CN113430018A - Method for removing organic sulfur by segmented hydrolysis and regenerating hydrogen production tail gas - Google Patents
Method for removing organic sulfur by segmented hydrolysis and regenerating hydrogen production tail gas Download PDFInfo
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- CN113430018A CN113430018A CN202110543538.7A CN202110543538A CN113430018A CN 113430018 A CN113430018 A CN 113430018A CN 202110543538 A CN202110543538 A CN 202110543538A CN 113430018 A CN113430018 A CN 113430018A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
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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
- B01D53/02—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
- B01D53/04—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 with stationary adsorbents
- B01D53/047—Pressure swing adsorption
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
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Abstract
The invention relates to the field of liquid phase methods for purifying waste gas, in particular to a method for removing organic sulfur by segmented hydrolysis and regenerating hydrogen production tail gas. A method for removing organic sulfur by segmented hydrolysis and regenerating hydrogen production tail gas comprises the following steps: also comprises the following steps: purifying; thirdly, primary hydrolysis; fourthly, secondary hydrolysis; and fifthly, desulfurization. The invention saves investment, has high energy utilization rate and reduces pollutant discharge.
Description
Technical Field
The invention relates to the field of liquid phase methods for purifying waste gas, in particular to a method for removing organic sulfur by segmented hydrolysis and regenerating hydrogen production tail gas.
Background
At present, the steel rolling system of the steel mill in China generally uses the mixed gas of coke oven gas, blast furnace gas and converter gas which are byproducts of the steel mill as the fuel of a heating furnace, wherein the gas contains hydrogen sulfide, hydroxyl sulfur (COS) and CS2Sulfur components such as thiophene and the like are burnt to form SO in flue gas2Discharge to the atmosphere forms pollution. With the development of clean production technology and terminal treatment technology in the steel industry, five ministries of ecological environment department, etc. jointly issue the opinion on promoting implementation of ultra-low emission in the steel industry, which requires the ultra-low emission index limit value SO of steel rolling heat treatment furnace2Less than or equal to 50(mg/m3), the existing method for removing the hydrogen sulfide in the coal gas can not meet the requirement of ultra-low emission, and the COS and CS in the coke oven gas must be removed2And organic sulfur components are also removed, and the conventional iron oxide-based or activated carbon-based desulfurizing agent in the metallurgical industry is difficult to remove the organic sulfur. A process route for removing organic sulfur in coke oven gas in the coal chemical industry is as follows: organic sulfur in the coal gas is firstly converted into hydrogen sulfide which is easy to remove by adopting a hydrolysis method, and then the hydrogen sulfide is removed by adopting a dry method for adsorption. The principle is as follows:
1. a hydrolysis conversion stage:
COS、CS2under the action of catalysts such as aluminum, molybdenum, titanium, zinc, manganese and the like, the catalyst reacts with water vapor contained in the coal gas, and the reaction equation is as follows: COS + H2O=H2S+CO2，CS2+2H2O=2H2S+CO2；
2. And (3) a fine desulfurization stage:
when the coal gas passes through the bed layer, hydrogen sulfide in the coal gas contacts and reacts with a desulfurizing agent to generate iron sulfide, and the reaction equation is as follows:
Fe2O3•H2O+3H2S=Fe2S3•H2O+3H2O；
under the condition that oxygen exists in the coal gas, the generated iron sulfide reacts with the oxygen to generate iron oxide and separate out sulfur, and the reaction equation is as follows:
2Fe2S3•H2O+3O2=2Fe2O3•H2O+6S；
o in gas2And H2S is simultaneously adsorbed by the surface of the adsorbent to form a surface oxide which can be used as a catalytic active center, so that an oxidation reaction is generated, and the reaction equation is as follows:
2H2S+O2=2H2O+2S。
this method has the following disadvantages:
1. the current hydrolysis process can realize conversion under the working conditions of normal temperature or medium temperature and medium and low pressure. Hydrolysis catalyst pair COS and CS2And the organic sulfur conversion efficiency of smaller molecular structures is high, and the conversion capability of the organic sulfur compounds with macromolecules such as thiophene is poor. In principle, CS2Catalytic hydrolysis is more difficult than COS, and the coke oven gas (obtained by removing H by coal refining T-H method or FRC method in coking plant) as by-product of steel plant2S and then) the sulfur content in the sulfur-containing material comprises the following main components: COS (12.61-60.54%, average 23.38%), CS2(45.43-95.22% by weight, average 65.72%), and small amounts of mercaptan, thioether and thiophene. According to the method, the mixed gas of blast furnace gas and coke oven gas which are by-products of a steel mill is used as fuel by a steel rolling heating furnace, and if only the coke oven gas is subjected to fine desulfurization, SO in the flue gas discharged by the heating furnace is required to be satisfied2The concentration is less than or equal to 50mg/m3, the effective conversion rate of COS in the coke oven gas is more than or equal to 98 percent, and the CS2The effective conversion rate is more than or equal to 80 percent. In the currently used one-step hydrolysis method, the reaction temperature of the aluminum-based hydrolysis catalyst is 90-120 ℃, and the CS is at the temperature2The hydrolytic activity is poor, the effective conversion rate is about 50-60%, and the requirement cannot be met. If the hydrolysis reaction temperature is increased, the hydrolysis catalyst is easily poisoned by oxygen and is easily deactivated.
2. The regenerated gas of the purification section utilizes the clean gas after fine desulfurization, and coke resolved from the adsorbent of the purification section is enriched in the regenerated gasOil, naphthalene, H2S and other impurities must be sent to a user with a rear end provided with a desulfurization device to be used as fuel, otherwise, the emission of a new end user cannot reach the standard. In order to overcome the on-way resistance of the regeneration gas to the users, the delivery pressure of the regeneration gas needs to be ensured, and pressurization is generally needed, so that the investment and the operation cost are increased. Meanwhile, the clean gas is used as the regeneration gas, the treatment scale of the desulfurization device is increased, and the investment and operation cost is increased.
Disclosure of Invention
The invention discloses a method for removing organic sulfur by means of segmented hydrolysis and regenerating hydrogen production tail gas, aiming at overcoming the defects of the prior art and providing a treatment method for steel mill byproduct coke oven gas, which is low in investment, high in energy utilization rate and capable of reducing pollutant emission.
The invention achieves the purpose by the following technical scheme:
a method for removing organic sulfur by segmented hydrolysis and regenerating hydrogen production tail gas comprises the following steps: the steel mill coke oven gas pressure swing adsorption hydrogen production tail gas is used as regenerated gas and saturated steam and is input into a heater for heating, and the method is characterized in that: also comprises the following steps:
purification: the heated regeneration gas is input into a purifier for purification, the purified regeneration gas is input into a user,
the raw material gas is input into a gas-liquid separator for gas-liquid separation, the raw material gas after gas-liquid separation is input into a purifier for purification, and the purified raw material gas is input into a pressurizing tower for pressurization;
third, hydrolysis for one time: inputting the pressurized feed gas into a first preheater for primary preheating, inputting the feed gas subjected to primary preheating into a first hydrolysis tower for primary hydrolysis to hydrolyze COS, and arranging a hydrolysis catalyst in the first hydrolysis tower;
fourthly, secondary hydrolysis: the raw material gas after primary hydrolysis is input into a second preheater for secondary preheating, and the raw material gas after secondary preheating is input into a second hydrolysis tower for secondary hydrolysis to hydrolyze CS2A hydrolysis catalyst is arranged in the second hydrolysis tower;
and fifth, desulfurization: and (3) inputting the feed gas subjected to secondary hydrolysis into a cooling tower for cooling, inputting the cooled feed gas into a desulfurizing tower for fine desulfurization, and outputting the fine desulfurized feed gas to a user.
The method for removing organic sulfur and regenerating hydrogen production tail gas by segmented hydrolysis is characterized by comprising the following steps of:
thirdly, the pressurized feed gas is primarily preheated to 80-120 ℃ in a first preheater),
when the step IV is carried out, the raw material gas after primary hydrolysis is input into a second preheater to be secondarily preheated to 110-170 ℃;
in the fifth step, the raw material gas after the second hydrolysis is input into a cooling tower to be cooled to not higher than 45 ℃, and the cooling tower is water-cooled.
The hydrolysis process of the invention is divided into a normal temperature section and a medium temperature section, wherein the normal temperature section is 80-120 ℃, and the hydrolysis conversion of COS is mainly solved at the normal temperature section. The pressurized coal gas enters a first preheater, the temperature is raised to 80-120 ℃ (the heating temperature can be adjusted according to actual conditions), then the coal gas enters a first hydrolysis tower for reaction, enters from the bottom of the first hydrolysis tower, and after the coal gas contacts and reacts with a hydrolysis catalyst, COS and part of CS are reacted2Conversion to H2S。
The middle temperature section is 110-170 ℃, and the key point is to solve CS in the middle temperature section2The hydrolysis and transformation of (2). The coal gas is continuously heated to 110-170 ℃ through a second preheater (the heating temperature can be adjusted according to actual conditions), and then enters a second hydrolysis tower for reaction, and the residual CS is removed2. Cooling the reaction gas discharged from the second hydrolysis tower to a temperature of less than or equal to 45 ℃ by a cooling tower, and sending the reaction gas into a desulfurization tower for fine desulfurization to remove H2S。
The invention adopts a segmented hydrolysis mode, effectively solves the problem of CS at low temperature2The hydrolysis conversion rate is low, the hydrolysis catalyst is easy to be poisoned and inactivated by oxygen when the temperature is high COS, and the CS is effectively improved2The conversion efficiency. The invention is applied to the fine desulfurization of the by-product coke oven gas of a steel mill to remove COS and CS in the coke oven gas2The organic sulfur components are respectively converted into COS and CS mainly through segmented hydrolysis2The organic sulfur removal efficiency is improved, and the requirement of environmental protection and ultralow emission is met. Meanwhile, the invention utilizes the existing tail gas of the steel mill for producing hydrogen by pressure swing adsorption of the coke oven gas as the regeneration gas of the coke oven gas fine desulfurization device, and not only canThe pressure of the hydrogen production tail gas is fully utilized, a desulfurization regenerated gas pressurizing machine is omitted, and the treatment scale of a fine desulfurization device can be reduced, so that the investment and the operation cost are reduced.
The invention utilizes the existing coke oven gas in the steel mill to perform pressure swing adsorption on hydrogen production tail gas. The existing tail gas of the pressure swing adsorption hydrogen production of the coke oven gas of the steel mill is other components (including CH) left after most of hydrogen is extracted from the coke oven gas4About 43% and H2About 31% of CO, about 10% of CO, CO2About 3.5%, the rest of N2、O2、C2H6、C2H4、C3H6And trace amounts of tar, naphthalene, benzene, sulfur, ammonia, etc.), and the pressure of the pipe network is 15-20 kpa, and the gas is used as coke oven gas after being merged into a coke oven gas cabinet of a steel mill. The coke oven gas fine desulfurization device utilizes the hydrogen production tail gas as the regeneration gas, the quality of the hydrogen production tail gas has little influence on the efficiency and the service life of the adsorbent in the purification working section, the pressure of the hydrogen production tail gas can be fully utilized, a desulfurization regeneration gas pressurizing machine is omitted, the treatment scale of the fine desulfurization device can be reduced, and therefore the investment and the operation cost are reduced.
Drawings
FIG. 1 is a schematic flow diagram of the present invention.
Detailed Description
The invention is further illustrated by the following specific examples.
Example 1
A method for regenerating tail gas generated by removing organic sulfur and producing hydrogen by segmented hydrolysis comprises the following steps: also comprises the following steps:
regeneration treatment: the steel mill coke oven gas pressure swing adsorption hydrogen production tail gas is used as regenerated gas 101 and saturated steam 102 which are input into a heater 1 for heating;
purification: the heated regeneration gas is fed into a purifier 2 for purification, the purified regeneration gas is fed to a user 104,
the raw material gas 103 is input into a gas-liquid separator 3 for gas-liquid separation, the raw material gas after gas-liquid separation is input into a purifier 4 for purification, and the purified raw material gas is input into a pressurizing tower 4 for pressurization;
third, hydrolysis for one time: the pressurized feed gas is input into a first preheater 51 for primary preheating to 80-120 ℃, the feed gas after primary preheating is input into a first hydrolysis tower 61 for primary hydrolysis to hydrolyze COS, and a hydrolysis catalyst is arranged in the first hydrolysis tower 61;
fourthly, secondary hydrolysis: the raw material gas after the primary hydrolysis is input into a second preheater 52 for secondary preheating to 110-170 ℃, and the raw material gas after the secondary preheating is input into a second hydrolysis tower 62 for secondary hydrolysis to hydrolyze CS2A hydrolysis catalyst is arranged in the second hydrolysis tower 62;
and fifth, desulfurization: the feed gas after the secondary hydrolysis is input into a cooling tower 7 to be cooled to be not higher than 45 ℃, the cooling tower 7 adopts a water-cooled type, the cooled feed gas is input into a desulfurizing tower 8 to be subjected to fine desulfurization, and the feed gas after the fine desulfurization is input into a user 104.
The hydrolysis process of the embodiment is divided into a normal temperature section and a medium temperature section, wherein the normal temperature section is 80-120 ℃, and the hydrolysis conversion of COS is mainly solved at the normal temperature section. The pressurized coal gas enters a first preheater 51, the temperature is raised to 80-120 ℃ (the heating temperature can be adjusted according to actual conditions), then the coal gas enters a first hydrolysis tower 61 for reaction, enters from the bottom of the first hydrolysis tower 61, and after the coal gas contacts and reacts with a hydrolysis catalyst, COS and part of CS are reacted2Conversion to H2S。
The middle temperature section is 110-170 ℃, and the key point is to solve CS in the middle temperature section2The hydrolysis and transformation of (2). The coal gas is continuously heated to 110-170 ℃ through a second preheater 52 (the heating temperature can be adjusted according to actual conditions), and then enters a second hydrolysis tower 62 for reaction, and the residual CS is removed2. The reaction gas discharged from the second hydrolysis tower 62 is cooled to be less than or equal to 45 ℃ through a cooling tower 7, and is sent to a desulfurizing tower 8 for fine desulfurization to remove H2S。
Claims (2)
1. A method for removing organic sulfur by segmented hydrolysis and regenerating hydrogen production tail gas comprises the following steps: the steel mill coke oven gas pressure swing adsorption hydrogen production tail gas is used as regenerated gas (101) and saturated steam (102) and is input into a heater (1) for heating, and the method is characterized in that: also comprises the following steps:
purification: the heated regeneration gas is input into a purifier (2) for purification, the purified regeneration gas is input into a user (104),
the raw material gas (103) is input into a gas-liquid separator (3) for gas-liquid separation, the raw material gas after gas-liquid separation is input into a purifier (4) for purification, and the purified raw material gas is input into a pressurizing tower (4) for pressurization;
third, hydrolysis for one time: the pressurized feed gas is input into a first preheater (51) for primary preheating, the feed gas after primary preheating is input into a first hydrolysis tower (61) for primary hydrolysis to hydrolyze COS, and a hydrolysis catalyst is arranged in the first hydrolysis tower (61);
fourthly, secondary hydrolysis: the raw material gas after primary hydrolysis is input into a second preheater (52) for secondary preheating, and the raw material gas after secondary preheating is input into a second hydrolysis tower (62) for secondary hydrolysis to hydrolyze CS2A hydrolysis catalyst is arranged in the second hydrolysis tower (62);
and fifth, desulfurization: the feed gas after the secondary hydrolysis is input into a cooling tower (7) for cooling, the cooled feed gas is input into a desulfurizing tower (8) for fine desulfurization, and the feed gas after the fine desulfurization is input into a user (104).
2. The method for staged hydrolytic organic sulfur removal and hydrogen production tail gas regeneration as claimed in claim 1, wherein:
when the third step is carried out, the pressurized feed gas is primarily preheated to 80-120 ℃ in a first preheater (51),
when the step IV is carried out, the raw material gas after primary hydrolysis is input into a second preheater (52) to be secondarily preheated to 110-170 ℃;
in the fifth step, the raw material gas after the secondary hydrolysis is input into a cooling tower (7) to be cooled to be not higher than 45 ℃, and the cooling tower (7) adopts a water cooling type.
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| CN202110543538.7A CN113430018A (en) | 2021-05-19 | 2021-05-19 | Method for removing organic sulfur by segmented hydrolysis and regenerating hydrogen production tail gas |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0920351A1 (en) * | 1996-08-22 | 1999-06-09 | Shell Internationale Researchmaatschappij B.V. | Process for reducing total sulphur content in gases containing hydrogen sulphide and other sulphur components |
| CN110127613A (en) * | 2019-05-20 | 2019-08-16 | 广东国能中林实业有限公司 | A kind of efficiently advanced hydrogen production from coke oven gas technique |
| CN111808645A (en) * | 2020-07-16 | 2020-10-23 | 中国石油集团工程股份有限公司 | Process for deeply treating carbonyl sulfide and carbon disulfide in natural gas |
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2021
- 2021-05-19 CN CN202110543538.7A patent/CN113430018A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0920351A1 (en) * | 1996-08-22 | 1999-06-09 | Shell Internationale Researchmaatschappij B.V. | Process for reducing total sulphur content in gases containing hydrogen sulphide and other sulphur components |
| CN110127613A (en) * | 2019-05-20 | 2019-08-16 | 广东国能中林实业有限公司 | A kind of efficiently advanced hydrogen production from coke oven gas technique |
| CN111808645A (en) * | 2020-07-16 | 2020-10-23 | 中国石油集团工程股份有限公司 | Process for deeply treating carbonyl sulfide and carbon disulfide in natural gas |
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