CN107789969B - Method and device for treating refinery acid gas - Google Patents
Method and device for treating refinery acid gas Download PDFInfo
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- CN107789969B CN107789969B CN201610773555.9A CN201610773555A CN107789969B CN 107789969 B CN107789969 B CN 107789969B CN 201610773555 A CN201610773555 A CN 201610773555A CN 107789969 B CN107789969 B CN 107789969B
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- 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
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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
- B01D53/52—Hydrogen sulfide
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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
- B01D53/62—Carbon oxides
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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
- B01D53/96—Regeneration, reactivation or recycling of reactants
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
- C01B17/32—Hydrosulfides of sodium or potassium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
Abstract
The invention discloses a method and a device for treating refinery acid gas, which comprise the following steps: the absorption tower is provided with a stage I reaction area, a stage II reaction area and a stage III reaction area from top to bottom, sodium hydroxide solution as poor absorption liquid enters from the top of the reactor, refinery acid gas enters from the lower part of the reactor at multiple points, the sodium hydroxide solution reacts with the acid gas from top to bottom in the I, II and stage III reaction areas step by step, purified gas is discharged from the top of the absorption tower, NaHS in rich absorption liquid is separated out in the stage III reaction area in a crystal form and is filtered by a filter bag, filtrate enters a tower bottom liquid holding tank for recycling, and solid is recovered as a product; wherein the reaction temperature of the I-stage reaction zone is 50-80 ℃, the reaction temperature of the second-stage reaction zone is 70-90 ℃, and the reaction temperature of the III-stage reaction zone is 40-50 ℃. The treatment method can treat H in the purified gas2The concentration of S is controlled to be 5-20 mg/Nm3And meanwhile, the NaHS product meeting the solid first-class product requirements of industrial sodium hydrosulfide GB23937-2009 can be produced.
Description
Technical Field
The invention belongs to the waste gas treatment technology, and particularly relates to a treatment method and a treatment device for refinery acid gas.
Background
During the secondary processing of crude oil, such as hydrofinishing, hydrocracking, catalytic cracking, etc., a substantial portion of the sulfides in the crude oil are converted to hydrogen sulfide and are present in refinery acid gases. When the hydrogen sulfide is used as fuel or raw material, the corrosion of pipelines and equipment can be caused, and the hydrogen sulfide is also producedSulfur and sulfuric acid. At present, an acid gas in a refinery is subjected to hydrogen sulfide removal treatment by an alcohol amine solution, dry gas after hydrogen sulfide removal is merged into a gas pipe network, and hydrogen sulfide is used for producing sulfur. Due to the alcohol amine solution to H2S and CO2Has limited selectivity, and the treated acid gas of the refinery contains high concentration of H2S, and CO with higher concentration2Generally, the hydrogen sulfide content is about 85%, the carbon dioxide content is about 10%, and in addition, a small amount of hydrocarbon gas including methane, ethane and the like is also included.
The acid gas of large and medium-sized refinery is mainly used for producing sulfur, and two common technologies are available, one is Claus process, and the other is LO-CAT process developed by MERICHEM company in the United states. Claus process adopts conventional thermal reaction and two-stage low-temperature catalytic conversion process to produce sulfur, and has the advantages of mature process, suitability for annual sulfur production device with sulfur yield of more than 5000t, sulfur recovery rate of more than 99% at maximum, and partial sulfur still in SO form2The form of the exhaust gas is discharged into the atmosphere, so that an exhaust gas treatment device needs to be added. LO-CAT Process Using Multichelated iron catalyst for H2S is directly converted into elemental sulphur, H2The removal rate of S is over 99.9%. The LO-CAT process can be suitable for various working conditions with large fluctuation of acid gas amount and 0-100% of hydrogen sulfide content, but because the operation cost is high, the purity and color of the produced sulfur are slightly inferior to those of the Claus process, and sulfur particles generated in the production process can generate a blocking phenomenon, and the like, in small and medium-sized refineries, the technology is inferior to the Claus process in economy. For small refineries, the amount of acid gas is not large, and for many years, most of the acid gas is directly discharged into the atmosphere after being burned, so that a large amount of sulfur resources are wasted, and serious atmospheric pollution is caused. With the improvement of the national environmental protection standard, the acid gas treatment of small refineries draws more and more attention.
In order to increase the added value of products, many small-sized oil refineries produce sodium hydrosulfide by using acid gas as raw material, but because the hydrogen sulfide and carbon dioxide contained in the acid gas belong to the acid gas, the properties are similar, the content of the carbon dioxide has great influence on the quality and production cost of hydrogen sulfide derived products, and the sodium carbonate and the like are crystallizedThe blockage of pipelines, valves and the like brings great difficulty to the normal production operation of the device, and the purity of the sodium hydrosulfide product is greatly influenced. Therefore, H in acid gas is ensured2On the premise of standard discharge of S, the method has very important significance for utilizing acid gas, such as solving the blockage of pipe valves, instruments and the like in the production operation process of sodium hydrosulfide, improving the product purity and the like.
CN201310396214.0 uses 50% methyldiethanolamine as extractant to absorb H in acid gas in two stages, regenerate in two stages, exchange heat and condense2The concentration of S is increased to more than 99%. But the technical process is long, the equipment investment is large, and a large amount of steam is consumed. CN200880002473.8 first removes acid gases from the gas mixture with an absorption liquid to obtain an acid solution, and then obtains higher concentrations of hydrogen sulfide and carbon dioxide by regeneration of the acid solution and compression of the regenerator overhead gas. The technology is suitable for treating gas mixture with high hydrocarbon content and low acid gas content. CN201010210208.8 uses carbon monoxide transformation gas as raw material gas and uses low-temperature methanol solution as absorbent to produce carbon dioxide. After absorption and desorption, the H in the hydrogen sulfide-containing gas at the top of the methanol regeneration tower is discharged2The concentration of S is about 27 percent, and the sulfur can be used for preparing sulfur or preparing acid by hydrogen sulfide by a Claus sulfur recovery device. The technique is suitable for lower concentration H2The concentration of S gas has a long process, and relates to equipment such as a plurality of towers, heat exchangers, pumps and the like, so that the investment is high. CN103721531A utilizes membrane technology to separate and absorb carbon dioxide and hydrogen sulfide in refinery acid gas to produce sodium hydrosulfide, and has the defects of low efficiency and the like. CN103754833A uses the hypergravity technology to process refinery dry gas and produce sodium hydrosulfide products with higher purity, the product and by-product crystallization easily cause the unbalance of the operation of the hypergravity machine, and the technology of producing NaHS by using the hypergravity machine to process refinery acid gas is difficult to realize. CN104826463A, CN104826466A and the like have the same problems as CN103754833A, acid-base neutralization reaction occurs in a rotating bed, reaction heat is generated immediately, a large amount of carrier gas is required to ensure the temperature required by the reaction, and the realization is difficult.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method and a device for treating refinery acid gas. The treatment method can treat H in the purified gas2The concentration of S is controlled to be 5-20 mg/Nm3The NaHS can be directly discharged into a torch or gas pipe network, and meanwhile, the treatment method can be used for producing the NaHS, and the NaHS product meets the requirements of first-class solid products in the industrial sodium hydrosulfide GB 23937-2009.
The invention relates to a processing method of refinery acid gas, which comprises the following steps: the absorption tower is provided with a stage I reaction area, a stage II reaction area and a stage III reaction area from top to bottom, sodium hydroxide solution as poor absorption liquid enters from the top of the reactor, acid gas in a refinery enters from the lower part of the reactor at multiple points, the sodium hydroxide solution reacts with the acid gas from top to bottom in the stage I reaction area, the stage II reaction area and the stage III reaction area step by step, finally purified gas is discharged from the top of the absorption tower, NaHS in the rich absorption liquid is separated out in the stage III reaction area in a crystal form and is filtered by a filter bag, filtrate enters a tower bottom liquid holding tank for recycling, and solid is recovered as a product; wherein the reaction temperature of the I-stage reaction zone is 50-80 ℃, preferably 70-80 ℃, the reaction temperature of the second-stage reaction zone is 70-90 ℃, and the reaction temperature of the III-stage reaction zone is 40-50 ℃.
In the method, 4-40 layers of tower trays, preferably 10-30 layers, are arranged in the absorption tower from the upper stage I reaction zone, the stage II reaction zone and the stage III reaction zone to the lower stage I reaction zone, the openings of the tower trays are 10-10000 meshes, preferably 6000-10000 meshes, and each stage of tower trays is provided with a weir and a down-flow zone. The number of the trays corresponding to each stage of reaction zone can be adjusted according to the reaction requirement, and the difference of the number of the trays between each stage of reaction zone is preferably not more than 2 layers. Generally, the stage I reaction zone, the stage II reaction zone and the stage III reaction zone correspond to the upper part, the middle part and the lower part of the absorption tower, respectively. In the method, the trays are sequenced from top to bottom according to the 1 st to N (last layer), and unless the number of the tray layers is specially specified to be the number of the tray layers of a certain reaction area, the number of the tray layers is counted by the number of the tray layers of an absorption tower under the other conditions.
In the method of the invention, H in the refinery acid gas2S volume concentration 50% -95%, CO2The volume concentration is 5-20%, and the others are organic matters such as hydrocarbons; the mass concentration of the NaOH solution (poor absorption liquid) is 10-60%, preferably 20-40%.
In the method of the invention, the reaction states in each stage of reaction zone are as follows:
the acid gas in the stage I reaction zone contains a relatively high concentration of CO2And a lower concentration of H2S, NaOH solution (absorption liquid) and H in acid gas2S and CO2A chemical reaction takes place, the main product is Na2S、Na2CO3And NaHCO3(ii) a A circulating cooling water system is arranged on the tower tray of the I-stage reaction area, which can ensure H in acid gas2The reaction of S is complete;
h in acid gas in stage II reaction zone2The concentration of S is increased, and Na in the absorption liquid is2S、Na2CO3And NaHCO3With H in acid gases2Conversion of S to Na by reaction2S and NaHS; a circulating cooling water system is not arranged on a tower tray of the II-stage reaction area, the reaction temperature can be maintained through self reaction heat release, and meanwhile, a liquid phase is evaporated and concentrated to enable the solution to be in a supersaturated state and enter the III-stage reaction area;
fresh acid gas is introduced into the stage III reaction zone, and the acid gas contains excessive H2S, Na in the absorption liquid2S and NaHS are converted into NaHS; and a circulating cooling water system is arranged on the III-stage reaction zone tray, supersaturated absorption liquid enters the III-stage reaction zone to be quenched and cooled, and NaHS in a liquid phase is separated out in a crystal grain form.
In the method, the residence time of the gas phase in each stage of reaction is 1-20 s, preferably 1-5 s.
In the method, the absorption liquid is added from a liquid phase inlet of a first layer of tower tray of a stage I reaction area, and the refinery acid gas is added from a gas phase inlet on the lower side of the corresponding tower tray at 2-10 points of a stage III reaction area of the absorption tower.
In the method, any one layer or more layers of partial absorption liquid in the 3 rd to last layer tower trays, preferably the 3 rd to II-stage reaction zone last layer tower trays are circulated to the top liquid phase inlet, so that NaOH in the absorption liquid is fully utilized, and the liquid layer depth on the tower trays is kept, so that the gas-liquid mass transfer effect is ensured; the amount of the circulating liquid is 2-30 times, preferably 4-15 times of the addition amount of the lean absorption liquid.
In the method, the absorption liquid in the liquid holding tank at the bottom of the tower is circularly returned to any one or more layers of tower trays in the II-stage and/or III-stage reaction area of the absorption tower so as to ensure Na in the absorption liquid2And S is completely converted into NaHS and reaches a supersaturated state.
In the method, the pH value of the liquid phase on the tray of the layer 2 is 10-12, and the addition amount of the fresh NaOH solution is regulated to control so that H in purified gas discharged into a torch2S is kept at 5-20 mg/Nm3To ensure SO in the flare gas2The discharge reaches the standard.
In the method, the liquid layer depth of the tray at the lowest layer is controlled by the liquid level controller at the tower bottom to generate liquid seal and prevent H2S leaks from the liquid phase outlet to the environment.
In the method, the top of the absorption tower is provided with a demister, and the bottom of the absorption tower is provided with a liquid holding tank. The demister can be one of a fiber demister, a filler type demister or a wire mesh demister.
In the method, the lower end surface of the overflow weir of the upper stage tray is inserted below the liquid level of the absorption liquid of the lower stage tray to prevent short circuit of acidic gas.
In the method of the present invention, the purified gas discharged from the top of the absorption column further contains 5 to 20mg/Nm in concentration3H of (A) to (B)2S, can be discharged into a flare or a gas system.
The invention relates to a processing device of acid gas in a refinery, comprising: the device comprises an absorption tower 3, a primary circulating slurry pump 11, a secondary circulating slurry pump 15, a pH value online detection and control system 12 and a liquid level control system 10; wherein the absorption tower 3 comprises a demister 7, a tower tray 4, an overflow weir 5, a liquid descending zone 6 and a tower bottom liquid holding tank 17; an inlet of a first-stage circulating slurry pump 11 is connected with a circulating liquid phase outlet of a tower tray 3 of the absorption tower through a pipeline, and an outlet of the first-stage circulating slurry pump 11 is combined with a NaOH solution feeding pipeline through a pipeline and then is connected with a liquid phase inlet of a first-stage tower tray; an inlet of the secondary slurry circulating pump 15 is connected with a liquid phase outlet of the tower bottom liquid holding tank 17 through a pipeline, and an outlet is connected with a circulating liquid phase inlet of a tower tray of the absorption tower 3 through a pipeline; the liquid level control system 10 is arranged in the liquid descending area 6 of the tray at the last layer of the absorption tower bottom, the liquid descending area 6 is connected with a valve 20 through a pipeline, a filter bag 18 is arranged below the valve 20, and the filter bag 18 is connected to a liquid holding tank 17 at the tower bottom through a liquid phase channel 21.
Compared with the prior art, the invention has the following advantages:
(1) the stage III reaction zone at the lower part of the absorption tower is provided with multi-point air inlet, so that Na is continuously generated in the I, II stage reaction zone at the upper/middle part of the absorption tower2CO3、NaHCO3And Na2H in acid gas with S entering step by step and multiple points2S is reacted and finally converted into NaHS, so that the NaHS is continuously purified, and the NaHS purity at the bottom tray outlet is greatly improved;
(2) the liquid phase fluidizing medium in the absorption tower is acid gas and is in a boiling state from the upper part to the lower part of I, II and a III-grade reaction zone, so that Na generated in the reaction is completely avoided2S or NaHS particles are deposited, crystallized and coalesced, so that the blockage of a reactor or a pipeline is prevented, the gas-liquid-solid three-phase contact surface area is greatly increased by micro bubbles on each stage of tower tray, and the reaction is quicker, more uniform and more thorough;
(3) i, II and III level reaction zones in the absorption tower respectively adopt different temperature control modes, so that the absorption effect is improved to the utmost extent in the I level reaction zone, supersaturated absorption liquid obtained in the II level reaction zone enters the three level reaction zone to be cooled and separated out, and I, II and III level reaction zones are matched step by step, thereby effectively purifying acid gas and simultaneously producing a high-purity NaHS product, and being beneficial to industrial application.
Drawings
FIG. 1 is a flow chart of a refinery acid gas treatment method and apparatus according to the present invention.
Wherein: 1. refinery acid gas; 2. NaOH solution; 3. an absorption tower; 4. a tray; 5. an overflow weir; 6. a liquid descending zone; 7. a demister; 8. water is circularly supplied; 9. circulating water; 10. a liquid level controller; 11. a primary circulating slurry pump; 12. a pH detector; 13. purifying the gas; 14. adjusting a valve; 15. a secondary circulating slurry pump; 16. NaHS circulating absorption liquid; 17. a liquid holding tank; 18. a filter bag; 19. solid NaHS products; 20. an on-off valve; 21. a liquid phase channel;
I. a stage I reaction zone; II. A stage II reaction zone; III and III stage reaction zones.
Detailed Description
The process and apparatus of the present invention are described in more detail below with reference to specific examples, which are not intended to limit the invention thereto.
The treatment method of the refinery acid gas is carried out according to the following modes: acid gas 1 in a refinery enters an absorption tower from a III-grade reaction zone at the lower part of the absorption tower 3 at multiple points, contacts and reacts with NaOH solution 2 added from a first layer tower tray liquid phase inlet at the upper part of the absorption tower 3 from bottom to top in a I-grade reaction zone, the tower tray in the I-grade reaction zone is circularly cooled, the temperature of the absorption liquid (namely the reaction temperature) is ensured to be 50-80 ℃, the absorption liquid obtained by the reaction enters a II-grade reaction zone, and the II-grade reaction zone is not provided with a circulating cooling water system, through reaction heat, keeping the reaction temperature at 70-90 ℃, evaporating and concentrating the absorption liquid, keeping the absorption liquid in a supersaturated state, allowing the supersaturated absorption liquid to enter a III-stage reaction zone, circularly cooling, allowing the temperature of a tower tray absorption liquid to be 40-50 ℃, concentrating and crystallizing NaHS in the absorption liquid, allowing the concentrated and crystallized NaHS to enter a filter bag 18 through a valve 20 in a liquid descending zone 6, recovering the NaHS as a product through filtering, and allowing the filtrate to enter a tower bottom liquid holding tank 17 through a liquid phase channel 21; the absorption liquid in the tower bottom liquid holding tank (17) is pumped out by a secondary circulating slurry pump 15 and returns to the absorption tower; the first-stage circulating slurry pump 11 circulates part of absorption liquid of the absorption tower 3 to the liquid phase inlet of the first layer of tower tray; controlling the pH value of a liquid phase on the second layer of tower tray to be 10-12, and discharging H in purified gas discharged into a torch2S is kept at 5-20 mg/Nm3(ii) a The liquid seal is generated by controlling the liquid layer depth of the lowermost tray by the liquid level controller 10.
Example 1
The pressure of acid gas in a certain refinery is 0.30MPaG, the temperature is 30 ℃, and H in the acid gas2S accounts for 55%, CO2Concentration 10%, hydrocarbons 35%.
The operating conditions are as follows: (1) 20 stages of tower trays are arranged in the absorption tower, and the retention time of gas on liquid layers of the tower trays of each stage is 3 s; (2) introducing 8 acid gas branches from a gas phase inlet at the lower side of 13 th-20 th-stage tower trays, arranging circulating cooling water systems on liquid layers of 1 st-14 th-stage and 19 th-20 th-stage tower trays, and keeping the temperature of an absorption liquid on each stage tower tray to be 65-75 ℃; (3) the inlet of the first-stage circulating slurry pump is connected with the liquid phase outlet of the 6 th-stage tower tray, and the slurry circulating amount is 4 times of the amount of the fresh solution; (4) the inlet of the secondary circulating slurry pump is connected with a liquid phase outlet of a liquid holding tank at the bottom of the self-absorption tower, and the outlet returns to a liquid phase inlet of a 15 th-stage tower tray of the absorption tower; (5) the mass concentration of the fresh NaOH solution is 30 percent.
As a result: (1) purification of H from gas2S concentration 15mg/Nm3(ii) a (2) The temperature of an absorption liquid on a 15 th-18 th-stage tower tray of the absorption tower is 83 ℃; (3) the content of NaHS in the final product sodium hydrosulfide solid particles is 65 percent, and the requirements of GB23937-2009 sodium hydrosulfide Industrial Standard solid qualified products are met.
Example 2
The pressure of acid gas in a certain refinery is 0.30MPaG, the temperature is 30 ℃, and H in the acid gas2S accounts for 85%, and CO2Concentration 10%, hydrocarbons 5%.
The operating conditions are as follows: (1) 30 stages of trays are arranged in the absorption tower, and the retention time of gas on liquid layers of the trays of each stage is 3 s; (2) introducing 10 strands of acid gas from a gas phase inlet at the lower side of 21-30-stage tower trays, arranging circulating cooling water systems on liquid layers of 1-20-stage and 27-30-stage tower trays, and keeping the temperature of an absorption liquid on each stage tower tray to be 70-80 ℃; (3) the inlet of the first-stage circulating slurry pump is connected with the liquid phase outlet of the 7 th-stage tower tray, and the slurry circulating amount is 6 times of the amount of the fresh solution; (4) the inlet of the second-stage circulating slurry pump is connected with a liquid phase outlet of a liquid holding tank at the bottom of the self-absorption tower, and the outlet returns to a liquid phase inlet of a 21 st-stage tower tray of the absorption tower; (5) the mass concentration of the fresh NaOH solution is 30 percent.
As a result: (1) purification of H from gas2S concentration 15mg/Nm3(ii) a (2) The temperature of the absorption liquid on 21 st-26 th tower trays of the absorption tower is 85 ℃; (3) the content of NaHS in the final product sodium hydrosulfide solid particles is 65 percent, and the requirements of GB23937-2009 sodium hydrosulfide Industrial Standard solid qualified products are met.
Example 3
The pressure of acid gas in a certain refinery is 0.30MPaG, the temperature is 30 ℃, and H in the acid gas2S accounts for 92%, CO2Concentration 6%, hydrocarbons 2%.
The operating conditions are as follows: (1) 35 stages of tower trays are arranged in the absorption tower, and the retention time of gas on liquid layers of the tower trays of each stage is 4 s; (2) introducing 10 strands of acid gas from a gas phase inlet at the lower side of 25 th-35 th-stage tower trays, arranging circulating cooling water systems on liquid layers of 1 st-24 th-stage and 31 st-35 th-stage tower trays, and keeping the temperature of an absorption liquid on each stage tower tray to be 70-80 ℃; (3) the inlet of the first-stage circulating slurry pump is connected with the liquid phase outlet of the 9 th-stage tower tray, and the slurry circulating amount is 8 times of the amount of the fresh solution; (4) the inlet of the secondary circulating slurry pump is connected with a liquid phase outlet of a liquid holding tank at the bottom of the self-absorption tower, and the outlet returns to a liquid phase inlet of a 25 th-stage tower tray of the absorption tower; (5) the mass concentration of the fresh NaOH solution is 35 percent.
As a result: (1) purification of H from gas2The S concentration is 15mg/Nm 3; (2) the temperature of an absorption liquid on a 25 th-30 th-stage tower tray of the absorption tower is 82 ℃; (3) the content of NaHS in the final product sodium hydrosulfide solid particles is 65 percent, and the requirements of GB23937-2009 sodium hydrosulfide Industrial Standard solid qualified products are met.
Claims (9)
1. A method for treating refinery acid gas comprises the following steps: the absorption tower is provided with a stage I reaction area, a stage II reaction area and a stage III reaction area from top to bottom, sodium hydroxide solution as poor absorption liquid enters from the top of the absorption tower, the sodium hydroxide solution reacts with acid gas from top to bottom in the stage I reaction area, the stage II reaction area and the stage III reaction area step by step, finally purified gas is discharged from the top of the absorption tower, NaHS in rich absorption liquid is separated out in the stage III reaction area in a crystal form and is filtered by a filter bag, filtrate enters a tower bottom liquid holding tank for recycling, and solid is recovered as a product; the reaction temperature of the I-stage reaction zone is 50-80 ℃, the reaction temperature of the II-stage reaction zone is 70-90 ℃, the reaction temperature of the III-stage reaction zone is 40-50 ℃, 4-40 layers of tower trays are arranged in the absorption tower from top to bottom in the I-stage reaction zone, the II-stage reaction zone and the III-stage reaction zone, and each layer of tower tray is provided with an overflow weir and a liquid descending zone; adding refinery acid gas from a gas phase inlet on the lower side of a corresponding tower tray at 2-10 points of a III-stage reaction zone of the absorption tower; circulating part of one or more layers of absorption liquid in any one layer or the last layer of tower tray from 3 rd to last layer of tower tray back to the top liquid phase inlet, wherein the amount of the circulating liquid is 2-30 times of the addition amount of the lean absorption liquid; and the absorption liquid in the tower bottom liquid holding tank is circularly returned to any one or more layers of tower trays of the II-stage and/or III-stage reaction area of the absorption tower.
2. The method of claim 1, wherein: the tray is perforated with 10-10000 meshes.
3. The method of claim 1, wherein: h in the refinery acid gas2S volume concentration 50% -95%, CO2The volume concentration is 5-20%.
4. The method of claim 1, wherein: and circulating cooling water systems are arranged on the trays of the I-stage reaction area and the III-stage reaction area.
5. The method of claim 1, wherein: the residence time of the gas phase in each stage of reaction is 1-20 s.
6. The method of claim 1, wherein: the pH value of the liquid phase on the tower tray of the layer 2 is 10-12.
7. The method of claim 1, wherein: the liquid layer depth of the lowermost tray is controlled by a liquid level controller at the tower bottom; and a demister is arranged at the top of the absorption tower.
8. The method of claim 1, wherein: the lower end surface of the overflow weir of the tray on the upper layer is inserted below the liquid level of the absorption liquid of the tray on the lower layer.
9. A processing device of acid gas of a refinery is characterized by comprising: the device comprises an absorption tower (3), a primary circulating slurry pump (11), a secondary circulating slurry pump (15), a pH value on-line detection and control system (12) and a liquid level control system (10); wherein the absorption tower (3) comprises a demister (7), a tower tray (4), an overflow weir (5), a down-flow zone (6) and a tower bottom liquid holding tank (17); the absorption tower (3) is provided with a stage I reaction zone, a stage II reaction zone and a stage III reaction zone from top to bottom; adding refinery acid gas from a gas phase inlet on the lower side of a corresponding tower tray at 2-10 points of a III-stage reaction zone of an absorption tower (3); an inlet of the first-stage circulating slurry pump (11) is connected with any one or more layers of circulating liquid phase outlets in 3 rd to last-layer tower trays through a pipeline, and an outlet of the first-stage circulating slurry pump (11) is combined with a NaOH solution feeding pipeline through a pipeline and then connected to a liquid phase inlet of the first-layer tower tray; an inlet of a secondary circulating slurry pump (15) is connected with a liquid phase outlet of a tower bottom liquid holding tank (17) through a pipeline, and an outlet is connected with a circulating liquid phase inlet of any one or more layers of tower trays in a II-stage and/or III-stage reaction zone of the absorption tower through a pipeline; the liquid level control system (10) is arranged in the last tray down-flow area (6) at the bottom of the absorption tower, the last tray down-flow area (6) at the bottom of the absorption tower is connected with a valve (20) through a pipeline, a filter bag (18) is arranged below the valve (20), and the filter bag (18) is connected to a liquid holding tank (17) at the bottom of the absorption tower through a liquid phase channel (21).
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610773555.9A CN107789969B (en) | 2016-08-31 | 2016-08-31 | Method and device for treating refinery acid gas |
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| CN110548371B (en) * | 2019-10-15 | 2021-11-05 | 山东宜特装备制造有限公司 | Analytic tower with measuring apparatu is clear away foam |
| CN116251539A (en) * | 2023-05-15 | 2023-06-13 | 黑龙江莱睿普思环境科技发展有限公司 | Absorption reactor for preparing sodium hydrosulfide from acid gas |
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| US4278621A (en) * | 1977-12-22 | 1981-07-14 | Union Carbide Corporation | Vapor-liquid contacting system |
| CN2475459Y (en) * | 2000-12-27 | 2002-02-06 | 程培胜 | Tower tray type overall sucking tower |
| CN104971601A (en) * | 2014-04-10 | 2015-10-14 | 中国石油化工股份有限公司 | Acid gas vertical reactor and processing method |
| CN104971600A (en) * | 2014-04-10 | 2015-10-14 | 中国石油化工股份有限公司 | Acid gas tubular reactor and processing technical method |
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| FR2943924B1 (en) * | 2009-04-03 | 2011-04-01 | Inst Francais Du Petrole | COLUMN AND GAS-LIQUID CONTACT METHOD USING A COMBINATION OF TRAYS AND TRIMS |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4278621A (en) * | 1977-12-22 | 1981-07-14 | Union Carbide Corporation | Vapor-liquid contacting system |
| CN2475459Y (en) * | 2000-12-27 | 2002-02-06 | 程培胜 | Tower tray type overall sucking tower |
| CN104971601A (en) * | 2014-04-10 | 2015-10-14 | 中国石油化工股份有限公司 | Acid gas vertical reactor and processing method |
| CN104971600A (en) * | 2014-04-10 | 2015-10-14 | 中国石油化工股份有限公司 | Acid gas tubular reactor and processing technical method |
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