CN110684573A - Biological desulfurization method for low-sulfur natural gas - Google Patents
Biological desulfurization method for low-sulfur natural gas Download PDFInfo
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- CN110684573A CN110684573A CN201810738411.9A CN201810738411A CN110684573A CN 110684573 A CN110684573 A CN 110684573A CN 201810738411 A CN201810738411 A CN 201810738411A CN 110684573 A CN110684573 A CN 110684573A
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- sulfur
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention belongs to the field of gas separation, and provides a biological desulfurization method for natural gas with low sulfur content, which can purify natural gas with the hydrogen sulfide content of 0 ~ 5000ppm and the pressure grade of 5.0 ~ 9.0.0 MPa to less than 20mg/m3. The process of the invention is as follows: the low-sulfur natural gas enters an absorption tower and is in countercurrent contact with alkali liquor sprayed from top to bottom in the absorption tower, rich liquor at the bottom of the absorption tower enters a flash evaporation tank, part of dissolved methane is flashed out and then enters a bioreactor, sulfide is oxidized into sulfur under the action of thiobacillus and air in the bioreactor, the sulfur is separated in a settling tank after three-phase separation, and the sulfur is obtained as a 99.9% product through a sulfur melting kettle.
Description
Technical Field
The invention belongs to the field of gas separation, and relates to a biological desulfurization method for natural gas with low sulfur content.
Background
The natural gas desulfurization method includes dry desulfurization and wet desulfurization, the dry desulfurization adopts zinc oxide or ferric oxide and other desulfurizing agents to remove hydrogen sulfide in a fixed bed, and is generally used for fine desulfurization, the wet desulfurization comprises alcohol amine method, LOCAT method, biological desulfurization method and the like, the alcohol amine method is a common natural gas desulfurization method, and is used in occasions with large sulfur potential, after the natural gas is purified, a Claus method is needed to recover sulfur in acid gas, the LOCAT method adopts the principle of redox, sulfides contained in the natural gas are converted into sulfur, and iron-containing series salts are used as catalysts in the process.
Disclosure of Invention
The invention provides a biological desulfurization method for natural gas with low sulfur content.
The main technical scheme of the invention is as follows: the biological desulfurization method for the natural gas with low sulfur content is characterized by comprising the following steps: the low-sulfur natural gas enters an absorption tower and is in countercurrent contact with alkali liquor sprayed from top to bottom in the absorption tower, rich liquor at the bottom of the absorption tower enters a flash evaporation tank, part of dissolved methane is flashed out and then enters a bioreactor, sulfide is oxidized into sulfur under the action of thiobacillus and air in the bioreactor, the sulfur is separated in a settling tank after three-phase separation, and the sulfur is obtained as a 99.9% product through a sulfur melting kettle.
Preferably, the alkali liquor of the present invention is composed of one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, etc., and the PH of the alkali liquor is 7 ~ 10, preferably 8 ~ 9.
The pressure of the natural gas is 1.0 ~ 8.0.0 MPa, preferably 3.0 ~ 8.0.0 MPa, and the pressure of the flash drum is 0.3 ~ 0.8.8 MPa, preferably 0.4 ~ 0.6.6 MPa.
The structure of the bioreactor is an airlift circulating structure.
The bioreactor is added with a defoaming agent, the defoaming agent is polyether or silicone, and the concentration of the defoaming agent in a desulfurization system is 2 ~ 50ppm, preferably 3 ~ 10 ppm.
The thiobacillus is one or more of thiobacillus denitrificans and thiobacillus thioparus.
By the biological desulfurization method, natural gas with the hydrogen sulfide content of 0 ~ 5000ppm and the pressure grade of 5.0 ~ 9.0.0 MPa can be purified to be less than 20mg/m3。
Drawings
FIG. 1 is a process flow diagram of an embodiment of the invention.
In the figure, T101-absorption tower, P101-barren liquor pump, V101-flash drum, P101-bioreactor, P102-circulating pump, M101-centrifuge, P103-sulfur foam pump, V102-settling tank.
Detailed Description
The following examples will better illustrate the invention without limiting its scope.
Referring to the attached figure 1, after natural gas enters an absorption tower and is subjected to countercurrent contact reaction with alkali liquor sprayed at the top of the absorption tower for absorption, the pH of absorption liquid is controlled within the range of 7.0 ~ 10.0.0, and treated purified gas leaves from the top of the absorption tower.
The rich solution enters a flash evaporation tank from the bottom of the absorption tower, the rich solution enters a bioreactor after the dissolved methane is flashed out, the temperature of the rich solution is controlled within the range of 30 ~ 40 ℃, in the bioreactor, under the combined action of air and microbial bacteria, bacteria play a catalytic role in the reaction, the sulfide reacts with oxygen to generate elemental sulfur or sulfate, and meanwhile, the absorption solution is regenerated and recycled.
The regenerated alkali liquor rich in sulfur from the bioreactor is settled and separated in a settling tank to obtain sulfur slurry, and the sulfur slurry enters a centrifugal machine for further concentration into sulfur cakes. The separated liquid phase filtrate is returned to the solution storage tank. The supernatant liquid also enters the solution storage tank, and the barren solution enters the absorption tower for recycling.
Example 1
Natural gas quantity 1Nm3H, pressure 5.0MPa, hydrogen sulfide content 2000ppm, CO2The content is 10 percent, the air amount is 100L/H, the flow rate of barren solution is 20L/H, and H in purified gas is purified by a biological desulfurization process2The S content is 18mg/m3。
Example 2
Natural gas quantity 1Nm3H, pressure 7.0MPa, hydrogen sulfide content 2000ppm, CO2The content is 10 percent, the air amount is 200L/H, the barren solution flow is 20L/H, and H in purified gas is purified by a biological desulfurization process2The S content is 10mg/m3。
Example 3
Natural gas quantity 1Nm3H, pressure 9.0MPa, hydrogen sulfide content 2000ppm, CO2The content is 10 percent, the air amount is 200L/H, the barren solution flow is 20L/H, and H in purified gas is purified by a biological desulfurization process2The S content is 6mg/m3。
Example 4
Natural gas quantity 1Nm3H, pressure 5.0MPa, hydrogen sulfide content 3500ppm, CO2The content is 10 percent, the air amount is 200L/H, the barren solution flow is 20L/H, and H in purified gas is purified by a biological desulfurization process2The S content is 15mg/m3。
Example 5
Natural gas quantity 1Nm3H, pressure 7.0MPa, hydrogen sulfide content 3500ppm, CO2The content is 10 percent, the air amount is 300L/H, the flow rate of barren solution is 20L/H, and H in purified gas is purified by a biological desulfurization process2The S content is 12mg/m3。
Example 6
Natural gas quantity 1Nm3H, pressure 9.0MPa, hydrogen sulfide content 3500ppm, CO2The content is 10 percent, the air amount is 100L/H, the flow rate of barren solution is 20L/H, and H in purified gas is purified by a biological desulfurization process2The S content is 10mg/m3。
Example 7
Natural gas quantity 1Nm3H, pressure 5.0MPa, hydrogen sulfide content 5000ppm, CO2The content is 10 percent, the air amount is 300L/H, the flow rate of barren solution is 20L/H, and H in purified gas is purified by a biological desulfurization process2S containsThe amount is 19mg/m3。
Claims (10)
1. A method for biological desulfurization of natural gas with low sulfur content is characterized by comprising the following steps: the low-sulfur natural gas enters an absorption tower and is in countercurrent contact with alkali liquor sprayed from top to bottom in the absorption tower, rich liquor at the bottom of the absorption tower enters a flash evaporation tank, part of dissolved methane is flashed out and then enters a bioreactor, sulfide is oxidized into sulfur under the action of thiobacillus and air in the bioreactor, the sulfur is separated in a settling tank after three-phase separation, and the sulfur is obtained as a 99.9% product through a sulfur melting kettle.
2. The method of claim 1, wherein the low sulfur natural gas has a hydrogen sulfide content of 0 ~ 5000 ppm.
3. The method of claim 2, wherein the low sulfur natural gas has a hydrogen sulfide content of 0 ~ 2000 ppm.
4. The method of claim 1, wherein the alkali solution comprises one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, etc., and has a pH of 7 ~ 10.
5. The process according to claim 1 or 4, wherein the pH of the lye is 8 ~ 9.
6. The process of claim 1 wherein the pressure of the natural gas is 5.0 ~ 9.0.0 MPa and the pressure of the flash drum is 0.3 ~ 0.8.8 MPa.
7. The method of claim 1, wherein: the structure of the bioreactor is an airlift circulating structure.
8. The method of claim 1, wherein the antifoaming agent is one or more of polyether or silicone, and the concentration of the antifoaming agent in the desulfurization system is 2 ~ 50 ppm.
9. The method of claim 8, wherein the concentration of the defoaming agent in the desulfurization system is 3 ~ 10 ppm.
10. The method of claim 1, wherein: the thiobacillus is one or more of Naplesio thiobacillus, Thiobacillus denitrificans and thiobacillus thioparus.
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CN105498470A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Microorganism desulfurizing and sulfur recycling method |
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CN105498470A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Microorganism desulfurizing and sulfur recycling method |
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