the first reaction solution is used as the first absorption solution in the step (1); the second reaction solution is used as the second absorption solution in the step (2); carrying out solid-liquid separation on the third reaction liquid, and recycling the obtained clear liquid for the step (4);
the first absorption liquid and the second absorption liquid are respectively and independently buffer solutions containing sulfur-oxidizing microorganisms; the buffer solution containing sulfur-oxidizing microorganisms is Na2CO3And NaHCO3The buffer solution of (4); the pH value of the buffer solution containing the sulfur-oxidizing microorganisms is 9, and Na in the buffer solution+The concentration of (2) is 1.5 mol/L.
Comparative application example 3
The sulfur-containing gas desulfurization device system provided in comparative example 3 was applied to the comparative application example to treat sulfur-containing gas, which was simulated sulfur-containing gas, and the composition of the simulated sulfur-containing gas was the same as that in application example 1, and the process of treating sulfur-containing gas included the following steps:
(1) using first absorption liquid to perform countercurrent treatment on the sulfur-containing gas at the temperature of 30 ℃ to obtain primary purified gas and first sulfur-containing liquid; the liquid-gas ratio of the first absorption liquid to the sulfur-containing gas is 1:30, and the unit of the liquid-gas ratio is L/Nm3；
(2) Deeply adsorbing the first sulfur-containing liquid obtained in the step (1) at the temperature of 30 ℃ to obtain a sulfur adsorption liquid and an anaerobic treatment gas;
(3) carrying out countercurrent treatment on the anaerobic treatment gas obtained in the step (2) by using a second absorption liquid at the temperature of 30 ℃ to obtain a clean gas and a second sulfur-containing liquid; the liquid-gas ratio of the second absorption liquid to the anaerobic treatment gas is 1:30, and the unit of the liquid-gas ratio is L/Nm3；
(4) Mixing the sulfur adsorption solution obtained in the step (2) with the second sulfur-containing solution obtained in the step (3) to obtain a mixed solution;
(5) aerating the mixed liquor obtained in the step (4) by using oxygen-containing gas at the temperature of 30 ℃ to enable sulfur oxidizing microorganisms in the mixed liquor to be in an oxidizing sulfur production state to obtain reaction liquid; the oxidation-reduction potential of the aeration treatment is-350 mV; the pH value in the aeration treatment process is 9; the oxygen-containing gas is air;
(6) dividing the reaction solution into a first reaction solution, a second reaction solution and a third reaction solution, wherein the first reaction solution is used as the first absorption solution in the step (1); the second reaction solution is used as the second absorption solution in the step (3); carrying out solid-liquid separation on the third reaction liquid, and recycling the obtained clear liquid in the step (5);
the first absorption liquid and the second absorption liquid are respectively and independently buffer solutions containing sulfur-oxidizing microorganisms; the buffer solution containing sulfur-oxidizing microorganisms is Na2CO3And NaHCO3The buffer solution of (4); the pH value of the buffer solution containing the sulfur-oxidizing microorganisms is 9, and Na in the buffer solution+The concentration of (A) is 1.5 mol/L;
and (4) recycling part of the clean gas obtained in the step (3) for deep adsorption in the step (2).
Comparative application example 4
The sulfur-containing gas desulfurization device system provided in comparative example 4 was applied to the sulfur-containing gas in this comparative application example, the sulfur-containing gas was a simulated sulfur-containing gas, the composition of the simulated sulfur-containing gas was the same as in application example 1, and the process of treating the sulfur-containing gas included the following steps:
(1) using first absorption liquid to perform countercurrent treatment on the sulfur-containing gas at the temperature of 30 ℃ to obtain primary purified gas and first sulfur-containing liquid; the liquid-gas ratio of the first absorption liquid to the sulfur-containing gas is 1:30, and the unit of the liquid-gas ratio is L/Nm3；
(2) Carrying out countercurrent treatment on the primary purified gas obtained in the step (1) by using a second absorption liquid at the temperature of 30 ℃ to obtain a clean gas and a second sulfur-containing liquid; the liquid-gas ratio of the second absorption liquid to the anaerobic treatment gas is 1:30, and the unit of the liquid-gas ratio is L/Nm3；
(3) Reacting organic sulfur in the second sulfur-containing liquid with sulfur particles at 30 ℃ under an anaerobic condition, and mixing the first sulfur-containing liquid obtained in the step (1) with the reacted second sulfur-containing liquid to obtain a mixed liquid;
(4) aerating the mixed liquor obtained in the step (3) by using oxygen-containing gas at the temperature of 30 ℃ to enable sulfur oxidizing microorganisms in the mixed liquor to be in an oxidizing sulfur production state to obtain reaction liquid; the oxidation-reduction potential of the aeration treatment is-350 mV; the pH value in the aeration treatment process is 9; the oxygen-containing gas is air;
(5) dividing the reaction solution into a first reaction solution, a second reaction solution and a third reaction solution, wherein the first reaction solution is used as the first absorption solution in the step (1); the second reaction solution is used as the second absorption solution in the step (2); carrying out solid-liquid separation on the third reaction liquid, and recycling the obtained clear liquid for the step (4);
the first absorption liquid and the second absorption liquid are respectively and independently buffer solutions containing sulfur-oxidizing microorganisms; the buffer solution containing sulfur-oxidizing microorganisms is Na2CO3And NaHCO3The buffer solution of (4); the pH value of the buffer solution containing the sulfur-oxidizing microorganisms is 9, and Na in the buffer solution+The concentration of (A) is 1.5 mol/L;
and (3) recycling part of the clean gas obtained in the step (2) to provide an anaerobic environment in the step (3).
Application examples 1 to 5 andthe simulated sulfur-containing gas in comparative application examples 1 to 4 contained only H2Testing the elemental sulfur conversion rate during S, wherein each system runs stably during testing; then, H was contained in the simulated sulfur-containing gases of the corresponding application examples 1 to 5 and the comparative application examples 1 to 4 at the same time2And (3) testing the elemental sulfur conversion rate of S and methyl mercaptan, wherein each system runs stably during testing. The elemental sulfur conversion is the ratio of sulfur in the sulfur-containing gas to elemental sulfur, and the test results are shown in table 1.
TABLE 1
Figure BDA0002912235860000241
As can be seen from table 1, when no organic sulfur is added to the sulfur-containing gas, the elemental sulfur conversion rate of the sulfur-containing gas desulfurization apparatus system provided in example 1 is the highest, and the elemental sulfur conversion rates of the sulfur-containing gas desulfurization apparatus systems provided in comparative examples 3 and 4 are higher than those of the sulfur-containing gas desulfurization apparatus systems provided in comparative examples 1 and 2, which indicates that the provision of the deep absorption tower and the anaerobic conversion tower is advantageous for increasing the elemental sulfur conversion rate. Meanwhile, the introduction of organic sulfur reduces the elemental sulfur conversion rate of the deep adsorption tower and the anaerobic conversion tower provided in the example 1 and the comparative examples 1 to 4, but the reduction range of the example 1 is the smallest, the reduction range of the comparative examples 3 to 4 is smaller than that of the comparative examples 1 to 2, and the arrangement of the surface deep adsorption tower and the anaerobic conversion tower can avoid the inhibition of the biological desulfurization process by the organic sulfur.
In conclusion, the sulfur-containing gas desulfurization device system effectively reduces the inhibition of organic sulfur to the biological desulfurization process and strengthens the desulfurization of HS by the desulfurization bacteria through the arrangement of the deep adsorption device, the tail gas removal device and the anaerobic conversion device-Absorption and HS-The selection of oxidation route greatly reduces S in the treatment process2O3 2-And SO4 2-The formation improves the generation rate of the elemental sulfur, reduces the requirement on liquid caustic soda for adjusting the pH value and improves the generation rate of the elemental sulfur; the sulfur-containing gas desulfurization device system and the method provided by the invention effectively reduce the biological removal of sulfur-containing gasThe method has the advantages of solving the problem of inhibiting organic sulfur in the sulfur process, improving the generation rate of elemental sulfur, reducing the requirement on liquid caustic soda for adjusting pH, obviously improving the economical efficiency of the process, along with high treatment efficiency, low energy consumption, low operation cost, high added value of products, easiness in industrial popularization and good application prospect.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. The sulfur-containing gas desulfurization device system is characterized by comprising a biological purification device, a deep adsorption device, a tail gas removal device, an anaerobic conversion device, a biological regeneration device and a sulfur collection device;
the liquid outlet of the biological purification device is connected with the liquid inlet of the deep adsorption device;
the liquid outlet of the tail gas removing device is connected with the liquid inlet of the anaerobic conversion device;
the liquid outlet of the deep adsorption device and the liquid outlet of the anaerobic conversion device are respectively and independently connected with the liquid inlet of the biological regeneration device;
the liquid outlet of the biological regeneration device is respectively and independently connected with the liquid inlets of the biological purification device, the tail gas removal device and the sulfur collection device;
the sulfur collecting device is used for separating elemental sulfur, and clear liquid obtained by separation flows back to the biological regeneration device;
the gas outlet of the biological purification device and the gas outlet of the deep adsorption device are respectively and independently connected with the gas inlet of the tail gas removal device; and a gas outlet of the tail gas removing device is provided with a gas backflow branch, and the gas backflow branch is respectively and independently connected with a gas inlet of the anaerobic conversion device and an aeration piece in the deep adsorption device.
2. The sulfur-containing gas desulfurization apparatus system according to claim 1, wherein an aeration device is provided in said biological regeneration apparatus, said aeration device being adapted to supply an oxygen-containing gas to the biological regeneration apparatus.
3. The sulfur-containing gas desulfurization apparatus system according to claim 2, wherein said aeration device comprises an aeration pipe and/or an aeration tray;
preferably, the aeration member comprises an aeration pipe and/or an aeration disc.
4. The sulfur-containing gas desulfurization apparatus according to any one of claims 1 to 3, wherein a mechanical stirring device is provided in said deep absorption unit.
5. A method for desulfurizing a sulfur-containing gas, characterized in that the method is carried out in the system of the sulfur-containing gas desulfurization apparatus according to any one of claims 1 to 4.
6. The method for desulfurizing sulfur-containing gas according to claim 5, comprising the steps of:
(1) treating sulfur-containing gas by using a first absorption liquid to obtain a primary purified gas and a first sulfur-containing liquid;
(2) deeply adsorbing the first sulfur-containing liquid obtained in the step (1) to obtain a sulfur adsorption liquid and anaerobic treatment gas;
(3) treating the anaerobic treatment gas obtained in the step (2) by using a second absorption liquid to obtain a clean gas and a second sulfur-containing liquid;
(4) reacting organic sulfur in the second sulfur-containing liquid with sulfur particles under an anaerobic condition, and mixing the sulfur adsorption liquid obtained in the step (2) with the reacted second sulfur-containing liquid to obtain a mixed liquid;
(5) carrying out aeration treatment on the mixed solution obtained in the step (4) by using oxygen-containing gas to enable sulfur oxidizing microorganisms in the mixed solution to be in an oxidizing sulfur-producing state to obtain a reaction solution;
(6) dividing the reaction solution into a first reaction solution, a second reaction solution and a third reaction solution, wherein the first reaction solution is used as the first absorption solution in the step (1); the second reaction solution is used as the second absorption solution in the step (3); carrying out solid-liquid separation on the third reaction liquid, and recycling the obtained clear liquid in the step (5);
the first absorption liquid and the second absorption liquid are respectively and independently buffer solutions containing sulfur-oxidizing microorganisms;
and (4) recycling part of the clean gas obtained in the step (3) for deep adsorption in the step (2).
7. The method for desulfurizing a sulfur-containing gas according to claim 6, wherein the sulfur oxidizing microorganisms in the buffer solution containing the sulfur oxidizing microorganisms are sulfur oxidizing bacteria, preferably Vibrio thiolyticus;
preferably, the buffer solution containing sulfur-oxidizing microorganisms is Na2CO3And NaHCO3The buffer solution of (4);
preferably, the pH value of the buffer solution containing the sulfur oxidizing microorganisms is 8-11;
preferably, the first absorption liquid in the step (1) is used for treating sulfur-containing gas in a countercurrent manner;
preferably, the second treatment liquid in step (3) is used for treating anaerobic treatment gas in a countercurrent mode.
8. The sulfur-containing gas desulfurization method according to any one of claims 6 or 7, wherein the sulfur-containing gas of step (1) comprises H2S and organic sulfur;
preferably, the organic sulfur comprises any one of methyl mercaptan, ethyl mercaptan, propyl mercaptan, carbon disulfide, dimethyl sulfide, dimethyl disulfide or dimethyl trisulfide or a combination of at least two of the same;
preferably, the oxygen-containing gas of step (5) is oxygen and/or air;
preferably, the liquid-gas ratio of the first absorption liquid to the sulfur-containing gas in the step (1) is 1 (10-50), and the unit of the liquid-gas ratio is L/Nm3；
Preferably, the stepsThe liquid-gas ratio of the second absorption liquid to the anaerobic treatment gas in the step (3) is 1 (10-50), and the unit of the liquid-gas ratio is L/Nm3。
9. The sulfur-containing gas desulfurization method according to any one of claims 6 to 8, wherein the temperature of the treatment of step (1) is 20 to 40 ℃;
preferably, the temperature of the deep adsorption in the step (2) is 20-40 ℃;
preferably, the temperature of the treatment in the step (3) is 20-40 ℃;
preferably, the temperature of the reaction in the step (4) is 20-40 ℃;
preferably, the oxidation-reduction potential of the aeration treatment in the step (5) is-400 mV to-300 mV;
preferably, the pH value in the aeration treatment process in the step (5) is 8-11;
preferably, the temperature of the aeration treatment process in the step (5) is 20-40 ℃;
preferably, the solid-liquid separation method in the step (6) is gravity settling.
10. A sulfur-containing gas desulfurization method according to any one of claims 6 to 9, characterized by comprising the steps of:
(1) using a first absorption liquid to perform countercurrent treatment on the sulfur-containing gas at the temperature of 20-40 ℃ to obtain a primary purified gas and a first sulfur-containing liquid; the sulfur-containing gas comprises H2S and organic sulfur; the liquid-gas ratio of the first absorption liquid to the sulfur-containing gas is 1 (10-50), and the unit of the liquid-gas ratio is L/Nm3；
(2) Deeply adsorbing the first sulfur-containing liquid obtained in the step (1) at the temperature of 20-40 ℃ to obtain a sulfur adsorption liquid and anaerobic treatment gas;
(3) carrying out countercurrent treatment on the anaerobic treatment gas obtained in the step (2) by using a second absorption liquid at the temperature of 20-40 ℃ to obtain a clean gas and a second sulfur-containing liquid; the liquid-gas ratio of the second absorption liquid to the anaerobic treatment gas is 1 (10-50), and the unit of the liquid-gas ratio is L/Nm3；
(4) Reacting organic sulfur in the second sulfur-containing liquid with sulfur particles at 20-40 ℃ under anaerobic conditions, and mixing the sulfur adsorption liquid obtained in the step (2) with the reacted second sulfur-containing liquid to obtain a mixed liquid;
(5) aerating the mixed liquor in the step (4) by using oxygen-containing gas at the temperature of 20-40 ℃ to enable sulfur oxidizing microorganisms in the mixed liquor to be in an oxidizing sulfur-producing state to obtain reaction liquid; the oxidation-reduction potential of the aeration treatment is-400 mV to-300 mV; the pH value in the aeration treatment process is 8-11;
(6) dividing the reaction solution into a first reaction solution, a second reaction solution and a third reaction solution, wherein the first reaction solution is used as the first absorption solution in the step (1); the second reaction solution is used as the second absorption solution in the step (3); carrying out solid-liquid separation on the third reaction liquid, and recycling the obtained clear liquid in the step (5);
the first absorption liquid and the second absorption liquid are respectively and independently buffer solutions containing sulfur-oxidizing microorganisms; the buffer solution containing sulfur-oxidizing microorganisms is Na2CO3And NaHCO3The buffer solution of (4); the pH value of the buffer solution containing the sulfur-oxidizing microorganisms is 8-11;
and (4) recycling part of the clean gas obtained in the step (3) for deep adsorption in the step (2).
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