CN110559815A - Method for removing hydrogen sulfide and mercaptan in gas - Google Patents
Method for removing hydrogen sulfide and mercaptan in gas Download PDFInfo
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- CN110559815A CN110559815A CN201910876054.7A CN201910876054A CN110559815A CN 110559815 A CN110559815 A CN 110559815A CN 201910876054 A CN201910876054 A CN 201910876054A CN 110559815 A CN110559815 A CN 110559815A
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- Prior art keywords
- gas
- mercaptan
- hydrogen sulfide
- sodium hydroxide
- absorption tower
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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
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D53/52—Hydrogen sulfide
-
- 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
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/304—Alkali metal compounds of sodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/604—Hydroxides
-
- 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
Abstract
the invention belongs to the technical field of gas purification, and particularly relates to a method for removing hydrogen sulfide and mercaptan from gas, which specifically comprises the steps of adding a quinone compound into a sodium hydroxide desulfurization solution, spraying and mixing the sodium hydroxide desulfurization solution and the gas to be treated, and removing the hydrogen sulfide and the mercaptan from the gas through the covalent bond and the action of the quinone compound, the hydrogen sulfide and the mercaptan; the sodium hydroxide desulfurization solution contains quinone compounds with the concentration of 3-15 g/L. The process of the invention has the following characteristics: (1) the removal efficiency of hydrogen sulfide and mercaptan is high, the removal rate of mercaptan is more than 95%, and the total removal rate of sulfur is more than 99.5%; (2) the desulfurization solution has low cost. The method can be used for removing hydrogen sulfide and mercaptan in natural gas treatment and refinery.
Description
Technical Field
The invention belongs to the technical field of gas purification, and particularly relates to a method for removing hydrogen sulfide and mercaptan from gas, in particular to a covalent bonding desulfurization method by adding quinone compounds into sodium hydroxide desulfurization solution.
Background
It is known that industrial raw material gas containing hydrogen sulfide can cause corrosion of pipelines and equipment, and poisoning of catalysts, which affects product quality; the emission of waste gases containing hydrogen sulphide and mercaptans can cause serious environmental problems.
However, the methods for removing hydrogen sulfide in the prior art mainly include: (1) and dry desulfurization, such as an iron oxide method, a zinc oxide method, an activated carbon method and the like. (2) The alcohol amine method. (3) Wet oxidation processes such as ADA process, tannin extract process, MSQ process, PDS process, and complex iron process, etc. (4) Physical solvent methods such as low temperature methanol method, NHD method, etc.
The method for removing mercaptan mainly comprises the following steps: (1) physical adsorption methods such as AC (activated carbon) or modified activated carbon, etc. (2) Organic solvent method. (3) A strong oxidant method. (4) Alkali liquor absorption method.
With the exploitation of sulfur-containing oil field gas and high-sulfur-containing natural gas, the gas contains hydrogen sulfide and mercaptan, the refinery gas contains hydrogen sulfide and mercaptan, the hydrogen sulfide is usually removed by an amine method, and the gas from which the hydrogen sulfide is removed absorbs the mercaptan by alkali, so that the problems of environmental pollution, equipment corrosion and product quality caused by the complicated process of industrial raw material gas containing the hydrogen sulfide and the mercaptan exist, and the problems of complicated technical process, high cost and the like of the traditional dry desulfurization, wet oxidative desulfurization and alcohol amine desulfurization exist.
Disclosure of Invention
In order to effectively solve the problems, the invention provides a method for removing hydrogen sulfide and mercaptan from gas.
The specific technical scheme of the invention is as follows:
A method for removing hydrogen sulfide and mercaptan in gas is characterized in that sodium hydroxide desulfurization solution is sprayed and mixed with gas to be treated to remove hydrogen sulfide and mercaptan in gas;
The sodium hydroxide desulfurization solution contains quinone compounds with the concentration of 3-15 g/L.
Further, the quinone compound comprises one or more of p-benzoquinone, o-benzoquinone and 2, 6-dimethyl-p-benzoquinone.
Further, the temperature of the sodium hydroxide desulfurization solution in the process of treating gas is 30-40 ℃;
The pH value of the sodium hydroxide desulfurization solution is 9-12.
further, the method comprises the steps of:
A) Providing an absorption tower;
B) Introducing gas to be treated at the middle lower part of the absorption tower;
C) Introducing a sodium hydroxide desulfurization solution containing quinone compounds into the top of the absorption tower;
D) sodium hydroxide desulfurization solution and gas to be treated are mixed and stored to the bottom of the absorption tower, and sulfur-containing pregnant solution is subjected to hydrothermal treatment after being discharged from the bottom to generate sulfur-containing humus.
Further, the gas to be treated is stably fed to the lower middle position of the absorption tower through a buffer.
and further, discharging the desulfurization tail gas subjected to desulfurization treatment through the top of the absorption tower to finish desulfurization operation.
Further, a thermometer for monitoring the gas to be treated is arranged between the buffer and the absorption tower;
Sodium hydroxide desulfurization solution after passing through a thermometer for monitoring the liquid temperature, the sodium hydroxide desulfurization solution is introduced into the top of the absorption tower.
further, the temperature of the hydrothermal treatment of the sulfur-containing rich liquid in the step D) is 160-200 ℃.
Further, the sodium hydroxide desulfurization solution is sprayed into the absorption tower through a spray header arranged at the top in the absorption tower.
The principle of the invention is that hydrogen sulfide and mercaptan are converted into corresponding compound molecules in the absorption process of the sodium hydroxide alkaline desulfurization solution; under the action of quinone compounds, hydrogen sulfide and mercaptan with mercapto structures and the quinone compounds undergo nucleophilic addition reaction to generate polymers connected by C-S-C covalent bonds, the reacted solution generates macromolecular humus by a hydrothermal method, harmless removal is realized, and the treated gas is directly discharged.
further, converting hydrogen sulfide and mercaptan into macromolecular polymer covalently bonded by C-S-C by adopting sodium hydroxide alkaline absorption solution containing quinone compounds; the absorption liquid absorbing the hydrogen sulfide and the mercaptan is used for generating sulfur-containing humus harmless to the environment through a hydrothermal method, and meanwhile, the gas meets the emission requirement. The absorption liquid is sodium hydroxide alkaline desulfurization liquid, the absorption temperature and the hydrothermal temperature of the desulfurization liquid are respectively 30-40 ℃ and 160-200 ℃, and the pH value of the solution in the absorption and hydrothermal processes is controlled to be 9-12.
after the gas containing the hydrogen sulfide and the mercaptan is desulfurized, the total sulfur removal rate is over 99.5 percent.
The invention has the beneficial effects that: the method can be used for removing hydrogen sulfide and mercaptan in natural gas and refinery, the efficiency of removing the hydrogen sulfide and the mercaptan from the sodium hydroxide alkaline solution is improved after the quinone compound is added into the sodium hydroxide alkaline solution, the hydrogen sulfide and the mercaptan in the gas can be removed to the pipe transmission standard, the content of the hydrogen sulfide in the treated gas is 0.1-10%, and the content of the mercaptan is 5-1000 mg/Nm3Preferably, the hydrogen sulfide in the processing gas contains 0.1-5% of sulfur and 5-200 mg/Nm of mercaptan3。
Furthermore, the removal efficiency of hydrogen sulfide and mercaptan is high, the removal rate of mercaptan is more than 95%, and the total removal rate of sulfur is more than 99.5%; the desulfurization solution has low cost.
Drawings
FIG. 1 is a process flow diagram of a first embodiment of the present invention.
Detailed Description
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention and do not limit the application scope of the present invention, and it is obvious for a person skilled in the art to apply the present invention to other similar scenes according to the drawings without creative efforts;
As used in this specification and the appended claims, the singular forms "a", "an", and/or "the" include plural referents unless the context clearly dictates otherwise. In general, the terms "comprises" or "comprising" merely indicate that steps and elements which are explicitly identified are included, that these steps and elements do not constitute an exclusive list, and that a method or apparatus may also comprise other steps or elements. The term "based on" is "based, at least in part, on". The term "one embodiment" means "at least one embodiment"; the term "another embodiment" means "at least one additional embodiment".
The first embodiment of the present invention:
(1) Test conditions
In this embodiment, the test gas is a natural gas to which a certain amount of hydrogen sulfide and mercaptan are added, and is set as a sulfur-containing gas, and the test is performed, wherein the specific parameters are as follows:
The concentration of hydrogen sulfide prepared by natural gas is 8.6g/Nm3methyl mercaptan 160g/Nm3Ethanethiol 30g/Nm3the test gas of (1).
Test gas flow rate: 1Nm3Hour/hour
Gas pressure: 1MPa of
Liquid flow rate: 30L/hr
The absorption temperature is 30-40 ℃, and the hydrothermal temperature is 160-200 DEG C
Content of p-benzoquinone: 8g/L
The concentration of sodium hydroxide in the desulfurization solution is as follows: 3g/L
pH value of the solution 11
(2) Test method
As shown in figure 1, the invention uses sodium hydroxide alkaline desulfurization solution containing p-benzoquinone to remove hydrogen sulfide and mercaptan in gas, after sulfur-containing gas passes through a buffer from bottom to top, the gas temperature is monitored by a thermometer and then stably enters the bottom of an absorption tower, and after the stable temperature is set, desulfurization absorption liquid only passes through the top of the absorption tower from top to bottom through a distributor and a spray header and is in countercurrent contact with the sulfur-containing gas to carry out desulfurization reaction;
the content of hydrogen sulfide and mercaptan in the desulfurized gas is analyzed by a determinator, the rich solution absorbing sulfide is collected at the bottom of an absorption tower, the collected solution enters a hydrothermal unit for treatment, a sulfur-containing humus product is generated, and the regeneration and utilization of the sulfur-containing product are realized.
In this embodiment, the buffer is a buffer device for stabilizing gas pressure, which is commonly used in the art, the thermometer is a conventional device for measuring temperature in the art, the distributor and the shower head are conventional devices in gas treatment in the art, and the hydrothermal unit is a conventional hydrothermal treatment unit in the art, which is not specifically limited herein.
(3) Desulfurization effect
Under the above test conditions, aeration was continued for 72 hours, and the average content of hydrogen sulfide in the purified gas during absorption was 15mg/Nm3methyl mercaptan 870mg/Nm3Ethanethiol 32mg/Nm3。
second embodiment of the invention:
(1) Test conditions
Preparation of hydrogen sulfide with concentration of 9.2g/Nm from natural gas3methyl mercaptan 170g/Nm3Ethanethiol 34g/Nm3The test gas of (1).
Test gas flow rate: 1Nm3Hour/hour
Gas pressure: 1MPa of
Liquid flow rate: 32L/hr
The absorption temperature is 30-40 ℃, and the hydrothermal temperature is 160-200 DEG C
Content of p-benzoquinone: 3.5g/L
the content of o-benzoquinone is as follows: 5/L
the concentration of sodium hydroxide in the desulfurization solution is as follows: 3.4g/L
pH value of the solution 12
(2) The test method is the same as the content of the embodiment, and will not be described herein again;
(3) Desulfurization effect
Under the above test conditions, aeration was continued for 72 hours, and the average content of hydrogen sulfide in the purified gas during absorption was 16mg/Nm3Methyl mercaptan 850mg/Nm3Ethanethiol 30mg/Nm3。
Third embodiment of the invention:
(1) Test conditions
Preparing hydrogen sulfide with concentration of 20.6g/Nm by natural gas3methyl mercaptan 300g/Nm3ethanethiol 70g/Nm3The test gas of (1).
Test gas flow rate: 1Nm3Hour/hour
Gas pressure: 1MPa of
Liquid flow rate: 30L/hr
The absorption temperature is 30-40 ℃, and the hydrothermal temperature is 160-200 DEG C
The content of o-benzoquinone is as follows: 5g/L
2, 6-dimethyl-p-benzoquinone content: 5g/L
The concentration of sodium hydroxide in the desulfurization solution is as follows: 5g/L
pH value of the solution 11
(2) The test method is the same as the content of the embodiment, and will not be described herein again;
(3) Desulfurization effect
under the above test conditions, aeration was continued for 72 hours, and the average content of hydrogen sulfide in the purified gas during absorption was 20mg/Nm3Methyl mercaptan 900mg/Nm3Ethylenethiol 47mg/Nm3。
By applying the method for removing hydrogen sulfide and mercaptan from gas, the efficiency of removing hydrogen sulfide and mercaptan from sodium hydroxide alkaline solution is improved after quinone compounds are added into the sodium hydroxide alkaline solution, the hydrogen sulfide and mercaptan in the gas can be removed to the pipe transportation standard, the content of hydrogen sulfide in the treated gas is 0.1-10%, the mercaptan content is 5-1000 mg/Nm3, and preferably, the content of hydrogen sulfide in the treated gas is 0.1-5%, and the mercaptan content is 5-200 mg/Nm 3. The removal efficiency of hydrogen sulfide and mercaptan is high, the removal rate of mercaptan is more than 95%, and the total removal rate of sulfur is more than 99.5%; the desulfurization solution has low cost.
Claims (9)
1. A method for removing hydrogen sulfide and mercaptan in gas is characterized in that sodium hydroxide desulfurization solution is sprayed and mixed with gas to be treated to remove hydrogen sulfide and mercaptan in gas;
The sodium hydroxide desulfurization solution contains quinone compounds with the concentration of 3-15 g/L.
2. The method as claimed in claim 1, wherein the quinone compound comprises one or more of p-benzoquinone, o-benzoquinone and 2, 6-dimethyl-p-benzoquinone.
3. the method for removing hydrogen sulfide and mercaptan from gas as recited in claim 1, wherein the temperature of said sodium hydroxide desulfurization solution during the treatment of gas is 30-40 ℃;
the pH value of the sodium hydroxide desulfurization solution is 9-12.
4. A method for removing hydrogen sulphide and mercaptans from a gas according to any of claims 1-3, characterized in that the method comprises the following steps:
A) Providing an absorption tower;
B) Introducing gas to be treated at the middle lower part of the absorption tower;
C) Introducing a sodium hydroxide desulfurization solution containing quinone compounds into the top of the absorption tower;
D) Sodium hydroxide desulfurization solution and gas to be treated are mixed and stored to the bottom of the absorption tower, and sulfur-containing pregnant solution is subjected to hydrothermal treatment after being discharged from the bottom to generate sulfur-containing humus.
5. The method for removing hydrogen sulfide and mercaptan from gas as recited in claim 4, wherein said gas to be treated is stably fed to a lower middle position of said absorption tower through a buffer.
6. The method for removing hydrogen sulfide and mercaptan from gas as recited in claim 4, wherein the desulfurization tail gas after desulfurization treatment is discharged from the top of the absorption tower to complete the desulfurization operation.
7. The method for removing hydrogen sulfide and mercaptan from gas as recited in claim 5, wherein a thermometer for monitoring the gas to be treated is arranged between the buffer and the absorption tower;
Sodium hydroxide desulfurization solution after passing through a thermometer for monitoring the liquid temperature, the sodium hydroxide desulfurization solution is introduced into the top of the absorption tower.
8. The method for removing hydrogen sulfide and mercaptan from gas as recited in claim 4, wherein the temperature of the hydrothermal treatment of the sulfur-containing rich liquid in step D) is 160-200 ℃.
9. the method for removing hydrogen sulfide and mercaptan from gas as recited in claim 4, wherein said sodium hydroxide desulfurization solution is sprayed into said absorption tower through a spray header disposed at the top of said absorption tower.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910876054.7A CN110559815A (en) | 2019-09-17 | 2019-09-17 | Method for removing hydrogen sulfide and mercaptan in gas |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910876054.7A CN110559815A (en) | 2019-09-17 | 2019-09-17 | Method for removing hydrogen sulfide and mercaptan in gas |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0278419A (en) * | 1988-09-14 | 1990-03-19 | Tokyo Gas Co Ltd | Method for desulfurizing gas containing hydrogen sulfide and hydrogen cyanide |
| CN104711023A (en) * | 2015-03-11 | 2015-06-17 | 郝天臻 | Treatment method for liquefied petroleum gas sweetening tail gas and alkaline residues and special equipment used in method |
| CN106390168A (en) * | 2016-11-04 | 2017-02-15 | 广州市朗域环保科技有限公司 | Preparation method of compound deodorant |
| JP2017148710A (en) * | 2016-02-23 | 2017-08-31 | 新日鐵住金株式会社 | Wet type desulfurization method from hydrogen sulfide containing gas |
| WO2018173150A1 (en) * | 2017-03-22 | 2018-09-27 | 新日鐵住金株式会社 | Method for wet desulfurization from hydrogen sulfide-containing gas |
-
2019
- 2019-09-17 CN CN201910876054.7A patent/CN110559815A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0278419A (en) * | 1988-09-14 | 1990-03-19 | Tokyo Gas Co Ltd | Method for desulfurizing gas containing hydrogen sulfide and hydrogen cyanide |
| CN104711023A (en) * | 2015-03-11 | 2015-06-17 | 郝天臻 | Treatment method for liquefied petroleum gas sweetening tail gas and alkaline residues and special equipment used in method |
| JP2017148710A (en) * | 2016-02-23 | 2017-08-31 | 新日鐵住金株式会社 | Wet type desulfurization method from hydrogen sulfide containing gas |
| CN106390168A (en) * | 2016-11-04 | 2017-02-15 | 广州市朗域环保科技有限公司 | Preparation method of compound deodorant |
| WO2018173150A1 (en) * | 2017-03-22 | 2018-09-27 | 新日鐵住金株式会社 | Method for wet desulfurization from hydrogen sulfide-containing gas |
Non-Patent Citations (1)
| Title |
|---|
| 魏文德: "《有机化工原料大全 中卷》", 31 January 1999, 化学工业出版社 * |
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