Desulfurizing agent and application thereof

Abstract

The invention provides a desulfurizing agent and application thereof. The desulfurizing agent comprises a first complexing agent-iron complex, a second complexing agent-iron complex and ionic liquid, the first complexing agent is EDTA (Ethylene Diamine Tetraacetic Acid); the second complexing agent is selected from at least one of HEDTA, citric acid, salicylic acid, sulfosalicylic acid and tartaric acid; the ionic liquid comprises at least one of substituted or unsubstituted imidazole cations, pyridine cations, thiazole cations, piperidine cations, pyrazole cations and oxazole cations; and further comprises at least one of oxalate anions, acetate anions, salicylate anions, sulfosalicylate anions, citrate anions and tartrate anions. The desulfurizer has the advantage of high total sulfur removal rate.

Description

TECHNICAL FIELD

[0001] The present application relates to a desulfurizer and application, belonging to the field of petroleum refining. BACKGROUND

[0002] In a refining enterprise, the thermal efficiency of heating furnaces of atmospheric-vacuum distillation, catalytic cracking, catalytic hydrogenation and other production devices is about 91-93%, and there is still a large space for efficiency improvement. The main factor affecting the thermal efficiency of the heating furnace is the heat loss caused by the high exhaust gas temperature of the heating furnace. At present, the average exhaust gas temperature of the heating furnace is 120-160℃, and the reason is that the medium sulfide contained in the fuel gas is easy to generate sulfuric acid after combustion and oxidation, and when the exhaust gas temperature is too low, the sulfuric acid dew point corrosion phenomenon occurs, causing equipment corrosion. In order to avoid equipment corrosion, the exhaust gas temperature must be controlled above the sulfuric acid dew point corrosion temperature.

[0003] However, when the exhaust gas temperature is high, the heat contained in the flue gas cannot be recovered and utilized, resulting in low thermal efficiency of the heating furnace. If the sulfide content in the fuel gas can be reduced, the exhaust gas temperature of the heating furnace can be reduced, and thus the efficiency of the heating furnace can be improved.

[0004] At present, the desulfurizer for removing sulfides in fuel gas generally has the defect of low total sulfur removal efficiency. Therefore, developing a desulfurizer with high total sulfur removal efficiency has become the current research direction. SUMMARY

[0005] The present application provides a kind of desulfurizer, this kind of desulfurizer has the advantage that total sulfur removal efficiency is higher.

[0006] The present application also provides a method for removing sulfur compounds, which has the characteristics of simple operation and high desulfurization efficiency.

[0007] The present application provides a kind of desulfurizer, wherein, including first complexing agent-iron complex, second complexing agent-iron complex, ionic liquid;

[0008] The first complexing agent is EDTA;

[0009] The second complexing agent is selected from at least one of HEDTA, citric acid, salicylic acid, sulfosalicylic acid and tartaric acid;

[0010] The ionic liquid includes at least one of substituted or unsubstituted imidazole cation, pyridine cation, thiazole cation, piperidine cation, pyrazole cation and oxazole cation, and at least one of oxalate anion, acetate anion, salicylate anion, sulfosalicylate anion, citrate anion and tartrate anion.

[0011] The desulfurizer as described above, wherein the substituent of the cation in the ionic liquid comprises at least one of benzoic acid group, p-toluene sulfonic acid group, C1-C4 hydroxyalkyl group, and cyano group.

[0012] The desulfurizer as described above, wherein the substituent of the cation in the ionic liquid comprises at least one of phenolic hydroxyl group and quinone group.

[0013] The desulfurizer as described above, wherein the first complexing agent-iron complex and the second complexing agent-iron complex respectively comprise divalent iron and trivalent iron, and the molar ratio of the divalent iron to the trivalent iron is 1:3-1:5.

[0014] The desulfurizer as described above, wherein the molar ratio of the first complexing agent to the second complexing agent is 1:3-1:5; and / or,

[0015] The molar ratio of the iron element to the sum of the amounts of substance of the first complexing agent and the second complexing agent is 1:1.1-1:1.3.

[0016] The desulfurizer as described above, wherein the desulfurizer comprises, in terms of mass percentage, 5-20wt% of complexed iron, 20-60wt% of ionic liquid, and 20-75wt% of water.

[0017] The present application also provides a method for removing sulfur-containing compounds, which uses any of the above desulfurizers to contact with a to-be-treated substance and perform desulfurization treatment.

[0018] The method for removing sulfur-containing compounds as described above, wherein the liquid-gas ratio of the desulfurization treatment is 15-20L / m 3 , and the treatment temperature is 20-30℃.

[0019] The method for removing sulfur-containing compounds as described above, wherein the desulfurizer is contacted with the to-be-treated substance in a high gravity rotating packed bed to perform desulfurization treatment.

[0020] The method for removing sulfur-containing compounds as described above, wherein in the high gravity rotating packed bed, the packing is stainless steel wire mesh or stainless steel corrugated plate, the specific surface area of the packing is 1100-1200m 2 / m 3 , and the high gravity factor of the high gravity rotating packed bed is 140-220.

[0021] The desulfurizer provided by the present application has the characteristic of high total sulfur removal efficiency. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 It is a structural diagram of a high gravity rotating packed bed. DETAILED DESCRIPTION

[0023] In order to make the technical personnel in the art better understand the scheme of the present application, the present application is further described in detail below. The following specific embodiments are only used to describe the principles and characteristics of the present application, and the examples are used to explain the present application, but not to limit the scope of the present application. Based on the embodiments of the present application, all other embodiments obtained by the ordinary skilled in the art without creative labor are within the scope of protection of the present application.

[0024] The first aspect of the present application provides a desulfurizer, which comprises a first complexing agent-iron complex, a second complexing agent-iron complex, and an ionic liquid.

[0025] The first complexing agent is EDTA.

[0026] The second complexing agent is selected from at least one of HEDTA, citric acid, salicylic acid, sulfosalicylic acid, and tartaric acid.

[0027] The ionic liquid comprises at least one of a substituted or unsubstituted imidazole cation, a pyridine cation, a thiazole cation, a piperidine cation, a pyrazole cation, and an oxazole cation, and at least one of oxalate anion, acetate anion, salicylate anion, sulfosalicylate anion, citrate anion, and tartrate anion.

[0028] The desulfurizer provided by the present application is a mixture, which comprises a first complexing agent-iron complex, a second complexing agent-iron complex, and an ionic liquid. The first complexing agent-iron complex is a complex formed by the complexation of a first complexing agent with iron, and the second complexing agent-iron complex is a complex formed by the complexation of a second complexing agent with iron. In the present application, the first complexing agent is EDTA, and the second complexing agent is selected from at least one of HEDTA, citric acid, salicylic acid, sulfosalicylic acid, and tartaric acid.

[0029] The complex of iron realizes deep desulfurization of fuel gas on the premise of ensuring that the solution contains sufficient Fe 3 + in complex form, and the Fe 3+ in complex form can exist stably. The Fe 3+ in complex form can effectively oxidize sulfur elements in sulfur-containing compounds, thereby achieving the effect of desulfurization. The first complexing agent and the second complexing agent can form a composite complexing agent system to form a stable iron complex with a soluble iron salt, thereby maintaining strong oxidizing properties, thereby having strong desulfurization effect.

[0030] The present application does not limit the preparation method of the first complexing agent-iron complex and the second complexing agent-iron complex, and the complex satisfying the above requirements can be prepared. In an embodiment, at least one of ferric ammonium sulfate and ferrous ammonium sulfate is used to react with the first complexing agent and the second complexing agent respectively to obtain the above complex. The ammonium ion in the ferric ammonium sulfate and the ferrous ammonium sulfate can promote the formation of stable complex of iron salt and complexing agent, so that the desulfurizer has a higher total sulfur removal rate.

[0031] The ionic liquid is a salt in liquid state at room temperature, which is composed of cation and anion. In the ionic liquid used in the present application, the cation is selected from at least one of substituted or unsubstituted imidazole cation, pyridine cation, thiazole cation, piperidine cation, pyrazole cation and oxazole cation, i.e. the imidazole cation, pyridine cation, thiazole cation, piperidine cation, pyrazole cation and oxazole cation can be in substituted or unsubstituted form. The cation with the above characteristics can have a benzene carboxyl group, a p-toluene sulfonic acid group, a hydroxyalkyl group (carbon number 1-4), a cyano group, a phenolic hydroxyl group and a quinone group, etc. introduced into the molecular skeleton thereof to form a functional ionic liquid. The benzene carboxyl group, the p-toluene sulfonic acid group, the hydroxyalkyl group (carbon number 1-4), the cyano group can react with the hydroxyl radicals generated in the regeneration process of the complexed iron to play a role in scavenging the hydroxyl radicals, thereby effectively inhibiting the degradation of the complexed iron and improving the stability of the complexed iron; the phenolic hydroxyl group and the quinone group can improve the oxygen carrying capacity of the functional ionic liquid in the regeneration process of the complexed iron and effectively improve the regeneration efficiency of the complexed iron. Therefore, the functional ionic liquid with the above cation structure can make the desulfurizer provided by the present application have good chemical stability and oxidation regeneration capacity.

[0032] Further, the ionic liquid used in the present application further includes at least one of oxalate anion, acetate anion, salicylate anion, sulfosalicylate anion, citrate anion and tartrate anion. The ionic liquid with the above anion has high polarizability and weak coordination ability, good solubility and stable activation effect on transition metal complexes, thereby effectively improving the solubility of the first complexing agent-iron complex and the second complexing agent-iron complex and greatly increasing the effective concentration of the complexed iron in the desulfurizer compared with the prior art.

[0033] It can be understood that, since the iron element complex can stably exist in the aqueous phase, in an embodiment, the desulfurizer provided by the present application includes water. Since the ionic liquid itself has high viscosity, and after the ionic liquid forms a mixed system with water, the nanomicrostructure of the ionic liquid is changed through the van der Waals force, hydrogen bond and other effects between the water molecules and the anions of the ionic liquid, thereby effectively reducing the viscosity of the ionic liquid, improving the mass transfer efficiency of the sulfur-containing compounds in the iron complex-ionic liquid mixed system, and enhancing the deep desulfurization effect of the fuel gas.

[0034] The desulfurizer provided by the present application uses iron complexes to cooperate with ionic liquids, which improves the stability of the iron complexes and reduces the liquid viscosity of the desulfurizer, so that the desulfurizer can maintain strong oxidizability and has high mass transfer efficiency, thereby having the characteristics of high total sulfur removal efficiency.

[0035] In one embodiment, the substituents of the cation in the ionic liquid used by the desulfurizer provided by the present application are at least one of benzoic acid group, p-toluene sulfonic acid group, C1-C4 hydroxyalkyl group and cyano group.

[0036] When the cation in the ionic liquid used by the desulfurizer is at least one of imidazole cation with substituents, pyridine cation, thiazole cation, piperidine cation, pyrazole cation and oxazole cation, the above-mentioned cation can have at least one of benzoic acid group, p-toluene sulfonic acid group, C1-C4 hydroxyalkyl group and cyano substituent. The C1-C4 hydroxyalkyl group is an alkyl group including at least one alcohol hydroxyl group, and the number of carbon atoms of the alkyl group is 1-4, which can be a linear alkyl group or a branched alkyl group. Further, the present application does not limit the number and substitution position of the above-mentioned substituents, and the types of substituents meet the above-mentioned requirements.

[0037] After the iron complexes including ferric iron oxidize the sulfur-containing compounds, the iron complexes are reduced to ferrous iron, and need to be regenerated to ferric iron by oxidation for reuse. In the regeneration process of the complex iron, hydrogen peroxide is generated from oxygen and water in the presence of ferrous iron, and further Fenton reaction generates hydroxyl radicals. Due to the strong oxidation of the hydroxyl radicals, the iron complexes are easily degraded, thereby reducing the desulfurization effect of the desulfurizer. The benzoic acid group, p-toluene sulfonic acid group, hydroxyalkyl group and cyano substituent of the cation in the ionic liquid can effectively scavenge the hydroxyl radicals; at the same time, the benzoic acid group and the p-toluene sulfonic acid group react with the hydroxyl radicals to generate chelates, and the generated chelates can re-form complexes with the metal ions released from the degradation of the iron complexes, thereby effectively weakening the oxidative degradation of the iron complexes, so that the desulfurizer provided by the present application has the characteristics of long service life.

[0038] In one embodiment, the substituents of the cation in the ionic liquid include at least one of phenolic hydroxyl group and quinone group. In the regeneration process of the desulfurizer, the phenolic hydroxyl group and the quinone group on the cation skeleton have the function of carrying oxygen, which can effectively improve the mass transfer efficiency of oxygen molecules in the regeneration process. Therefore, the desulfurizer including the above-mentioned substituents has the advantage of high regeneration efficiency.

[0039] It can be understood that the cation in the ionic liquid used in the desulfurizer provided by the present application can be selected from at least one of imidazole cation, pyridine cation, thiazole cation, piperidine cation, pyrazole cation and oxazole cation, and each of the above cations can independently have or not have a substituent group. When the above cation has a substituent group, the present application does not limit the number, type and substitution position of the substituent group. For example, in an embodiment, the cation in the ionic liquid is a pyridine cation having a substituent group, and the substituent group is a cyano group and a quinone group.

[0040] The regeneration method of the desulfurizer is not limited in the present application, and a commonly used regeneration method in the art can be used to oxidize at least part of the divalent iron in the desulfurizer to trivalent iron. In an embodiment, the following regeneration method is used: using a pressurized supergravity device, under the conditions of a supergravity factor of 80-120, a temperature of 20-30°C, and an oxygen pressure of 0.3-0.5 MPa, oxygen is reacted with the complex iron solution to be regenerated in a supergravity reactor for 2-3 h.

[0041] Compared with the conventional method, the advantage of this regeneration method is that the mass transfer driving force of oxygen can be effectively improved under pressure conditions, and the mass transfer efficiency of oxygen and the complex iron solution can be further improved by combining with the pressurized supergravity device, thereby improving the oxidation regeneration capacity of the complex iron.

[0042] In an embodiment, the first complexing agent-iron complex and the second complexing agent-iron complex respectively include divalent iron and trivalent iron, and the molar ratio of divalent iron to trivalent iron is 1:3-1:5.

[0043] When the first complexing agent-iron complex and the second complexing agent-iron complex respectively include divalent iron and trivalent iron, the total sulfur removal effect of the desulfurizer provided by the present application is better. The inventors speculate that the reason may be that the presence of divalent iron and trivalent iron in the system at the same time can improve the redox potential of the desulfurizer, so that it has stronger oxidizing property, and thus the total sulfur removal effect is better. Further, controlling the molar ratio of divalent iron to trivalent iron to be 1:3-1:5 can further enhance the total sulfur removal effect of the desulfurizer.

[0044] In an embodiment, the molar ratio of the first complexing agent to the second complexing agent is 1:3-1:5. Controlling the first complexing agent and the second complexing agent to be in the above ratio can further increase the stability of the iron complex, so that the total sulfur removal rate of the desulfurizer provided by the present application is further improved; further, controlling the molar ratio of the sum of the amounts of substance of the iron element and the first complexing agent and the second complexing agent to be 1:1.1-1:1.3 can further improve the total sulfur removal rate of the desulfurizer.

[0045] In one embodiment, the desulfurizer provided by the present application comprises, in terms of mass percentage, 5-20 wt% of complexed iron, 20-60 wt% of ionic liquid, and 20-75 wt% of water.

[0046] Since the ionic liquid itself has a large viscosity, water can form a mixed system with the ionic liquid, and the microstructure of the ionic liquid can be changed by the Van der Waals force, hydrogen bond, and other interactions between water molecules and the anions of the ionic liquid, effectively reducing the viscosity of the ionic liquid, improving the mass transfer efficiency of the sulfur-containing compounds in the iron complex-ionic liquid mixed system, and improving the total sulfur removal rate of the desulfurizer.

[0047] The present application does not limit the preparation method of the desulfurizer, and any of the above desulfurizers can be prepared. In one embodiment, the desulfurizer is prepared by using the following method:

[0048] First, the soluble iron salt, the first complexing agent, the second complexing agent, and a certain proportion of water are mixed at 20-30°C, the stirring speed is controlled to be 80-120 r / min, an aqueous solution of iron complex is formed, and the pH value of the solution is adjusted to 7.0-9.0 by using triethanolamine, sodium carbonate, etc.; then the ionic liquid and a certain proportion of water are mixed at 20-30°C, the stirring speed is controlled to be 80-120 r / min, an aqueous solution of ionic liquid is obtained; finally, the aqueous solution of iron complex and the aqueous solution of ionic liquid are fully mixed, the stirring speed is controlled to be 70-100 r / min, and the pH value of the mixed solution system is adjusted to 7.0-9.0 by using triethanolamine, sodium carbonate, etc., to obtain a homogeneous and stable composite desulfurizer.

[0049] The second aspect of the present application provides a method for removing sulfur-containing compounds, which comprises contacting any of the above desulfurizers with a to-be-treated substance to perform desulfurization treatment. Since the desulfurizer provided by the present application has a high total sulfur removal rate, and the desulfurization can be completed by contacting the desulfurizer with the to-be-treated substance, the method for removing sulfur-containing compounds provided by the present application has the characteristics of simple operation and high desulfurization efficiency when the desulfurizer is used to remove sulfur-containing compounds.

[0050] Further, in one embodiment, the liquid-gas ratio of the desulfurization treatment is 15-20 L / m 3 , and the treatment temperature is 20-30°C. In this embodiment, the to-be-treated substance of the desulfurization treatment is fuel gas containing sulfur-containing compounds, and the liquid-gas ratio is the volume ratio of the desulfurizer to the fuel gas. Using the above liquid-gas ratio can make the method for removing sulfur-containing compounds provided by the present application have a higher total sulfur removal rate.

[0051] In one embodiment, the method for removing sulfur-containing compounds provided by the present application comprises contacting the desulfurizer with the to-be-treated substance in a high-gravity rotating packed bed to perform desulfurization treatment.

[0052] Figure 1 The structure diagram of the supergravity rotating packed bed, the process of contacting the desulfurizer with the to-be-treated substance in the supergravity rotating packed bed includes: introducing the fuel gas into the supergravity rotating packed bed from the gas inlet at the lower part of the supergravity rotating packed bed by a blower, introducing the desulfurizer into the supergravity rotating packed bed from the liquid inlet at the upper part of the supergravity rotating packed bed, under the action of centrifugal force, the desulfurizer is distributed on the surface of the packing along the radial direction of the rotating packed bed, the fuel gas is contacted with the desulfurizer on the surface of the packing in countercurrent to carry out gas-liquid mass transfer, the sulfur compounds in the fuel gas are selectively absorbed by the desulfurizer, and the treated fuel gas is discharged through the gas outlet of the supergravity rotating packed bed.

[0053] The present application does not limit the type of packing used in the supergravity rotating packed bed, nor the supergravity factor (i.e. the operating acceleration of the supergravity rotating packed bed) of the supergravity rotating packed bed. In one embodiment, stainless steel wire mesh or stainless steel corrugated plate is used as the packing, the specific surface area of the packing is 1100-1200 m 2 / m 3 , and the supergravity factor is 140-220. When the contacting process meets the above conditions, the method for removing sulfur compounds provided by the present application has a higher total sulfur removal rate.

[0054] The desulfurizer and its application provided by the present application are further described below through examples.

[0055] Example 1

[0056] In this embodiment, the desulfurizer is prepared by the following method:

[0057] 1) Mix 195.51 g of NH4Fe(SO4)2, 69.58 g of (NH4)2Fe(SO4)2, 78.9 g of EDTA, 155.62 g of citric acid and 3.0 kg of deionized water to obtain a first mixed solution;

[0058] 2) Mix 2.0 kg of functional ionic liquid (the cation skeleton is imidazole, the cation functional group is benzoic acid group and phenolic hydroxyl group, and the anion is citrate, and the structure of the anion and the cation is shown as formula 1) and 4.5 kg of deionized water to obtain a second mixed solution;

[0059]

[0060] 3) Mix the first mixed solution and the second mixed solution to obtain a desulfurizer A1;

[0061] The pH value of the desulfurizer is measured to be 7.0.

[0062] Example 2

[0063] In this embodiment, the desulfurizer is prepared by the following method:

[0064] 1) 421.74 g of NH4Fe(S04)2, 128.65 g of (NH4)2Fe(S04)2, 155.18 g of EDTA, 293.32 g of salicylic acid and 2.7 kg of deionized water were mixed to obtain a first mixed solution;

[0065] 2) 3.0 kg of functional ionic liquid (the cation skeleton is thiazole, the cation functional group is p-toluenesulfonic acid group and phenolic hydroxyl, and the anion is salicylate, and the structure of the anion and the cation is shown in formula 2) and 3.3 kg of deionized water were mixed to obtain a second mixed solution;

[0066]

[0067] 3) The first mixed solution and the second mixed solution were mixed to obtain a desulfurizer A2;

[0068] The pH value of the desulfurizer was measured to be 7.5.

[0069] Example 3

[0070] The desulfurizer was prepared by using the following method:

[0071] 1) 730.97 g of NH4Fe(S04)2, 195.11 g of (NH4)2Fe(S04)2, 200.6 g of EDTA, 872.49 g of sulfosalicylic acid and 1.8 kg of deionized water were mixed to obtain a first mixed solution;

[0072] 2) 5.0 kg of functional ionic liquid (the cation skeleton is pyrazole, the cation functional group is hydroxyalkyl with a carbon number of 2 and quinone group, and the anion is sulfosalicylate, and the structure of the anion and the cation is shown in formula 3) and 1.2 kg of deionized water were mixed to obtain a second mixed solution;

[0073]

[0074] 3) The first mixed solution and the second mixed solution were mixed to obtain a desulfurizer A3;

[0075] The pH value of the desulfurizer was measured to be 8.6.

[0076] Example 4

[0077] The desulfurizer was prepared by using the following method:

[0078] 1) 515.91 g of NH4Fe(S04)2, 122.4 g of (NH4)2Fe(S04)2, 198.69 g of EDTA, 662.45 g of N-hydroxyethyl ethylenediamine tetraacetic acid (HEDTA) and 1.5 kg of deionized water were mixed to obtain a first mixed solution;

[0079] 2) 6.0 kg of functionalized ionic liquid (pyridine as the cation skeleton, cyano and quinone as the cation functional group, and acetate as the anion, and the structure of the anion and the cation is shown in formula 4) was mixed with 1.0 kg of deionized water to obtain a second mixed solution;

[0080]

[0081] The molar ratio of cation 1 to cation 2 is 1:1.

[0082] 3) The first mixed solution and the second mixed solution were mixed to obtain desulfurizer A4.

[0083] The pH value of the desulfurizer was measured to be 7.8.

[0084] Example 5

[0085] The desulfurizer was prepared by using the following method:

[0086] 1) 861.84 g of NH4Fe(SO4)2, 184.03 g of (NH4)2Fe(SO4)2, 226.8 g of EDTA, 524.88 g of tartaric acid, and 1.9 kg of deionized water were mixed to obtain a first mixed solution;

[0087] 2) 4.5 kg of functionalized ionic liquid (piperidine as the cation skeleton, benzoic acid and quinone as the cation functional group, and tartaric acid as the anion, and the structure of the anion and the cation is shown in formula 5) was mixed with 1.8 kg of deionized water to obtain a second mixed solution;

[0088]

[0089] The molar ratio of cation 1 to cation 2 is 1:1.

[0090] 3) The first mixed solution and the second mixed solution were mixed to obtain desulfurizer A5.

[0091] The pH value of the desulfurizer was measured to be 9.0.

[0092] Example 6

[0093] The desulfurizer was prepared by using the following method:

[0094] 1) 540.51 g of NH4Fe(SO4)2, 144.27 g of (NH4)2Fe(SO4)2, 177.8 g of EDTA, 336.29 g of salicylic acid, and 2.2 kg of deionized water were mixed to obtain a first mixed solution;

[0095] 2) 4.0 kg of functionalized ionic liquid (the cation skeleton is oxazole, the cation functional group is a hydroxyalkyl with a carbon number of 4 and a phenolic hydroxyl group, and the anion is salicylate, the structure of the anion and the cation is as shown in formula 6) is mixed with 2.6 kg of deionized water to obtain a second mixed solution;

[0096] Formula 6) and 2.6 kg of deionized water to obtain a second mixed solution;

[0097]

[0098] The molar ratio of cation 1 to cation 2 is 1:2;

[0099] 3) The first mixed solution and the second mixed solution are mixed to obtain a desulfurizer A6;

[0100] The pH value of the desulfurizer is measured to be 8.0.

[0101] Example 7

[0102] The desulfurizer is prepared by the following method:

[0103] 1) 699.58 g of NH4Fe(SO4)2, 149.38 g of (NH4)2Fe(SO4)2, 199.88 g of EDTA, 950.48 g of N-hydroxyethyl ethylenediaminetetraacetic acid (HEDTA) and 2.0 kg of deionized water are mixed to obtain a first mixed solution;

[0104] 2) 4.5 kg of functionalized ionic liquid (the cation skeleton is imidazole, the cation functional group is a cyano group and a phenolic hydroxyl group, and the anion is a sulfosalicylate, the structure of the anion and the cation is as shown in formula 7) is mixed with 1.5 kg of deionized water to obtain a second mixed solution;

[0105]

[0106] 3) The first mixed solution and the second mixed solution are mixed to obtain a desulfurizer A7;

[0107] The pH value of the desulfurizer is measured to be 8.5.

[0108] Example 8

[0109] This example is basically the same as Example 1, except that in step 1), 265.09 g of NH4Fe(SO4)2, 78.9 g of EDTA, 155.62 g of citric acid and 3.0 kg of deionized water are mixed to obtain a first mixed solution.

[0110] A desulfurizer A8 is prepared;

[0111] The pH value of the desulfurizer is measured to be 7.6.

[0112] Comparative Example 1

[0113] The comparative example is basically the same as example 1, except that the second mixed solution is not prepared, and the first mixed solution is used as the desulfurizer B1.

[0114] Comparative example 2

[0115] The comparative example is basically the same as example 1, except that in step 1), 195.51 g of NH4Fe(SO4)2, 69.58 g of (NH4)2Fe(SO4)2, 234.52 g of EDTA and 3.0 kg of deionized water are mixed to obtain the first mixed solution.

[0116] The desulfurizer B2 is prepared.

[0117] Comparative example 3

[0118] The comparative example is basically the same as example 1, except that in step 1), 195.51 g of NH4Fe(SO4)2, 69.58 g of (NH4)2Fe(SO4)2, 234.52 g of citric acid and 3.0 kg of deionized water are mixed to obtain the first mixed solution.

[0119] The desulfurizer B3 is prepared.

[0120] Test example

[0121] 1. The desulfurizer A1 is added to the liquid storage tank of the supergravity absorption device, and the supergravity absorption test device is controlled to simulate the fuel gas inlet amount of 20 m 3 / h, the supergravity factor of 140, the liquid-gas ratio of 20 L / m 3 , the absorption temperature of 15-25℃, and a variety of total sulfur content gas sources are used to carry out sulfur compound absorption test. The total sulfur removal rate is obtained by measuring the total sulfur concentration of the inlet and outlet gas, wherein the total sulfur removal rate = (inlet total sulfur-outlet total sulfur) / inlet total sulfur x 100%.

[0122] The total sulfur content in the gas is determined according to "Determination of Sulfur Compounds in Natural Gas-Part 8: Determination of Total Sulfur Content by Ultraviolet Fluorescence Photometry" (GB / T 11060.8-2012) and using a German Photon LAB TS total sulfur analyzer. The results of the simulated fuel gas absorption test are shown in Table 1.

[0123] Table 1

[0124]

[0125] 2. The desulfurizer A2 is added to the liquid storage tank of the supergravity absorption device, and the supergravity absorption test device is controlled to simulate the fuel gas inlet amount of 20 m 3 / h, the supergravity factor of 220, the liquid-gas ratio of 5 L / m 3, the total sulfur removal rate was obtained by measuring the total sulfur concentration of the inlet gas and the outlet gas, wherein the total sulfur removal rate = (total sulfur of inlet gas - total sulfur of outlet gas) / total sulfur of inlet gas x 100%, and the detection method was the same as that of Test Example 1.

[0126] The results of the simulated fuel gas absorption test are shown in Table 2.

[0127] Table 2

[0128]

[0129]

[0130] 3, Desulfurizer A3 was added to the liquid storage tank of the high gravity absorption device, the simulated fuel gas inlet amount of the high gravity absorption test device was controlled to be 20 m 3 / h, the high gravity factor was 160, the liquid-gas ratio was 30 L / m 3 , the absorption temperature was 20-30℃, and the sulfur compound absorption test was carried out using a gas source with multiple total sulfur contents. The total sulfur removal rate was obtained by measuring the total sulfur concentration of the inlet gas and the outlet gas, wherein the total sulfur removal rate = (total sulfur of inlet gas - total sulfur of outlet gas) / total sulfur of inlet gas x 100%, and the detection method was the same as that of Test Example 1.

[0131] The results of the simulated fuel gas absorption test are shown in Table 3.

[0132] Table 3

[0133]

[0134] 4, Desulfurizer A4 was added to the liquid storage tank of the high gravity absorption device, the simulated fuel gas inlet amount of the high gravity absorption test device was controlled to be 20 m 3 / h, the high gravity factor was 180, the liquid-gas ratio was 25 L / m 3 , the absorption temperature was 20-25℃, and the sulfur compound absorption test was carried out using a gas source with multiple total sulfur contents. The total sulfur removal rate was obtained by measuring the total sulfur concentration of the inlet gas and the outlet gas, wherein the total sulfur removal rate = (total sulfur of inlet gas - total sulfur of outlet gas) / total sulfur of inlet gas x 100%, and the detection method was the same as that of Test Example 1.

[0135] The results of the simulated fuel gas absorption test are shown in Table 4.

[0136] Table 4

[0137]

[0138]

[0139] 5, Add desulfurizer A5 to the liquid storage tank of the supergravity absorption device, control the supergravity absorption test device to simulate the fuel gas inlet amount of 20 m 3 / h, the supergravity factor is 210, the liquid-gas ratio is 18 L / m 3 , the absorption temperature is 20-35℃, use multiple gas sources with different total sulfur contents to perform sulfur compound absorption tests, obtain the total sulfur removal rate by measuring the total sulfur concentrations of the inlet and outlet gases, wherein the total sulfur removal rate = (inlet total sulfur - outlet total sulfur) / inlet total sulfur x 100%, and the detection method is the same as that in test example 1.

[0140] The simulation fuel gas absorption test results are shown in Table 5.

[0141] Table 5

[0142]

[0143] 6, Add desulfurizer A6 to the liquid storage tank of the supergravity absorption device, control the supergravity absorption test device to simulate the fuel gas inlet amount of 20 m 3 / h, the supergravity factor is 200, the liquid-gas ratio is 15 L / m 3 , the absorption temperature is 25-40℃, use multiple gas sources with different total sulfur contents to perform sulfur compound absorption tests, obtain the total sulfur removal rate by measuring the total sulfur concentrations of the inlet and outlet gases, wherein the total sulfur removal rate = (inlet total sulfur - outlet total sulfur) / inlet total sulfur x 100%, and the detection method is the same as that in test example 1.

[0144] The simulation fuel gas absorption test results are shown in Table 6.

[0145] Table 6

[0146]

[0147]

[0148] 7, Add desulfurizer A7 to the liquid storage tank of the supergravity absorption device, control the supergravity absorption test device to simulate the fuel gas inlet amount of 20 m 3 / h, the supergravity factor is 220, the liquid-gas ratio is 20 L / m 3 , the absorption temperature is 20-35℃, use multiple gas sources with different total sulfur contents to perform sulfur compound absorption tests, obtain the total sulfur removal rate by measuring the total sulfur concentrations of the inlet and outlet gases, wherein the total sulfur removal rate = (inlet total sulfur - outlet total sulfur) / inlet total sulfur x 100%, and the detection method is the same as that in test example 1.

[0149] The simulation fuel gas absorption test results are shown in Table 7.

[0150] Table 7

[0151]

[0152] 8. The total sulfur removal rate of the desulfurizer A8 was measured.

[0153] The experimental conditions and the measuring method were the same as those of Test Example 1.

[0154] The results of the simulated fuel gas absorption test are shown in Table 8.

[0155] Table 8

[0156]

[0157]

[0158] Test Example 9

[0159] The total sulfur removal rate of the desulfurizer B1 was measured.

[0160] The experimental conditions and the measuring method were the same as those of Test Example 1. The results of the simulated fuel gas absorption test are shown in Table 9.

[0161] Table 9

[0162]

[0163] Test Example 10

[0164] The total sulfur removal rate of the desulfurizer B2 was measured.

[0165] The experimental conditions and the measuring method were the same as those of Test Example 1. The results of the simulated fuel gas absorption test are shown in Table 10.

[0166] Table 10

[0167]

[0168] Test Example 11

[0169] The total sulfur removal rate of the desulfurizer B3 was measured.

[0170] The experimental conditions and the measuring method were the same as those of Test Example 1.

[0171] The results of the simulated fuel gas absorption test are shown in Table 11.

[0172] Table 11

[0173]

[0174] From Tables 1-11, it can be seen that the desulfurizers A1-A8 prepared in the present application have higher total sulfur removal rates than the desulfurizers B1-B3 in the sulfur compound absorption test. In addition, the total sulfur removal rate of A8 is lower than that of A1-A7, and the inventors speculate that the reason may be that when only trivalent iron exists in the desulfurizer A8 system, the redox potential of the desulfurizer is lower than when both divalent iron and trivalent iron exist, so the oxidizing property of the desulfurizer is slightly lower than that of A1-A7.

[0175] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, and not to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent substitutions for part or all of the technical features; and these modifications or substitutions do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A desulfurizer characterized by comprising: comprise a first complexing agent-iron complex, a second complexing agent-iron complex, an ionic liquid; the first complexing agent is EDTA; the second complexing agent is at least one selected from HEDTA, citric acid, salicylic acid, sulfosalicylic acid, and tartaric acid; the ionic liquid comprises at least one of substituted or unsubstituted imidazolium cation, pyridinium cation, thiazolium cation, piperidinium cation, pyrazolium cation, and oxazolium cation, and at least one of oxalate anion, acetate anion, salicylate anion, sulfosalicylate anion, citrate anion, and tartrate anion.

2. The desulfurizer according to claim 1, characterized by in the ionic liquid, the substituent of the cation comprises at least one of benzoic acid group, p-toluene sulfonic acid group, C1-C4 hydroxyalkyl group, and cyano group.

3. The desulfurizer according to claim 1 or 2, characterized by in the ionic liquid, the substituent of the cation comprises at least one of phenolic hydroxyl group and quinone group.

4. The desulfurizer according to any one of claims 1 to 3, characterized by, the first complexing agent-iron complex and the second complexing agent-iron complex each comprise divalent iron and trivalent iron, and the molar ratio of the divalent iron to the trivalent iron is 1:3-1:

5.

5. The desulfurizer according to any one of claims 1 to 4, characterized by, the molar ratio of the first complexing agent to the second complexing agent is 1:3-1:5; the molar ratio of the iron element to the sum of the amounts of the first complexing agent and the second complexing agent is 1:1.1-1:1.

3.

6. The desulfurizer according to any one of claims 1 to 5, characterized by, the desulfurizer comprises, in terms of mass percentage, 5-20wt% of complexing iron, 20-60wt% of ionic liquid, and 20-75wt% of water.

7. A method for removing sulfur-containing compounds, characterized by, contacting the desulfurizer of claims 1-6 with a material to be treated to perform desulfurization treatment.

8. The method of claim 7, wherein, The liquid-gas ratio of the desulfurization treatment is 15-20 L / m 3 The treatment temperature is 20-30℃.

9. The method according to claim 7 or 8, characterized in that, contacting the desulfurizer with the material to be treated in a high gravity rotating packed bed to perform desulfurization treatment.

10. The method of claim 9, wherein, The super gravity rotating packed bed, wherein the packing is stainless steel wire mesh or stainless steel corrugated plate, the specific surface area of the packing is 1100-1200 m 2 / m 3 ; the super gravity factor of the super gravity rotating packed bed is 140-220.

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