Efficient desulfurizing agent, desulfurizing equipment and method for removing H2S and / or organic sulfur in gas

Abstract

The invention provides an efficient desulfurizer, which is used for removing H2S and / or organic sulfur in gas, and comprises an organic solvent and organic alcohol amine, optionally, the efficient desulfurizing agent further comprises at least one of an antioxidant, a corrosion inhibitor and a defoaming agent. The invention also provides desulfurization equipment and a method for removing H2S or organic sulfur in sulfur-containing process gas or sulfur-containing waste gas. The high-efficiency desulfurizing agent provided by the invention overcomes the defects of low sulfur load, high regeneration energy consumption, easiness in degradation, incapability of removing organic sulfur and the like of the traditional desulfurizing agent. The method is suitable for desulfurization and purification treatment of sulfur-containing gases such as high-acidity natural gas, refinery dry gas, liquefied gas and sulfur recovery tail gas.

Description

Technical Field

[0001] The invention belongs to the field of gas purification, and in particular relates to a high-efficiency desulfurizing agent, desulfurizing equipment and method for removing H2S and / or organic sulfur from gas. Background Art

[0002] In recent years, with the development of heavy oil catalytic cracking technology in my country and the increase in the processing of imported crude oil with high sulfur content, the content of these impurities in refinery gas (catalytic cracking dry gas, coking dry gas and liquefied gas, etc.) has increased significantly, and the total sulfur content is generally 2000mg / Nm 3 -100000mg / Nm 3 Refinery gas is an important source of industrial fuel, petrochemical raw materials and civilian fuel, which contains impurities such as H2S, CO2, COS, RSR, RSH, RSSR, etc. At present, traditional desulfurizers with MDEA as the main component are widely used to treat sulfur-containing gas. This process has three significant deficiencies. First, in addition to H2S, most sulfur-containing gas sources also contain organic sulfur, and the acidity of organic sulfur is weak. Traditional desulfurizers are not effective in removing organic sulfur. Traditional desulfurizers cannot treat sulfur-containing process gases containing organic sulfur (COS, RSH, etc.), and need to add alkaline washing methods to further treat organic sulfur; second, because traditional desulfurizers generally contain 50%-80% water (the specific heat of water is relatively high, at 4.18kg / kg / K), the sensible heat of temperature rise and latent heat of gasification of the desulfurizer during the regeneration process absorb a large amount of heat, resulting in a high regeneration energy consumption problem; third, in the traditional desulfurization process, CO2 in the sulfur-containing process gas competes with H2S for absorption, especially when the carbon-sulfur ratio is high (>10), the desulfurization efficiency and desulfurization load of traditional desulfurizers are significantly reduced.

[0003] Researchers believe that the desulfurization of H2S by alcohol amines can be divided into thermodynamically selective desulfurization and kinetic selective desulfurization. Thermodynamically selective desulfurization is achieved by studying the influence of reaction process conditions on the chemical reaction equilibrium constant; kinetic selective desulfurization is achieved by utilizing the different reaction rates between amine absorbents and H2S and CO2. A large number of studies have shown that it is the reaction rate rather than the process conditions that affect the selectivity of the desulfurization process. There is currently no satisfactory method to improve the selectivity of the desulfurization process by changing the process conditions (using thermodynamic methods). Therefore, the ability of hindered amine desulfurization solution to absorb H2S can be increased by about 50%, steam consumption can be reduced by more than 20%, solvent consumption can be reduced by more than 50%, production operation can be stable, and it has good energy-saving effects and economic benefits. Researchers use alcohol amine compounds (such as tert-butylaminoethanol and diisopropanolamine) with different degrees of steric hindrance characteristics to improve the desulfurization effect of the desulfurizer. Organic solvents such as sulfolane have good solubility for H2S and organic sulfur, and good selectivity for H2S. This type of dissolution is physical dissolution and is suitable for use in situations with higher acidic gas partial pressure. The rate factor of organic sulfur absorption by the sulfoneamine system (sulfolane and diisopropanolamine aqueous solution) is higher than that of MDEA. Under equilibrium conditions, the organic sulfur removal rate of the sulfoneamine solvent is greatly improved compared with that of the MDEA solvent. However, due to the small difference in the rate factor, the absorption rate is not significantly accelerated, and a longer gas-liquid contact time is required to reach equilibrium.

[0004] CN106474901A discloses a desulfurizer, which uses 95%-98% MDEA as a core component, and uses a 25%-30% aqueous solution of the desulfurizer for desulfurization during use. It is essentially an improvement of the MDEA desulfurizer, but the total sulfur load of the desulfurizer is low, and the removal effect of organic sulfur is poor. CN103357261A discloses a desulfurizer and a preparation method thereof, wherein the core components include 30%-40% MDEA, 40%-50% sterically hindered amine, and 10%-29% physical absorbent, wherein the physical absorption solvent includes polyethylene glycol dimethyl ether, N-methylpyrrolidone, piperazine and its derivatives, morpholine and its derivatives, and can effectively remove organic sulfides such as COS, mercaptans, etc. The disadvantage is that the H2S load of the desulfurizer is low, a larger liquid-to-gas ratio is required, and it is not suitable for treating sulfur-containing gas sources with high H2S content. CN108355463A discloses a desulfurization method and device for sulfur tail gas, which specifically implements hydrogenation reduction, alcohol amine absorption, and fine desulfurization on the sulfur tail gas in sequence, and can achieve deep removal of H2S and organic sulfur, with H2S content less than 5mg / Nm 3 , organic sulfur content <20mg / Nm 3 The disadvantages of this method are that the desulfurization process is long (including rough desulfurization and fine desulfurization), the equipment is complex (the number of floating valve tower trays is up to 30 layers), the desulfurizer regeneration temperature is as high as 135°C, the operating cost is high, and more importantly, this method is not suitable for organic sulfur content exceeding 100mg / Nm3 Purification of sulfur-containing gases.

[0005] In summary, there is an urgent need to develop an efficient desulfurizer and its desulfurization equipment and method for removing H2S and small molecular organic sulfur in gas, which can be suitable for the desulfurization of sulfur-containing gas sources with high organic sulfur content and high carbon-sulfur ratio, so as to achieve the purpose of increasing the total sulfur loading capacity of the desulfurizer and reducing the regeneration energy consumption and degradation of the desulfurizer. Summary of the invention

[0006] To this end, the object of the present invention is to provide a high-efficiency desulfurizer, desulfurization equipment and method for removing H2S and / or organic sulfur in gas, which is suitable for the desulfurization of sulfur-containing gas sources with high organic sulfur content and high carbon-sulfur ratio, and can achieve the purpose of increasing the total sulfur loading of the desulfurizer and reducing the regeneration energy consumption and degradation of the desulfurizer.

[0007] To achieve the above-mentioned purpose, the present invention provides a high-efficiency desulfurizer for removing H2S and / or organic sulfur in gas, wherein the high-efficiency desulfurizer comprises an organic solvent and an organic alcohol amine; optionally, the high-efficiency desulfurizer also comprises at least one of an antioxidant, a corrosion inhibitor and a defoaming agent.

[0008] Specifically, the high-efficiency desulfurizer of the present invention is compounded with an organic solvent and an organic alcohol amine. Compared with the traditional desulfurizer (30w% MDEA aqueous solution), its absorption capacity for H2S in the gas is increased by more than 50%, the maximum saturated H2S load is 0.76mol H2S / mol amine, the H2S loading amount can reach 60g / L, the desulfurization selectivity can reach more than 20, the CO2 co-absorption rate is reduced to less than 5%, and the organic sulfur (CH3SH, COS) removal rate reaches more than 90%; since the organic solvent has a smaller specific heat than water, the high-efficiency desulfurizer provided by the present invention has high regeneration efficiency, and the regeneration energy consumption is reduced by 30%-40% compared with the regeneration energy consumption of the traditional desulfurizer.

[0009] Specifically, when the high-efficiency desulfurizer of the present invention treats relatively pure sulfur-containing gas, it is not necessary to add a corrosion inhibitor. If the sulfur-containing gas contains more impurities and more corrosive substances are carried and generated during the treatment process, a corrosion inhibitor needs to be added; if the treated sulfur-containing process gas contains a small amount of oxygen or oxidizing substances or the desulfurizer of the present invention contacts the air due to poor nitrogen sealing effect, an antioxidant needs to be added; if the treated sulfur-containing process gas contains FeS, hydrocarbons and other substances that are easy to cause the desulfurizer to foam, a defoaming agent needs to be added.

[0010] As a specific embodiment of the present invention, preferably, the gas includes at least one of sulfur-containing process gas and sulfur-containing waste gas. Further preferably, the H2S content in the gas is 1000 mg / Nm 3 -100000mg / Nm 3, and / or organic sulfur content of 100 mg / Nm 3 -1000mg / Nm 3 .

[0011] As a specific embodiment of the present invention, preferably, the organic sulfur is a small molecule organic sulfide with a relative molecular mass of less than 100, and further preferably, the organic sulfur includes at least one of carbon oxysulfide COS and methyl mercaptan CH3SH; and / or the organic alcohol amine is a hindered amine.

[0012] As a specific embodiment of the present invention, preferably, the organic solvent includes at least one of DMSO, DMA, sulfolane, and 3-methylsulfolane; and / or the organic alcohol amine is a tertiary amine.

[0013] As a specific embodiment of the present invention, preferably, the organic alcohol amine is selected from at least one of 1,3-di(dimethylamino)-2-propanol (BDMAP), 1,3-di(diethylamino)-2-propanol (BDMEP), 1,3-di-tert-butylamino-2-propanol, N-methyldiethanolamine (MDEA), N-tert-butylaminodiethanolamine and triethanolamine.

[0014] As a specific embodiment of the present invention, preferably, based on the total molar amount of the organic alcohol amine and the organic solvent, in the high-efficiency desulfurizer, the molar content of the organic alcohol amine is 10%-40%, and the molar content of the organic solvent is 60%-90%; and / or, the concentration of the corrosion inhibitor in the high-efficiency desulfurizer is 100mg / L-1000mg / L; and / or, the concentration of the defoaming agent in the high-efficiency desulfurizer is 100mg / L-1000mg / L; and / or, the concentration of the antioxidant in the high-efficiency desulfurizer is 100mg / L-1000mg / L.

[0015] In order to achieve the above-mentioned purpose, the present invention also provides a desulfurization equipment for removing H2S or organic sulfur in sulfur-containing process gas or sulfur-containing waste gas using the above-mentioned high-efficiency desulfurizer. The desulfurization equipment includes a desulfurization reactor and a regeneration reactor. Preferably, a sulfur-containing gas inlet is provided at the bottom of the desulfurization reactor, a gas distributor is provided inside the desulfurization reactor and above the sulfur-containing gas inlet, a desulfurization reaction agitator is provided inside the desulfurization reactor and above the gas distributor, a desulfurization reactor lean liquid inlet is provided at the bottom of the desulfurization reactor, a desulfurization reactor rich liquid outlet is provided at the top of the desulfurization reactor, a desulfurizer injection port, a purified gas outlet and a desulfurization reactor pressure gauge are provided at the top of the desulfurization reactor; a heater is provided at the bottom of the regeneration reactor. The lower part of the regeneration reactor is provided with a regeneration reactor lean liquid outlet, the regeneration reactor is provided with a regeneration reactor agitator, the upper part of the regeneration reactor is provided with a regeneration reactor rich liquid inlet, and the top of the regeneration reactor R-2 is provided with a vent control valve, a regeneration reactor pressure gauge and a regeneration reactor sulfide gas outlet; the desulfurization reactor rich liquid outlet of the desulfurization reactor is connected with the regeneration reactor rich liquid inlet of the regeneration reactor through a heat exchanger, the regeneration reactor lean liquid outlet of the regeneration reactor is connected with the desulfurization reactor lean liquid inlet of the desulfurization reactor through the heat exchanger and the cooler, a rich liquid pump is provided between the desulfurization reactor rich liquid outlet and the heat exchanger, and a lean liquid pump is provided between the regeneration reactor lean liquid outlet and the heat exchanger.

[0016] Specifically, the high-efficiency desulfurizer of the present invention is compounded with an organic solvent and an organic alcohol amine, and has a higher viscosity than the traditional desulfurizer using water as a solvent. Therefore, the desulfurization reactor and the regeneration reactor provided by the present invention are provided with an agitator, and no filler or tray is provided, which greatly reduces the system pressure drop and saves system energy consumption.

[0017] As a specific embodiment of the present invention, preferably, the heater is electrically heated or steam heated; and / or the height-to-diameter ratio of the desulfurization reactor is 3:1-10:1; and / or the volume of the desulfurization reactor is 200L-20m 3 and / or the height-to-diameter ratio of the regeneration reactor is 2:1-10:1, and / or the volume of the regeneration reactor is 200L-20m 3 ; and / or the pressure of the regeneration reactor is 100kPa-220kPa, preferably 100kPa-200kPa.

[0018] To achieve the above object, the present invention also provides a method for removing H2S or organic sulfur from sulfur-containing process gas or sulfur-containing waste gas. The desulfurization reaction is carried out in the above desulfurization equipment, comprising the following steps:

[0019] (1) replacing the air in the reaction system with nitrogen;

[0020] (2) adding the above-mentioned high-efficiency desulfurizer into the desulfurization reactor, and starting the rich liquid pump and the lean liquid pump to drive the high-efficiency desulfurizer to flow inside the desulfurization reactor and the regeneration reactor;

[0021] (3) Desulfurization reaction conditions and regeneration reaction conditions are set. After the reaction is stable, desulfurization reaction is carried out in the desulfurization reactor, and regeneration reaction is carried out in the regeneration reactor.

[0022] As a specific embodiment of the present invention, preferably, the desulfurization reaction conditions include: temperature of 10°C-50°C, pressure of 0.4MPa-4.0MPa, gas-liquid ratio of 200:1-2000:1, stirring rate of 10r / min-100r / min; and / or the regeneration reaction conditions include: regeneration temperature of 100°C-120°C, regeneration pressure of 100kPa-220kPa, regeneration gas-liquid ratio of 200:1-2000:1, regeneration stirring rate of 10-100r / min, and the regeneration pressure is further preferably 100kPa-200kPa.

[0023] As a specific embodiment of the present invention, preferably, the desulfurization reaction conditions also include: the desulfurization agent circulation rate is set at 100 kg / h according to the pilot scale, the air intake rate is 20 Nm 3 / h.

[0024] The present invention has the following advantages:

[0025] 1. The high-efficiency desulfurizer provided by the present invention is used to remove H2S or organic sulfur from sulfur-containing process gas or sulfur-containing waste gas. The absorption capacity of H2S is increased by 50% compared with the traditional desulfurizer (30w% MDEA aqueous solution), the maximum saturated H2S load is 0.76mol H2S / mol amine, the H2S loading amount can reach 60g / L, the desulfurization selectivity can reach more than 20, the CO2 co-absorption rate is reduced to less than 5%, and the organic sulfur (CH3SH, COS) removal rate reaches more than 90%;

[0026] 2. The high-efficiency desulfurizer provided by the present invention has high regeneration efficiency due to the reduced specific heat of the organic solvent, and the regeneration energy consumption is reduced by 30%-40% compared with the regeneration energy consumption of the traditional desulfurizer;

[0027] 3. The desulfurization equipment provided by the present invention increases the viscosity of the system after using an organic solvent. Therefore, the desulfurization reactor and the regeneration reactor do not need to be filled with fillers or provided with tower plates, which greatly reduces the system pressure drop and saves energy consumption.

[0028] In summary, the high-efficiency desulfurizer provided by the present invention overcomes the disadvantages of traditional desulfurizers, such as low sulfur load, high regeneration energy consumption, easy degradation, and inability to remove organic sulfur. It is suitable for desulfurization and purification of sulfur-containing gases such as highly acidic natural gas, refinery dry gas, liquefied gas, and sulfur recovery tail gas. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a schematic diagram of a complete set of desulfurization equipment and process involved in the present invention, wherein:

[0030] R-1——desulfurization reactor; R-2——regeneration reactor; R-3——desulfurizer tank; R-4——sulfur-containing gas source; R-5——gas distributor; R-6——purified gas flowmeter; R-7——raw gas flowmeter; R-8——desulfurizer injection port; R-9——purified gas outlet; R-10——desulfurization reactor rich liquid outlet; R-11——sulfur-containing gas inlet; R-12——desulfurization reactor lean liquid inlet; R-13——regeneration reactor rich liquid inlet; R-14——regeneration reactor lean liquid outlet; R-15——regeneration reactor sulfide gas outlet;

[0031] C-1——Sulfur-containing gas source control valve; C-2——Gas inlet control valve; C-3——Pressure reduction control valve; C-4——Purified gas outlet control valve; C-5——Back pressure valve; C-6——Desulfurization reactor pressure gauge; C-7——Regeneration reactor pressure gauge; C-8——Desulfurization reactor inlet lean liquid temperature display; C-9——Regeneration reactor outlet lean liquid temperature display; C-10——Regeneration reactor inlet rich liquid temperature display; C-11——Venting control valve;

[0032] P-1——desulfurization agent pump; P-2——lean liquid pump; P-3——rich liquid pump; P-4——desulfurization reaction agitator; P-5——regeneration reaction agitator; P-6——desulfurization agitator blades; P-7——regeneration agitator blades;

[0033] E-1——heat exchanger; E-2——cooler; E-3——heater. DETAILED DESCRIPTION

[0034] In order to make the purpose and advantages of the present invention clearer, the following examples are used to describe the implementation steps of the present invention in detail. The GC-9560 gas chromatograph, 1ml syringe, 250ml conical flask, etc., and 0.1mol / L zinc acetate, 0.05mol / L iodine standard solution, 0.01mol / L dilute hydrochloric acid, 0.1mol / L sodium thiosulfate standard solution, starch indicator, sulfolane (chemically pure), methyl sulfolane (chemically pure), corrosion inhibitor (industrial product) and other related terms involved in the test do not limit the present invention, but are only for the purpose of describing specific embodiments, and are not intended to limit the present invention, and should not be interpreted as being limited to the embodiments set forth herein. Obviously, the following embodiments are only a part of the embodiments in the present invention, rather than all of the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work premise belong to the scope of protection of the present invention.

[0035] The sulfur-containing gas source and composition selected in the embodiment of the present invention are shown in Table 1, and the desulfurizing agent and composition selected in the embodiment of the present invention are shown in Table 2.

[0036] Table 1 Composition of sulfur-containing gas source

[0037]

[0038]

[0039] Table 2 Desulfurization agent composition

[0040]

[0041] See also Figure 1 As shown, Figure 1The desulfurization equipment provided by the present invention includes a desulfurization reactor R-1 and a regeneration reactor R-2. The bottom of the desulfurization reactor R-1 is provided with a sulfur-containing gas inlet R-11. A gas distributor R-5 is provided inside the desulfurization reactor R-1 and above the sulfur-containing gas inlet R-11. A desulfurization reactor agitator P-4 with a desulfurization stirring blade P-6 is provided inside the desulfurization reactor R-1 and above the gas distributor R-5. A desulfurization reactor lean liquid inlet R-12 is provided at the bottom of the desulfurization reactor R-1. A desulfurization reactor rich liquid outlet R-10 is provided at the top of the desulfurization reactor R-1. A desulfurizer injection port R-8, a purified gas outlet R-9 and a desulfurization reactor pressure gauge C-6 are provided at the top of R-1; a heater E-3 is provided at the bottom of the regeneration reactor R-2, a regeneration reactor lean liquid outlet R-14 is provided at the lower part of the regeneration reactor R-2, a regeneration reactor agitator P-5 with a regeneration stirring blade P-7 is provided inside the regeneration reactor R-2, a regeneration reactor rich liquid inlet R-13 is provided at the upper part of the regeneration reactor R-2, and a vent control valve C-11, a regeneration reactor pressure gauge C-7 and a regeneration reactor sulfide gas outlet R-15 are provided at the top of the regeneration reactor R-2.

[0042] Along the direction of material flow, the desulfurizer tank R-3 is connected to the desulfurizer injection port R-8 through a pipeline equipped with a desulfurizer pump P-1. The sulfur-containing gas source R-4 is connected to the sulfur-containing gas inlet R-11 through a pipeline equipped with a sulfur-containing gas source control valve C-1, a gas inlet control valve C-2, a pressure reducing control valve C-3, and a raw gas flowmeter R-7 in sequence. The pipeline connected to the purified gas outlet R-9 is equipped with a purified gas outlet control valve C-4, a back pressure valve C-5 and a purified gas flowmeter R-6 in sequence. The desulfurization reactor rich liquid outlet R- 10 is connected to the heat exchanger E-1 through a pipeline provided with a rich liquid pump P-3, and the heat exchanger E-1 is connected to the desulfurization reactor lean liquid inlet R-12 through a pipeline provided with a cooler E-2 and a desulfurization reactor inlet lean liquid temperature display C-8; the heat exchanger E-1 is connected to the regeneration reactor R-2 through a pipeline provided with a regeneration reactor inlet rich liquid temperature display C-10, and the regeneration reactor lean liquid outlet R-14 is connected to the heat exchanger E-1 through a pipeline provided with a regeneration reactor outlet lean liquid temperature display C-9 and a lean liquid pump P-2.

[0043] The sulfur-containing gas source R-4 can be a steel cylinder, a gas cabinet or sulfur-containing process gas, sulfur-containing waste gas, etc. from upstream; the purified gas flow meter R-6 and the raw gas flow meter R-7 can display and control the gas flow; the pressure reducing control valve C-3 is used to adjust the pressure of the desulfurization reactor, and the back pressure valve C-5 can control the pressure of the desulfurization reactor.

[0044] When the desulfurization equipment of the present invention is used to remove H2S and / or organic sulfur in gas, it comprises the following steps:

[0045] First, open the vent valve C-11 and replace the air in the reaction system with nitrogen. After completion, close the vent valve C-11. The desulfurizer pump P-1 pumps the desulfurizer from the desulfurizer tank R-3 into the desulfurization reactor R-1 through the desulfurizer injection port R-8 until the desulfurizer fills the desulfurization reactor R-1. Then, open the rich liquid pump P-3 to extract the desulfurizer from the rich liquid outlet R-10 of the desulfurization reactor and drive the desulfurizer to flow inside the reaction system. The desulfurizer flows through the shell side of the heat exchanger E-1 and the rich liquid inlet R-13 of the regeneration reactor in turn and enters the regeneration reactor R-2. When the desulfurizer fills the regeneration reactor R-2, stop the desulfurizer pump P-1 and open the lean liquid pump P-2 to drive the desulfurizer back to the sulfur reactor R-1. The desulfurizer leaves the regeneration reactor R-2 from the regeneration reactor lean liquid outlet R-14, flows through the heat exchanger E-1 tube pass, cooler E-2 in sequence, and enters the bottom of the desulfurization reactor R-1 from the desulfurization reactor lean liquid inlet R-12.

[0046] Then, set the heater E-3 at the bottom of the regeneration reactor R-2, control the temperature of the desulfurizer in the regeneration reactor R-2 to 100℃-120℃, adjust the cooler E-2 to ensure that the temperature of the lean liquid entering the desulfurization reactor R-1 is 10℃-50℃, set the speed of the desulfurization reaction agitator P-4 to 10-100r / min, and set the speed of the regeneration reaction agitator P-5 to 10-100r / min. After the reaction system is stable, open the sulfur-containing gas source control valve C-1 of the sulfur-containing gas source R-4, open the gas inlet control valve C-2, and the sulfur-containing gas flows through the gas inlet control valve C-2, the pressure reducing control valve C-3, and the raw gas flowmeter R-7 in turn, and enters the gas distributor R-5 from the sulfur-containing gas inlet R-11. Adjust the pressure reducing control valve C-3 to the pressure range required by the desulfurization process, adjust the raw gas flowmeter R-7 to control the flow rate of the sulfur-containing gas, and contact and react with the desulfurizer in the desulfurization reactor R-1. Under the shearing action of the desulfurization stirring blades P-6, the sulfur-containing gas is fully in contact with the desulfurizer, and the H2S and organic sulfur in the gas phase enter the desulfurizer phase. The gas after desulfurization purification is discharged from the purified gas outlet R-9, and passes through the purified gas outlet control valve C-4, the back pressure valve C-5, and the purified gas flowmeter R-6 in turn to enter the next treatment process. The sulfide-loaded desulfurizer (called rich liquid) is pumped into the shell side of the heat exchanger E-1 through the rich liquid outlet R-10 of the desulfurization reactor by the rich liquid pump P-3 for heat exchange with the lean liquid in the tube side of the heat exchanger E-1, and enters the regeneration reactor R-2 through the rich liquid inlet R-13 of the regeneration reactor. The rich liquid is heated to 100℃-120℃ inside the regeneration reactor R-2. Under the action of the pressure reduction and the regeneration stirring blades P-7, the sulfide (H2S, organic sulfur) is desorbed and enters the subsequent treatment process through the sulfide gas outlet R-15 of the regeneration reactor. The rich liquid is regenerated into lean liquid and returned to the tube side of the heat exchanger E-1 by the lean liquid pump P-2 through the lean liquid outlet R-14 of the regeneration reactor. After being cooled in the cooler E-2, it returns to the desulfurization reactor R-1.

[0047] Secondly, determine the acid gas load of the desulfurizer: (1) Use a 1ml syringe to accurately measure 1ml of amine solution before absorbing acid gas and weigh it to obtain the mass of the amine solution before absorption m (g). Add 20ml of 0.1mol / L zinc acetate solution to a 250ml conical flask, use a dried syringe to extract 1ml of rich solution, accurately weigh m' (g), and insert the syringe containing rich solution into the conical flask, slowly inject the solution to the bottom of the solution, and shake the conical flask repeatedly to wash it. Wash the syringe three times, add 0.01 mol / L dilute hydrochloric acid to the conical flask to adjust the pH value of the solution to 6.5-7.0, add 15 ml of iodine standard solution to the conical flask, seal and place in a dark place for 10 min, and titrate the unreacted iodine with sodium thiosulfate standard solution. First, titrate with sodium thiosulfate standard solution until it turns light yellow. (2) Add 100 mg / L-1000 mg / L starch indicator and continue to titrate with sodium thiosulfate until the blue color just disappears.

[0048] H2S loading of desulfurizer H2S 、H2S load L H2S Calculate according to the following formula:

[0049]

[0050]

[0051]

[0052]

[0053] CO2 loading capacity of desulfurizer CO2 、CO2 load L CO2 Calculate according to the following formula:

[0054]

[0055]

[0056]

[0057] The H2S selectivity S of the desulfurizer is calculated according to the following formula:

[0058]

[0059] The calculation formula of regeneration energy consumption of desulfurizer is:

[0060] N(kj / t desulfurizer)=Cp*(T1-T2)*1000 / η...................9

[0061] Where: n H2S is the molar amount of H2S absorbed by 1ml desulfurizer, mol; m H2S is the mass of H2S absorbed by 1ml of desulfurizer, g; v 脱硫剂 is the volume of the desulfurizer accurately measured, which is 1 ml; m is the mass of 1 ml of desulfurizer before absorbing acid gas, g; m' is the mass of 1 ml of desulfurizer after absorbing acid gas, g; C a is the amine concentration in the desulfurizer, mol / L; M H2S is the relative molecular weight of H2S, g / mol; is the relative molecular weight of CO2, g / mol; V1 is the volume of the iodine standard solution, ml; C1 is the concentration of the iodine standard solution, mol / L; V NaS2O3 is the volume of sodium thiosulfate standard solution consumed, ml; C NaS2O3 is the concentration of sodium thiosulfate standard solution consumed, mol / L; LH2S is the H2S load of the desulfurizer, mol H2S / mol a; l H2S is the H2S loading of the desulfurizer, g / L; L CO2 is the CO2 load of the desulfurizer, mol CO2 / mol a; l CO2 is the CO2 loading of the desulfurizer, g / L; y H2S is the H2S content in the sulfur-containing gas source, mg / Nm 3 ;y CO2 is the CO2 content in the sulfur-containing gas source, mg / Nm 3 ; N is the regeneration energy consumption of desulfurizer, kJ / t desulfurizer; C p is the constant pressure specific heat capacity of the desulfurizer, kJ / kg / k; T1 is the regeneration temperature of the desulfurizer, °C; T2 is the heat exchange final temperature of the desulfurizer, °C; η is the heating efficiency;

[0062] The organic sulfur removal rate E is calculated according to the following formula:

[0063]

[0064] In the formula is the concentration of organic sulfur in the sulfur-containing gas source, mg / Nm 3 , φ is the concentration of organic sulfur after the sulfur-containing gas source is purified, mg / Nm 3 , x is the volume fraction of the component absorbed by the solvent in the raw gas after passing through the absorption tower, %.

[0065] Example 1

[0066] Option 1 # The desulfurization agent was used to evaluate the desulfurization of GAS-8. The first step was to open the vent valve and replace the air in the system with nitrogen. After completion, the vent valve C-11 was closed. The second step was to use the desulfurizer pump P-1 to pump 1 # The desulfurizer is injected into the desulfurization reactor R-1 through the desulfurizer injection port R-8, and the rich liquid pump P-3 and the lean liquid pump P-2 are turned on to drive the desulfurizer to flow inside the desulfurization reactor and the regeneration reactor; the third step is to set the desulfurization and regeneration reaction conditions according to the operating parameters given in Table 3. After the system is stable, open the sulfur-containing gas source control valve C-1 of the sulfur-containing gas source R-4, open the gas inlet control valve C-2, the pressure reducing control valve C-3, and the raw gas flow meter R-7, and adjust the raw gas flow meter R-7 to control the flow rate of the sulfur-containing gas to 173Nm 3 / h, and carries out contact reaction with the desulfurizer in the desulfurization reactor R-1.

[0067] Table 3 Desulfurization evaluation conditions of Example 1

[0068]

[0069] After the desulfurization evaluation test is completed, the GC-9560 gas chromatograph is used to analyze the H2S and CO2 contents in the purified gas (see Table 18), and the following steps are used to determine 1 # Acid gas load of desulfurizer: (1) Use a 1ml syringe to accurately measure 1ml of 1ml before absorbing acid gas. # The desulfurizer and the rich liquid after absorbing the acid gas were weighed, m was 1.1562g, and m' was 1.2162g; (2) 20ml of 0.1mol / L zinc acetate solution was added to a 250ml conical flask, the syringe containing the rich solution was inserted into the 250ml conical flask, the solution was slowly injected into the bottom of the solution, and the conical flask was shaken, the syringe was repeatedly washed 3 times, 0.01mol / L dilute hydrochloric acid was added to the conical flask to adjust the pH value of the solution to 6.5, 40ml of iodine standard solution (0.05mol / L) was added to the conical flask, sealed and placed in a dark place for 10min; 3. Unreacted iodine was titrated with sodium thiosulfate standard solution (0.1mol / L), first titrated with sodium thiosulfate standard solution until light yellow, then added 100mg / L starch indicator, and continued to titrate with 4.72ml sodium thiosulfate until the blue color just disappeared.

[0070] According to the calculation method above, calculate 1 # H2S loading of desulfurizer H2S 、H2S load L H2S 、CO2 loading capacity CO2 、CO2 load L CO2 And the regeneration energy consumption N.

[0071]

[0072]

[0073]

[0074]

[0075] N (MJ / t desulfurizer) = Cp*(T1-T2)*1000 / η = 2.50*(110-95)*1000 / 1000 / η = 62.5 MJ / t Desulfurizer Example 2

[0076] Select 1 according to the method in Example 1 # The desulfurization agent was used to evaluate the desulfurization of GAS-6. The desulfurization agent evaluation conditions were based on the operating parameters given in Table 4. The raw gas flow meter R-7 was adjusted to control the flow rate of sulfur-containing gas to 86.5 Nm 3 / h, and carries out contact reaction with the desulfurizer in the desulfurization reactor R-1.

[0077] Table 4 Desulfurization evaluation conditions of Example 2

[0078]

[0079]

[0080] After the desulfurization evaluation test is completed, the contents of H2S and CO2 in the purified gas are analyzed by GC-9560 gas chromatograph (see Table 18), and the steps of Example 1 are followed to determine 1 # The acid gas load of the desulfurizer, where m is 1.1562g, m' is 1.1651g; the iodine standard solution (0.05mol / L) is 15ml, and the sodium thiosulfate titration solution (0.1mol / L) is 14.42ml. Calculate 1 according to the calculation method in the above manual. # H2S loading of desulfurizer H2S 、H2S load L H2S 、CO2 loading capacity CO2 、CO2 load L CO2 , regeneration energy consumption N and selectivity S.

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088] N(MJ / t desulfurizer)=Cp*(T1-T2)*1000=2.50*(100-95)*1000 / 1000 / η=20.8MJ / t desulfurizer

[0089]

[0090] Example 3

[0091] Select 1 according to the method in Example 1 # The desulfurization agent was used to evaluate the desulfurization of GAS-x. The desulfurization agent evaluation conditions were based on the operating parameters given in Table 5. The raw gas flow meter R-7 was adjusted to control the flow rate of sulfur-containing gas to 43.25 Nm 3 / h, and carries out contact reaction with the desulfurizer in the desulfurization reactor R-1.

[0092] Table 5 Desulfurization evaluation conditions of Example 3

[0093]

[0094]

[0095] After the desulfurization evaluation test is completed, the contents of H2S and CO2 in the purified gas are analyzed by GC-9560 gas chromatograph (see Table 18), and the steps of Example 1 are followed to determine 1 # The acid gas load of the desulfurizer, where m is 1.1562g, m' is 1.2091g; the iodine standard solution (0.05mol / L) is 35ml, and the sodium thiosulfate titration solution (0.1mol / L) is 5.6ml. Calculate 1 according to the calculation method in the above manual. # H2S loading of desulfurizer H2S 49.98g / L, H2S load L H2S is 0.3808 molH2S / mol amine, CO2 loading l CO2 2.72g / L, CO2 load L CO2 0.016 mol CO2 / mol amine, the selectivity S of the desulfurizer is 27.25, and the regeneration energy consumption N of the desulfurizer is 104.2MJ / t desulfurizer. The results are shown in Table 18.

[0096] Example 4

[0097] Select 1 according to the method in Example 1 # The desulfurization agent was used to evaluate the desulfurization of GAS-2. The desulfurization agent evaluation conditions were based on the operating parameters given in Table 6. The raw gas flow meter R-7 was adjusted to control the flow rate of sulfur-containing gas to 43.25 Nm 3 / h, and carries out contact reaction with the desulfurizer in the desulfurization reactor R-1.

[0098] Table 6 Desulfurization evaluation conditions of Example 4

[0099]

[0100] After the desulfurization evaluation test was completed, the GC-9560 gas chromatograph was used to analyze the H2S and CO2 contents in the purified gas (see Table 18), and the acid gas load of the 1# desulfurizer was determined according to the steps of Example 1, where m was 1.1562g, m' was 1.1991g; the iodine standard solution (0.05mol / L) was 30ml, and the sodium thiosulfate titration solution (0.1mol / L) was 6.48ml. The H2S loading of the 1# desulfurizer was calculated according to the calculation method in the above specification. H2S 39.98g / L, H2S load LH2S 0.3047 mol H2S / mol amine, CO2 loading l CO2 2.92g / L, CO2 load L CO2 It is 0.0172 mol CO2 / mol amine, the selectivity S of the desulfurizer is 25.97, and the regeneration energy consumption N of the desulfurizer is 104.2 MJ / t desulfurizer. The results are shown in Table 18.

[0101] Example 5

[0102] Select 1 according to the method in Example 1 # The desulfurization agent was used to evaluate the desulfurization of GAS-4. The desulfurization agent evaluation conditions were based on the operating parameters given in Table 7. The raw gas flow meter R-7 was adjusted to control the flow rate of sulfur-containing gas to 43.25 Nm 3 / h, and carries out contact reaction with the desulfurizer in the desulfurization reactor R-1.

[0103] Table 7 Desulfurization evaluation conditions of Example 5

[0104]

[0105] After the desulfurization evaluation test is completed, the contents of H2S and CO2 in the purified gas are analyzed by GC-9560 gas chromatograph (see Table 18), and the steps of Example 1 are followed to determine 1 # The acid gas load of the desulfurizer, where m is 1.1562g, m' is 1.1697g; the iodine standard solution (0.05mol / L) is 15ml, and the sodium thiosulfate titration solution (0.1mol / L) is 9.12ml. Calculate 1 according to the calculation method in the above manual. # H2S loading of desulfurizer H2S 10.00g / L, H2S load L H2S 0.0762 molH2S / mol amine, CO2 loading l CO2 3.50g / L, CO2 load L CO2 It is 0.0206 molCO2 / molamine, the selectivity S of the desulfurizer is 21.41, and the regeneration energy consumption N of the desulfurizer is 20.8 MJ / t desulfurizer. The results are shown in Table 18.

[0106] Example 6

[0107] Select 1 according to the method in Example 1 # The desulfurization agent was used to evaluate the desulfurization of GAS-y. The desulfurization agent evaluation conditions were based on the operating parameters given in Table 8. The raw gas flow meter R-7 was adjusted to control the flow rate of sulfur-containing gas to 17.3 Nm 3 / h, and carries out contact reaction with the desulfurizer in the desulfurization reactor R-1.

[0108] Table 8 Desulfurization evaluation conditions of Example 6

[0109]

[0110] After the desulfurization evaluation test is completed, the contents of H2S and CO2 in the purified gas are analyzed by GC-9560 gas chromatograph (see Table 18), and the steps of Example 1 are followed to determine 1 # The acid gas load of the desulfurizer, where m is 1.1562g, m' is 1.1604g; iodine standard solution (0.05mol / L) 10ml, sodium thiosulfate titration solution (0.1mol / L) 7.65ml. Calculate 2 # H2S loading of desulfurizer H2S 3.99g / L, H2S load L H2S 0.0304 mol H2S / mol amine, CO2 loading l CO2 0.21g / L, CO2 load L CO2 It is 0.0012 mol CO2 / mol amine, the selectivity S of the desulfurizer is 19.58, and the regeneration energy consumption N of the desulfurizer is 62.5 MJ / t desulfurizer. The results are shown in Table 18.

[0111] Example 7

[0112] Select 2 according to the method in Example 1 # The desulfurization agent was used to evaluate the desulfurization of GAS-3. The desulfurization agent evaluation conditions were based on the operating parameters given in Table 9. The raw gas flow meter R-7 was adjusted to control the flow rate of sulfur-containing gas to 43.44 Nm 3 / h, and carries out contact reaction with the desulfurizer in the desulfurization reactor R-1.

[0113] Table 9 Desulfurization evaluation conditions of Example 7

[0114]

[0115] After the desulfurization evaluation test is completed, the contents of H2S and CO2 in the purified gas are analyzed by GC-9560 gas chromatograph (see Table 18), and the steps of Example 1 are followed to determine 2 # The acid gas load of the desulfurizer, where m is 1.1513g, m' is 1.1783g; the iodine standard solution (0.05mol / L) is 10ml, and the sodium thiosulfate titration solution (0.1mol / L) is 5.30ml. Calculate 2 # H2S loading of desulfurizer H2S 24.99g / L, H2S load L H2S0.2723 mol H2S / mol amine, CO2 loading l CO2 2.01g / L, CO2 load L CO2 It is 0.0169 molCO2 / molamine, the selectivity S of the desulfurizer is 12.45, and the regeneration energy consumption N of the desulfurizer is 20.8 MJ / t desulfurizer. The results are shown in Table 18.

[0116] Example 8

[0117] Select 2 according to the method in Example 1 # The desulfurization agent was used to evaluate the desulfurization of GAS-z. The desulfurization agent evaluation conditions were based on the operating parameters given in Table 10. The raw gas flow meter R-7 was adjusted to control the flow rate of sulfur-containing gas to 43.44 Nm 3 / h, and carries out contact reaction with the desulfurizer in the desulfurization reactor R-1.

[0118] Table 10 Desulfurization evaluation conditions of Example 8

[0119]

[0120]

[0121] After the desulfurization evaluation test is completed, the contents of H2S and CO2 in the purified gas are analyzed by GC-9560 gas chromatograph (see Table 18), and the steps of Example 1 are followed to determine 2 # The acid gas load of the desulfurizer, where m is 1.1513g, m' is 1.1733g; the iodine standard solution (0.05mol / L) is 15ml, and the sodium thiosulfate titration solution (0.1mol / L) is 6.18ml. Calculate 2 # H2S loading of desulfurizer H2S 14.99 g / L, H2S load L H2S 0.1633 mol H2S / mol amine, CO2 loading l CO2 7.00g / L, CO2 load L CO2 It is 0.059 mol CO2 / mol amine, the selectivity of the desulfurizer is 10.69, and the regeneration energy consumption of the desulfurizer is 62.5 MJ / t desulfurizer. The results are shown in Table 18.

[0122] Example 9

[0123] Select 3 according to the method in Example 1 # The desulfurization agent was used to evaluate the desulfurization of GAS-4. The desulfurization agent evaluation conditions were based on the operating parameters given in Table 11. The raw gas flow meter R-7 was adjusted to control the flow rate of sulfur-containing gas to 44.84 Nm 3 / h, and carries out contact reaction with the desulfurizer in the desulfurization reactor R-1.

[0124] Table 11 Desulfurization evaluation conditions of Example 9

[0125]

[0126]

[0127] After the desulfurization evaluation test is completed, the contents of H2S and CO2 in the purified gas are analyzed by GC-9560 gas chromatograph (see Table 18), and the steps of Example 1 are followed to determine 3 # The acid gas load of the desulfurizer, where m is 1.1154g, m' is 1.1285g; the iodine standard solution (0.05mol / L) is 15ml, and the sodium thiosulfate titration solution (0.1mol / L) is 9.12ml. Calculate 3 according to the calculation method in the above manual # H2S loading of desulfurizer H2S 9.99g / L, H2S load L H2S 0.1872 mol H2S / mol amine, CO2 loading l CO2 3.10g / L, CO2 load L CO2 It is 0.0442 mol CO2 / mol amine, the selectivity S of the desulfurizer is 24.55, and the regeneration energy consumption N of the desulfurizer is 20.8 MJ / t desulfurizer. The results are shown in Table 18.

[0128] Example 10

[0129] Select 3 according to the method in Example 1 # The desulfurization agent was used to evaluate the desulfurization of GAS-z. The desulfurization agent evaluation conditions were based on the operating parameters given in Table 12. The raw gas flow meter R-7 was adjusted to control the flow rate of sulfur-containing gas to 44.84 Nm 3 / h, and carries out contact reaction with the desulfurizer in the desulfurization reactor R-1.

[0130] Table 12 Desulfurization evaluation conditions of Example 10

[0131]

[0132] After the desulfurization evaluation test is completed, the contents of H2S and CO2 in the purified gas are analyzed by GC-9560 gas chromatograph (see Table 18), and the steps of Example 1 are followed to determine 3 #The acid gas load of the desulfurizer, where m is 1.1154g, m' is 1.1334g; the iodine standard solution (0.05mol / L) is 20ml, and the sodium thiosulfate titration solution (0.1mol / L) is 11.18ml. Calculate 3 according to the calculation method in the above manual # H2S loading of desulfurizer H2S 14.99 g / L, H2S load L H2S 0.2808 molH2S / mol amine, CO2 loading l CO2 3.00g / L, CO2 load L CO2 It is 0.0440 mol CO2 / mol amine, the selectivity S of the desulfurizer is 24.66, and the regeneration energy consumption N of the desulfurizer is 104.2 MJ / t desulfurizer. The results are shown in Table 18.

[0133] Embodiment 11

[0134] Select 4 according to the method in Example 1 # The desulfurization agent was used to evaluate the desulfurization of GAS-w. The desulfurization agent evaluation conditions were based on the operating parameters given in Table 13. The raw gas flow meter R-7 was adjusted to control the flow rate of sulfur-containing gas to 17.55 Nm 3 / h, and carries out contact reaction with the desulfurizer in the desulfurization reactor R-1.

[0135] Table 13 Desulfurization evaluation conditions of Example 11

[0136]

[0137] After the desulfurization evaluation test is completed, the contents of H2S and CO2 in the purified gas are analyzed by GC-9560 gas chromatograph (see Table 18), and the steps of Example 1 are followed to determine 4 # The acid gas load of the desulfurizer, where m is 1.1438g, m' is 1.1675g; the iodine standard solution (0.05mol / L) is 15ml, and the sodium thiosulfate titration solution (0.1mol / L) is 3.24ml. Calculate 4 # H2S loading of desulfurizer H2S 19.99g / L, H2S load L H2S is 0.7133 molH2S / mol amine, CO2 loading l CO2 3.71g / L, CO2 load L CO2 It is 0.1045 molCO2 / molamine, the selectivity S of the desulfurizer is 10.55, and the regeneration energy consumption N of the desulfurizer is 62.5 MJ / t desulfurizer. The results are shown in Table 18.

[0138] Example 12

[0139] Select 5 according to the method in Example 1 # The desulfurization agent was used to evaluate the desulfurization of GAS-7. The desulfurization agent evaluation conditions were based on the operating parameters given in Table 14. The raw gas flow meter R-7 was adjusted to control the flow rate of sulfur-containing gas to 81.06 Nm 3 / h, and carries out contact reaction with the desulfurizer in the desulfurization reactor R-1.

[0140] Table 14 Desulfurization evaluation conditions of Example 12

[0141]

[0142] After the desulfurization evaluation test is completed, the contents of H2S and CO2 in the purified gas are analyzed by GC-9560 gas chromatograph (see Table 18), and the steps of Example 1 are followed to determine 5 # The acid gas load of the desulfurizer, where m is 1.2325g, m' is 1.2416g; the iodine standard solution (0.05mol / L) is 15ml, and the sodium thiosulfate titration solution (0.1mol / L) is 14.45ml. Calculate 5 # Organic sulfur loading of desulfurizer CH3SH is 0.94 g / L, and the organic sulfur load is L CH3SH 0.01mol CH3SH / mol amine, CO2 loading l CO2 8.17g / L, CO2 load L CO2 It is 0.0947 mol CO2 / mol amine, the selectivity S of the desulfurizer is 3.92, and the regeneration energy consumption N of the desulfurizer is 104.2 MJ / t desulfurizer. The results are shown in Table 18.

[0143] Embodiment 13

[0144] Select 6 according to the method in Example 1 # The desulfurization agent was used to evaluate the desulfurization of GAS-3. The desulfurization agent evaluation conditions were based on the operating parameters given in Table 15. The raw gas flow meter R-7 was adjusted to control the flow rate of sulfur-containing gas to 40.62Nm 3 / h, and carries out contact reaction with the desulfurizer in the desulfurization reactor R-1.

[0145] Table 15 Desulfurization evaluation conditions of Example 13

[0146]

[0147] After the desulfurization evaluation test is completed, the contents of H2S and CO2 in the purified gas are analyzed by GC-9560 gas chromatograph (see Table 18), and the steps of Example 1 are followed to determine 6 #The acid gas load of the desulfurizer, where m is 1.2317g, m' is 1.2587g; the iodine standard solution (0.05mol / L) is 25ml, and the sodium thiosulfate titration solution (0.1mol / L) is 10.30ml. Calculate 6 # H2S loading of desulfurizer H2S 24.99g / L, H2S load L H2S is 0.7658 molH2S / mol amine, CO2 loading l CO2 2.01g / L, CO2 load L CO2 It is 0.0476 mol CO2 / mol amine, the selectivity S of the desulfurizer is 12.43, and the regeneration energy consumption N of the desulfurizer is 20.8 MJ / t desulfurizer. The results are shown in Table 18.

[0148] Embodiment 14

[0149] Select 7 according to the method in Example 1 # The desulfurization agent was used to evaluate the desulfurization of GAS-1. The desulfurization agent evaluation conditions were based on the operating parameters given in Table 16. The raw gas flow meter R-7 was adjusted to control the flow rate of sulfur-containing gas to 28.30 Nm 3 / h, and carries out contact reaction with the desulfurizer in the desulfurization reactor R-1.

[0150] Table 16 Desulfurization evaluation conditions of Example 14

[0151]

[0152]

[0153] After the desulfurization evaluation test is completed, the contents of H2S and CO2 in the purified gas are analyzed by GC-9560 gas chromatograph (see Table 18), and the steps of Example 1 are followed to determine 7 # The acid gas load of the desulfurizer, where m is 1.0629g, m' is 1.0931g; the iodine standard solution (0.05mol / L) is 20ml, and the sodium thiosulfate titration solution (0.1mol / L) is 2.36ml. Calculate 7 # H2S loading of desulfurizer H2S 29.99g / L, H2S load L H2S is 0.3938 molH2S / mol amine, CO2 loading l CO2 0.21g / L, CO2 load L CO2 It is 0.0022 molCO2 / molamine, the selectivity S of the desulfurizer is 13.83, and the regeneration energy consumption N of the desulfurizer is 104.2 MJ / t desulfurizer. The results are shown in Table 18.

[0154] Embodiment 15

[0155] Select 8 according to the method in Example 1 # The desulfurization agent was used to evaluate the desulfurization of GAS-3. The desulfurization agent evaluation conditions were based on the operating parameters given in Table 17. The raw gas flow meter R-7 was adjusted to control the flow rate of sulfur-containing gas to 27.78 Nm 3 / h, and carries out contact reaction with the desulfurizer in the desulfurization reactor R-1.

[0156] Table 17 Desulfurization evaluation conditions of Example 15

[0157]

[0158]

[0159] After the desulfurization evaluation test is completed, the contents of H2S and CO2 in the purified gas are analyzed by GC-9560 gas chromatograph (see Table 18), and the steps of Example 1 are followed to determine 8 # The acid gas load of the desulfurizer, where m is 1.0836g, m' is 1.0993g; the iodine standard solution (0.05mol / L) is 25ml, and the sodium thiosulfate titration solution (0.1mol / L) is 11.18ml. Calculate 8 respectively according to the calculation method in the above manual # H2S loading of desulfurizer H2S 14.99 g / L, H2S load L H2S 0.3528 molH2S / mol amine, CO2 loading l CO2 0.71g / L, CO2 load l CO2 It is 0.0128 molCO2 / molamine, the selectivity S of the desulfurizer is 21.30, and the regeneration energy consumption N of the desulfurizer is 20.8 MJ / t desulfurizer. The results are shown in Table 18.

[0160] Comparative Example 1

[0161] According to the method in Example 1, a common MDEA desulfurizer (30w% MDEA aqueous solution) was selected to carry out a desulfurization evaluation test on GAS-3, wherein the desulfurizer evaluation conditions were based on the operating parameters given in Table 17, and the raw gas flow meter R-7 was adjusted to control the flow rate of the sulfur-containing gas to 27.78Nm 3 / h, and carries out contact reaction with the desulfurizer in the desulfurization reactor R-1.

[0162] Table 17 Desulfurization evaluation conditions of Example 16

[0163]

[0164] After the desulfurization evaluation test was completed, the contents of H2S and CO2 in the purified gas were analyzed by GC-9560 gas chromatograph (see Table 18), and the acid gas load of the common MDEA desulfurizer (30w% MDEA aqueous solution) was determined according to the steps of Example 1, where the H2S load was l H2S 13.89 g / L, H2S load L H2S 0.1621 molH2S / mol amine, CO2 loading l CO2 is 2.4282g / L, CO2 load l CO2 It is 0.0219 molCO2 / molamine, the selectivity S of the desulfurizer is 5.74, and the regeneration energy consumption N of the desulfurizer is 172.5 MJ / t desulfurizer. The results are shown in Table 18.

[0165] Table 18 Summary of results

[0166]

[0167] As shown in Table 18, the desulfurizer of the present invention has high selectivity and saturated H2S load in removing H2S gas source. At 0.4Mpa, the optimal H2S load reaches 0.7658mol H2S / mol amine, the optimal H2S load is close to 59.97gH2S / L, the optimal selectivity for H2S reaches 27.25, and the regeneration energy consumption is greatly reduced. Among them, Example 15 and Comparative Example 1 are the evaluation results of the desulfurizer of the present invention and the ordinary MDEA desulfurizer under the same gas source (GAS-3) and the same evaluation conditions (same temperature, pressure, gas-liquid ratio, etc.), which are comparable. After comparison, the H2S load of the desulfurizer of the present invention is increased by 117.6%, the selectivity for H2S is significantly improved, and the regeneration energy consumption of the desulfurizer is reduced by 39.2%.

[0168] Organic sulfur removal example

[0169] Example 16

[0170] According to the method in Example 1, select 1 in the present invention # The desulfurizer was used to evaluate the removal of organic sulfur from GAS-7. The desulfurizer evaluation conditions were based on the operating parameters given in Table 14. The raw gas flow meter R-7 was adjusted to control the flow rate of sulfur-containing gas to 81.06 Nm 3 / h, and carries out contact reaction with the desulfurizer in the desulfurization reactor R-1.

[0171] After the desulfurization evaluation test is completed, the GC-9560 gas chromatograph is used to analyze the contents of H2S, CO2 and organic sulfur (CH3SH, COS) in the purified gas, and the organic sulfur removal rate is calculated. The results are shown in Table 19.

[0172] Comparative Example 2

[0173] According to the method in Example 17, ordinary MDEA (30w% MDEA aqueous solution) was selected to conduct an organic sulfur removal evaluation test on GAS-7.

[0174] After the desulfurization evaluation test is completed, the GC-9560 gas chromatograph is used to analyze the contents of H2S, CO2 and organic sulfur (CH3SH, COS) in the purified gas, and the organic sulfur removal rate is calculated. The results are shown in Table 19.

[0175] Table 19 Comparison of organic sulfur removal effects

[0176]

[0177] As shown in Table 19, the desulfurizer in the present invention has a high removal rate of organic sulfur in the sulfur-containing gas source, reaching more than 90%; the organic sulfur content in the purified gas is reduced to 100 mg / Nm 3 the following.

[0178] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A highly efficient desulfurizer for removing H2S and / or organic sulfur from gas, characterized in that: The high-efficiency desulfurizer includes an organic solvent and an organic alcohol amine; optionally, the high-efficiency desulfurizer also includes at least one of an antioxidant, a corrosion inhibitor and a defoaming agent.

2. The high-efficiency desulfurizer according to claim 1, characterized in that: The organic solvent includes at least one of DMSO, DMA, sulfolane, and 3-methylsulfolane; and / or the organic alcohol amine is a tertiary amine.

3. The high-efficiency desulfurizer according to claim 1, characterized in that: The organic sulfur is a small molecular organic sulfide with a relative molecular mass of less than 100. Preferably, the organic sulfur includes at least one of carbon oxysulfide COS and methyl mercaptan CH3SH; and / or the organic alcohol amine is a hindered amine.

4. The high-efficiency desulfurizing agent according to any one of claims 1 to 3, characterized in that: The organic alcohol amine is selected from at least one of 1,3-di(dimethylamino)-2-propanol (BDMAP), 1,3-di(diethylamino)-2-propanol (BDMEP), 1,3-di-tert-butylamino-2-propanol, N-methyldiethanolamine (MDEA), N-tert-butylaminodiethanolamine, and triethanolamine.

5. The high-efficiency desulfurizing agent according to any one of claims 1 to 4, characterized in that: Based on the total molar amount of the organic alcohol amine and the organic solvent, in the high-efficiency desulfurizer, the molar content of the organic alcohol amine is 10%-40%, and the molar content of the organic solvent is 60%-90%; and / or, the concentration of the corrosion inhibitor in the high-efficiency desulfurizer is 100mg / L-1000mg / L; and / or, the concentration of the defoaming agent in the high-efficiency desulfurizer is 100mg / L-1000mg / L; and / or, the concentration of the antioxidant in the high-efficiency desulfurizer is 100mg / L-1000mg / L.

6. The high-efficiency desulfurizing agent according to any one of claims 1 to 5, characterized in that: The gas includes at least one of sulfur-containing process gas and sulfur-containing waste gas. Preferably, the H2S content in the gas is 1000 mg / Nm 3 -100000mg / Nm 3 , and / or organic sulfur content of 100 mg / Nm 3 -1000mg / Nm 3 .

7. A desulfurization device for removing H2S or organic sulfur from sulfur-containing process gas or sulfur-containing waste gas using the high-efficiency desulfurizer according to any one of claims 1 to 6, characterized in that: The desulfurization equipment comprises a desulfurization reactor and a regeneration reactor. Preferably, a sulfur-containing gas inlet is provided at the bottom of the desulfurization reactor, a gas distributor is provided inside the desulfurization reactor and above the sulfur-containing gas inlet, a desulfurization reaction agitator is provided inside the desulfurization reactor and above the gas distributor, a desulfurization reactor lean liquid inlet is provided at the bottom of the desulfurization reactor, a desulfurization reactor rich liquid outlet is provided at the top of the desulfurization reactor, a desulfurizer injection port, a purified gas outlet and a desulfurization reactor pressure gauge are provided at the top of the desulfurization reactor; a heater is provided at the bottom of the regeneration reactor, a regeneration reactor lean liquid outlet is provided at the bottom of the regeneration reactor, and a regeneration reactor A regeneration reactor is provided inside the reactor, a regeneration reactor rich liquid inlet is provided on the upper part of the regeneration reactor, and a vent control valve, a regeneration reactor pressure gauge and a regeneration reactor sulfide gas outlet are provided on the top of the regeneration reactor; the desulfurization reactor rich liquid outlet of the desulfurization reactor is connected with the regeneration reactor rich liquid inlet of the regeneration reactor through a heat exchanger, and the regeneration reactor lean liquid outlet of the regeneration reactor is connected with the desulfurization reactor lean liquid inlet of the desulfurization reactor through the heat exchanger and the cooler, a rich liquid pump is provided between the desulfurization reactor rich liquid outlet and the heat exchanger, and a lean liquid pump is provided between the regeneration reactor lean liquid outlet and the heat exchanger.

8. The desulfurization equipment according to claim 7, characterized in that: The heater is electrically heated or steam heated; and / or the height-to-diameter ratio of the desulfurization reactor is 3:1-10:1; and / or the volume of the desulfurization reactor is 200L-20m 3 and / or the height-to-diameter ratio of the regeneration reactor is 2:1-10:1, and / or the volume of the regeneration reactor is 200L-20m 3 ; and / or the pressure of the regeneration reactor is 100kPa-220kPa, preferably 100kPa-200kPa.

9. A method for removing H2S or organic sulfur from sulfur-containing process gas or sulfur-containing waste gas, characterized in that: The desulfurization reaction is carried out in the desulfurization equipment according to claim 7 or 8, comprising the following steps: (1) replacing the air in the reaction system with nitrogen; (2) adding the high-efficiency desulfurizer according to any one of claims 1 to 6 into the desulfurization reactor, and starting the rich liquid pump and the lean liquid pump to drive the high-efficiency desulfurizer to flow inside the desulfurization reactor and the regeneration reactor; (3) Desulfurization reaction conditions and regeneration reaction conditions are set. After the reaction is stable, desulfurization reaction is carried out in the desulfurization reactor, and regeneration reaction is carried out in the regeneration reactor.

10. The method according to claim 9, characterized in that The desulfurization reaction conditions include: temperature of 10°C-50°C, pressure of 0.4MPa-4.0MPa, gas-liquid ratio of 200:1-2000:1, and stirring rate of 10r / min-100r / min; and / or the regeneration reaction conditions include: regeneration temperature of 100°C-120°C, regeneration pressure of 100kPa-220kPa, regeneration gas-liquid ratio of 200:1-2000:1, and regeneration stirring rate of 10-100r / min, and the regeneration pressure is preferably 100kPa-200kPa.

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