Resin substrate-based iron oxyhydroxide desulfurizing agent and preparation method therefor

Abstract

The present invention relates to the technical field of gas purification treatment. Disclosed are a resin substrate-based iron oxyhydroxide desulfurizing agent and a preparation method therefor. In the present invention, sodium percarbonate is used as a raw material to prepare iron oxyhydroxide, wherein the sodium percarbonate has the effect of an alkaline precipitant, and also has the effect of an oxidizing agent; a linear phenolic resin is formed by condensation polymerization of p-aminophenol and formaldehyde, then the linear phenolic resin is modified by using terephthalyl alcohol, and a resin of a cross-linked network structure is formed by means of connection; and the resin is used as a substrate, so that the resin substrate-based iron oxyhydroxide desulfurizing agent is obtained. The present invention involves a simple preparation method, involves great sulfur capacity and desulfurization efficiency, and can be used for removing hydrogen sulfide in waste gas.

Description

A resin-based iron oxyhydroxide desulfurizer and preparation method thereof Technical Field

[0001] The invention belongs to the technical field of gas purification and treatment, and in particular relates to a resin-based iron oxyhydroxide desulfurizer and a preparation method thereof. Background Art

[0002] Hydrogen sulfide, present in the production of chemical raw materials from coal and petroleum, and during oil refining, can poison and deactivate catalysts in subsequent processes. Many industrial waste gases also contain significant amounts of hydrogen sulfide, and direct discharge can pollute the environment or cause poisoning in humans and animals. Existing high-sulfur-capacity desulfurizers, primarily iron oxyhydroxide desulfurizers, are widely used to remove sulfur-containing tail gases from natural gas, associated oilfield gas, coalbed methane, and biogas.

[0003] Patent CN106185988A discloses "a process for preparing high-specific-surface-area ferric oxyhydroxide and co-producing ammonium sulfate." This method uses solid ferrous sulfate and solid ammonium carbonate and / or solid ammonium bicarbonate as raw materials to react, and then oxidizes the filter cake after the reaction with hydrogen peroxide to produce ferric oxyhydroxide with a large specific surface area. The patent details the preparation methods of these desulfurizers.

[0004] Patent CN108516591A discloses a "high-surface-area iron oxyhydroxide desulfurizer and its preparation method." This method uses a ferrous salt solution and a precipitant as raw materials, supplemented with hydrogen peroxide and oxygen, and then extruded and dried to produce the desulfurizer. After the hydrogen peroxide is added dropwise, oxidation is continued through air for 2 to 5 hours.

[0005] The above two methods respectively involve adding hydrogen peroxide or hydrogen peroxide and air to oxidize rust, and then filtering, washing, and drying to produce ferric hydroxide. The traditional method for producing ferric hydroxide is divided into two units: (1) a neutralization unit, in which ferrous sulfate reacts with an alkaline precipitant such as sodium carbonate or ammonium bicarbonate to produce green rust; (2) an oxidation unit, in which green rust is converted into ferric hydroxide by adding hydrogen peroxide or blowing air. However, the traditional method has the following disadvantages: first, the traditional method is divided into two units, with high equipment investment and long process flow; second, hydrogen peroxide is used for oxidation, which poses a safety hazard during transportation; third, if air is used for oxidation, the oxidation time is long, which reduces the yield.

[0006] The adsorption capacity of single ferric hydroxide is limited, while adsorption resin is a type of porous, highly cross-linked polymer copolymer with a large specific surface area and pore sizes of varying sizes, which can be used for gas adsorption. Therefore, how to combine the two to develop a new ferric hydroxide desulfurizer is of great significance.

[0007] Summary of the Invention

[0008] To solve the above problems, the present invention aims to provide a resin-based iron oxyhydroxide desulfurizer and a preparation method thereof.

[0009] To achieve the above-mentioned purpose, the present invention is implemented through the following technical solutions:

[0010] A resin-based iron oxyhydroxide desulfurizer, wherein the iron oxyhydroxide is added to the resin base, and the mass ratio of the iron oxyhydroxide to the resin is 40-80:5-10;

[0011] The resin is a linear phenolic resin formed by polycondensation of p-aminophenol and formaldehyde, which is then modified by p-phenylenediol to form a cross-linked network structure.

[0012] The iron oxyhydroxide is prepared according to the following method:

[0013] (1) Preparing a precipitant solution: adding the precipitant to water and mixing uniformly at 35-40° C. to obtain a precipitant solution;

[0014] The precipitant is a mixture of sodium percarbonate and sodium carbonate, wherein the molar ratio of sodium percarbonate to sodium carbonate is 1.1 to 1.3:1;

[0015] The concentration of the precipitant solution is 1.5 to 2.5 mol / L;

[0016] (2) preparing a ferrous salt solution: adding solid ferrous salt to water and mixing uniformly at 35-40° C. to obtain a ferrous salt solution;

[0017] The molar ratio of the solid ferrous salt to the precipitant in step (1) is 1:1 to 1.2;

[0018] The concentration of the ferrous salt solution is 0.5 to 0.8 mol / L;

[0019] (3) adding the precipitant solution prepared in step (1) dropwise to the ferrous salt solution prepared in step (2) at 35-40° C., and after the addition of the precipitant solution is complete, continuing aging for 1-3 hours to obtain a mixture;

[0020] (4) Filter the mixture obtained in step (3), wash the filter cake obtained with water 3 to 5 times, and dry it to obtain iron oxyhydroxide.

[0021] The solid ferrous salt in step (2) is one or both of ferrous sulfate heptahydrate and ferrous chloride.

[0022] The drying in step (4) is air-drying or drying at 60-90°C.

[0023] The resin is prepared according to the following method:

[0024] 1) adding 1 part of p-aminophenol, 0.55-0.7 parts of formaldehyde aqueous solution, and 0.01 parts of sulfuric acid to a reactor, heating and refluxing for 1.5 hours, adding 2-3 parts of water after the reaction is complete, separating the aqueous phase, and continuing to heat to 150° C., evacuating to 0.05-0.1 MPa, and reacting for 1-2 hours to obtain a phenolic resin;

[0025] 2) In parts by weight, 0.3-0.5 parts of the phenolic resin obtained in step 1), 1 part of terephthalic acid methanol, 3.8-4.5 parts of triphenylphosphine, and 3-3.5 parts of diisopropyl azodicarboxylate are added to 10-15 parts of tetrahydrofuran, stirred to dissolve, and then heated to 60-80° C. for reaction for 4-8 hours. After completion of the reaction, the solvent is removed by distillation under reduced pressure, and the resulting solid is washed 2-3 times with ethanol to obtain a resin.

[0026] The mass concentration of the formaldehyde aqueous solution in step 1) is 35-40%.

[0027] The method for preparing the resin-based iron oxyhydroxide desulfurizer comprises the following steps:

[0028] In parts by weight, 40 to 80 parts of ferric oxyhydroxide and 5 to 10 parts of resin are put into a reactor, 150 to 250 parts of water are added thereto, the mixture is heated to 50 to 60°C, and stirred for 2 to 3 hours. After stirring, the obtained mixture is filtered, and the obtained filter cake is dried at 90°C for 3 to 5 hours to obtain a resin-based ferric oxyhydroxide desulfurizer.

[0029] Compared with the prior art, the present invention has the following advantages:

[0030] The resin-based ferric oxyhydroxide desulfurizer of the present invention adopts sodium percarbonate as a raw material to prepare ferric oxyhydroxide. Sodium percarbonate has the functions of both an alkaline precipitant and an oxidant, and can combine two process units in the prior art into one unit, thereby reducing equipment investment and occupying a small area. In addition, sodium percarbonate, as a solid, is safer than hydrogen peroxide. Secondly, sodium percarbonate, as an oxidant, has a faster oxidation rate than air, and can significantly increase production.

[0031] The resin-based ferric oxyhydroxide desulfurizer of the present invention first forms a linear phenolic resin by polycondensation of p-aminophenol and formaldehyde, and then uses p-phenylenediol to modify the linear phenolic resin to form a resin with a cross-linked network structure. The resin prepared by the present invention has porosity and can be used for adsorbing hydrogen sulfide gas. At the same time, the resin contains amino groups and hydroxyl groups, which can react with hydrogen sulfide gas, thereby increasing the active sites for capturing hydrogen sulfide, thereby increasing the sulfur capacity and desulfurization efficiency of the resin-based ferric oxyhydroxide desulfurizer.

[0032] The resin-based iron oxyhydroxide desulfurizer of the present invention has a simple preparation method, and has a large sulfur capacity and desulfurization efficiency, and can be used for removing hydrogen sulfide in waste gas. DETAILED DESCRIPTION

[0033] In order to better understand the technical solutions of the present invention, the following is a further detailed description of the above content of the present invention through specific implementation methods in the form of examples. However, this should not be construed as limiting the scope of the above subject matter of the present invention to the following examples. All technologies implemented based on the above content of the present invention fall within the scope of the present invention.

[0034] Example 1

[0035] Preparation of iron oxyhydroxide:

[0036] (1) Add 0.25 kg of sodium percarbonate and 0.075 kg of sodium carbonate to 1 L of water and mix them at 35°C to obtain a precipitant solution;

[0037] (2) Add 0.42 kg of ferrous sulfate heptahydrate to 3 L of water and mix well at 35°C to obtain a ferrous salt solution;

[0038] (3) adding the precipitant solution dropwise to the ferrous salt solution at 35° C., and continuing aging for 1 h after the addition of the precipitant solution is complete to obtain a mixture;

[0039] (4) The obtained mixture was filtered, and the filter cake was washed with water three times and dried naturally to obtain iron oxyhydroxide.

[0040] Preparation of resin:

[0041] 1) 1 kg of p-aminophenol, 0.55 kg of a 40% formaldehyde aqueous solution, and 0.01 kg of sulfuric acid were added to a reactor and heated under reflux for 1.5 hours. After the reaction was complete, 2 kg of water was added, the aqueous phase was separated, and the temperature was further raised to 150° C., evacuated to 0.05 MPa, and reacted for 1 hour to obtain a phenolic resin;

[0042] 2) 0.3 kg of phenolic resin, 1 kg of terephthalic acid methanol, 3.8 kg of triphenylphosphine and 3 kg of diisopropyl azodicarboxylate were added to 10 kg of tetrahydrofuran, stirred and dissolved, and heated to 60°C for 4 hours. After the reaction, the solvent was removed by distillation under reduced pressure, and the obtained solid was washed twice with ethanol to obtain a resin.

[0043] Preparation of resin-based iron oxyhydroxide desulfurizer:

[0044] 4 kg of ferric oxyhydroxide and 0.5 kg of resin were put into a reactor, 15 kg of water was added thereto, heated to 50°C, and stirred for 2 hours. After the stirring was completed, the resulting mixture was filtered, and the resulting filter cake was dried at 90°C for 3 hours to obtain a resin-based ferric oxyhydroxide desulfurizer.

[0045] Example 2

[0046] Preparation of iron oxyhydroxide:

[0047] (1) 0.3 kg of sodium percarbonate and 0.091 kg of sodium carbonate were added to 1 L of water and mixed at 36°C to obtain a precipitant solution;

[0048] (2) Add 0.48 kg of ferrous sulfate heptahydrate to 3.1 L of water and mix well at 36°C to obtain a ferrous salt solution;

[0049] (3) adding the precipitant solution dropwise to the ferrous salt solution at 35° C., and continuing aging for 1.5 h after the addition of the precipitant solution is complete to obtain a mixture;

[0050] (4) The obtained mixture was filtered, and the filter cake was washed with water four times and dried at 60° C. to obtain iron oxyhydroxide.

[0051] Preparation of resin:

[0052] 1) 1 kg of p-aminophenol, 0.6 kg of a 38% aqueous formaldehyde solution, and 0.01 kg of sulfuric acid were added to a reactor and heated under reflux for 1.5 hours. After the reaction was complete, 2.2 kg of water was added, the aqueous phase was separated, and the temperature was further raised to 150° C., evacuated to 0.06 MPa, and reacted for 1.2 hours to obtain a phenolic resin;

[0053] 2) 0.35 kg of phenolic resin, 1 kg of terephthalic acid methanol, 4 kg of triphenylphosphine and 3.1 kg of diisopropyl azodicarboxylate were added to 11 kg of tetrahydrofuran, stirred and dissolved, and heated to 65°C for 5 hours. After the reaction, the solvent was removed by distillation under reduced pressure, and the obtained solid was washed twice with ethanol to obtain a resin.

[0054] Preparation of resin-based iron oxyhydroxide desulfurizer:

[0055] 5 kg of ferric oxyhydroxide and 0.6 kg of resin were put into a reactor, 18 kg of water was added thereto, heated to 55 ° C, and stirred for 2.2 hours. After the stirring was completed, the obtained mixture was filtered, and the obtained filter cake was dried at 90 ° C for 3.5 hours to obtain a resin-based ferric oxyhydroxide desulfurizer.

[0056] Example 3

[0057] Preparation of iron oxyhydroxide:

[0058] (1) 0.34 kg of sodium percarbonate and 0.095 kg of sodium carbonate were added to 1 L of water and mixed at 38°C to obtain a precipitant solution;

[0059] (2) Add 0.23 kg of ferrous chloride to 3 L of water and mix well at 38 °C to obtain a ferrous salt solution;

[0060] (3) adding the precipitant solution dropwise to the ferrous salt solution at 37°C, and continuing aging for 2 h after the addition of the precipitant solution is complete to obtain a mixture;

[0061] (4) The obtained mixture was filtered, and the filter cake was washed with water four times and dried at 70° C. to obtain iron oxyhydroxide.

[0062] Preparation of resin:

[0063] 1) adding 1 kg of p-aminophenol, 0.65 kg of a 36% aqueous formaldehyde solution, and 0.01 kg of sulfuric acid to a reactor, heating and refluxing for 1.5 hours, adding 2.5 kg of water after the reaction is complete, separating the aqueous phase, and continuing to heat to 150° C., evacuating to 0.07 MPa, and reacting for 1.5 hours to obtain a phenolic resin;

[0064] 2) 0.38 kg of phenolic resin, 1 kg of terephthalic acid methanol, 4.2 kg of triphenylphosphine and 3.3 kg of diisopropyl azodicarboxylate were added to 13 kg of tetrahydrofuran, stirred and dissolved, and heated to 70°C for reaction for 5.5 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and the obtained solid was washed three times with ethanol to obtain a resin.

[0065] Preparation of resin-based iron oxyhydroxide desulfurizer:

[0066] 6 kg of ferric oxyhydroxide and 0.75 kg of resin were put into a reactor, 20 kg of water was added thereto, heated to 55 ° C, and stirred for 2.5 hours. After the stirring was completed, the obtained mixture was filtered, and the obtained filter cake was dried at 90 ° C for 4 hours to obtain a resin-based ferric oxyhydroxide desulfurizer.

[0067] Example 4

[0068] Preparation of iron oxyhydroxide:

[0069] (1) 0.38 kg of sodium percarbonate and 0.11 kg of sodium carbonate were added to 1 L of water and mixed at 36°C to obtain a precipitant solution;

[0070] (2) Add 0.24 kg of ferrous chloride to 2.7 L of water and mix well at 38°C to obtain a ferrous salt solution;

[0071] (3) adding the precipitant solution dropwise to the ferrous salt solution at 37°C, and continuing aging for 2.5 hours after the addition of the precipitant solution is complete to obtain a mixture;

[0072] (4) The obtained mixture was filtered, and the filter cake was washed with water four times and dried at 80° C. to obtain iron oxyhydroxide.

[0073] Preparation of resin:

[0074] 1) 1 kg of p-aminophenol, 0.68 kg of a 36% aqueous formaldehyde solution, and 0.01 kg of sulfuric acid were added to a reactor and heated under reflux for 1.5 hours. After the reaction was complete, 2.8 kg of water was added, the aqueous phase was separated, and the temperature was further raised to 150° C., evacuated to 0.08 MPa, and reacted for 1.8 hours to obtain a phenolic resin;

[0075] 2) 0.45 kg of phenolic resin, 1 kg of terephthalic acid methanol, 4.4 kg of triphenylphosphine and 3.3 kg of diisopropyl azodicarboxylate were added to 14 kg of tetrahydrofuran, stirred and dissolved, and heated to 75°C for 6 hours. After the reaction, the solvent was removed by distillation under reduced pressure, and the obtained solid was washed with ethanol three times to obtain a resin.

[0076] Preparation of resin-based iron oxyhydroxide desulfurizer:

[0077] 7 kg of ferric oxyhydroxide and 0.8 kg of resin were put into a reactor, 22 kg of water was added thereto, heated to 58 ° C, and stirred for 2.8 hours. After the stirring was completed, the obtained mixture was filtered, and the obtained filter cake was dried at 90 ° C for 4.5 hours to obtain a resin-based ferric oxyhydroxide desulfurizer.

[0078] Example 5

[0079] Preparation of iron oxyhydroxide:

[0080] (1) 0.44 kg of sodium percarbonate and 0.12 kg of sodium carbonate were added to 1 L of water and mixed at 40° C. to obtain a precipitant solution;

[0081] (2) adding 0.58 kg of ferrous sulfate heptahydrate to 2.6 L of water and mixing uniformly at 40° C. to obtain a ferrous salt solution;

[0082] (3) adding the precipitant solution dropwise to the ferrous salt solution at 40° C., and continuing aging for 3 h after the addition of the precipitant solution is complete to obtain a mixture;

[0083] (4) The obtained mixture was filtered, and the filter cake was washed with water five times and dried at 90° C. to obtain iron oxyhydroxide.

[0084] Preparation of resin:

[0085] 1) 1 kg of p-aminophenol, 0.7 kg of a 35% aqueous formaldehyde solution, and 0.01 kg of sulfuric acid were added to a reactor and heated under reflux for 1.5 hours. After the reaction was complete, 3 kg of water was added, the aqueous phase was separated, and the temperature was further raised to 150° C., evacuated to 0.1 MPa, and reacted for 2 hours to obtain a phenolic resin;

[0086] 2) 0.5 kg of phenolic resin, 1 kg of terephthalic acid methanol, 4.5 kg of triphenylphosphine and 3.5 kg of diisopropyl azodicarboxylate were added to 15 kg of tetrahydrofuran, stirred and dissolved, and heated to 80° C. to react for 8 h. After the reaction was completed, the solvent was distilled off under reduced pressure, and the obtained solid was washed with ethanol three times to obtain a resin.

[0087] Preparation of resin-based iron oxyhydroxide desulfurizer:

[0088] 8 kg of ferric oxyhydroxide and 1 kg of resin were put into a reactor, 25 kg of water was added thereto, heated to 60°C, and stirred for 3 hours. After the stirring was completed, the obtained mixture was filtered, and the obtained filter cake was dried at 90°C for 5 hours to obtain a resin-based ferric oxyhydroxide desulfurizer.

[0089] Example 6

[0090] Preparation of iron oxyhydroxide:

[0091] (1) 0.41 kg of sodium percarbonate and 0.12 kg of sodium carbonate were added to 1 L of water and mixed at 35°C to obtain a precipitant solution;

[0092] (2) Add 0.7 kg of ferrous sulfate heptahydrate to 3.1 L of water and mix well at 40°C to obtain a ferrous salt solution;

[0093] (3) adding the precipitant solution dropwise to the ferrous salt solution at 40° C., and after the addition of the precipitant solution is complete, aging is continued for 1 h to obtain a mixture;

[0094] (4) The obtained mixture was filtered, and the filter cake was washed with water three times and dried naturally to obtain iron oxyhydroxide.

[0095] Preparation of resin:

[0096] 1) adding 1 kg of p-aminophenol, 0.55 kg of a 35% aqueous formaldehyde solution, and 0.01 kg of sulfuric acid to a reactor, heating and reflux reaction for 1.5 hours, adding 3 kg of water after the reaction is complete, separating the aqueous phase, and continuing to heat to 150° C., evacuating to 0.09 MPa, and reacting for 1 hour to obtain a phenolic resin;

[0097] 2) 0.4 kg of phenolic resin, 1 kg of terephthalic acid methanol, 3.8 kg of triphenylphosphine and 3.5 kg of diisopropyl azodicarboxylate were added to 15 kg of tetrahydrofuran, stirred and dissolved, and heated to 80° C. for 4 h. After the reaction, the solvent was removed by distillation under reduced pressure, and the obtained solid was washed with ethanol three times to obtain a resin.

[0098] Preparation of resin-based iron oxyhydroxide desulfurizer:

[0099] 4 kg of ferric oxyhydroxide and 1 kg of resin were put into a reactor, 20 kg of water was added thereto, heated to 50°C, and stirred for 3 hours. After the stirring was completed, the resulting mixture was filtered, and the resulting filter cake was dried at 90°C for 3.5 hours to obtain a resin-based ferric oxyhydroxide desulfurizer.

[0100] The iron oxyhydroxide prepared in Example 3 was used as a comparative example; the performance indicators of the resin-based iron oxyhydroxide desulfurizers prepared in Examples 1 to 6 and the iron oxyhydroxide of the comparative example were respectively tested, and the sulfur capacity test was carried out according to the method in HG / T 5759-2020 Normal Temperature Iron Oxide Desulfurizer. The results are shown in Table 1.

[0101] Table 1 Performance indicators of the products of the embodiments and comparative examples

[0102] It can be seen from the results in Table 1 that, due to the porosity of the resin and the adsorption of hydrogen sulfide, the resin-based iron oxyhydroxide desulfurizer prepared in the present invention has a larger sulfur capacity than a single iron oxyhydroxide desulfurizer.

[0103] In order to verify the desulfurization rate of the resin-based hydroxy iron oxide desulfurizer prepared by the present invention, the resin-based hydroxy iron oxide desulfurizer prepared in Examples 1 to 6 and the hydroxy iron oxide prepared in the comparative example were respectively tested for desulfurization rate in a micro fixed bed reactor. The size of the reactor was Φ10mm*12mm*300mm, the loading amount of the desulfurizer was 0.5g, and the upper and lower ends of the reactor were filled with quartz sand. A hydrogen sulfide and nitrogen mixer was used as a simulated raw gas, wherein the hydrogen sulfide content was 20mg / L. The hydrogen sulfide not removed by the desulfurizer was absorbed by the tail gas absorption liquid, and the hydrogen sulfide in the absorption liquid was detected every 5 minutes using the iodine method. When the concentration of the purified gas was 10% of the hydrogen sulfide gas concentration in the simulated raw gas, the desulfurizer was considered to have completely penetrated, the experiment was stopped, and its penetration time was recorded. The desulfurization rate was calculated based on the sulfur content in the absorption liquid after the adsorption was completed. The calculation formula is:

[0104] Where η is the desulfurization rate of the desulfurizer (%), V is the total gas volume (L), W H2Sis the hydrogen sulfide content in the sample gas (mg / L), C1 is the concentration of the I2 standard solution (mol / L), V1 is the volume of the I2 standard solution added (mL), C2 is the concentration of the Na2S2O3 standard solution (mol / L), V2 is the volume of the Na2S2O3 standard solution consumed during titration (mL), and 34 is the molar mass of hydrogen sulfide (g / mol). The desulfurization rate and breakthrough time test results are shown in Table 2.

[0105] Table 2 Desulfurization rate (η) of the products of the embodiments and comparative examples

[0106] It can be seen from the results in Table 2 that the resin-based iron oxyhydroxide desulfurizer prepared by the present invention has a higher desulfurization rate due to the capture of hydrogen sulfide by hydroxyl and amino groups in the resin, and the higher the sulfur capacity, the longer the penetration time and the greater the desulfurization efficiency.

[0107] Although the above describes the specific implementation methods of the present invention, it does not limit the scope of protection of the present invention. Based on the technical solution of the present invention, various modifications or variations that can be made by those skilled in the art without creative work are still within the scope of protection of the present invention.

Claims

1. A resin-based iron oxyhydroxide desulfurizer, characterized in that: Adding iron oxyhydroxide to a resin base, wherein the mass ratio of the iron oxyhydroxide to the resin is 40-80:5-10; The resin is prepared by polycondensing p-aminophenol and formaldehyde to form a linear phenolic resin, and then modifying the linear phenolic resin with p-phenylenediol.

2. The resin-based iron oxyhydroxide desulfurizer according to claim 1, characterized in that: The iron oxyhydroxide is prepared according to the following method: (1) preparing a precipitant solution: adding a precipitant into water and mixing uniformly at 35 to 40° C. to obtain a precipitant solution; The precipitant is a mixture of sodium percarbonate and sodium carbonate, wherein the molar ratio of sodium percarbonate to sodium carbonate is 1.1 to 1.3:1; The concentration of the precipitant solution is 1.5 to 2.5 mol / L; (2) preparing a ferrous salt solution: adding solid ferrous salt to water and mixing uniformly at 35-40° C. to obtain a ferrous salt solution; The molar ratio of the solid ferrous salt to the precipitant in step (1) is 1:1 to 1.2; The concentration of the ferrous salt solution is 0.5-0.8 mol / L; (3) adding the precipitant solution prepared in step (1) dropwise to the ferrous salt solution prepared in step (2) at 35 to 40° C., and after the precipitant solution is added, continuing aging for 1 to 3 hours to obtain a mixture; (4) filtering the mixture obtained in step (3), washing the filter cake obtained with water for 3 to 5 times, and drying to obtain iron oxyhydroxide.

3. The resin-based iron oxyhydroxide desulfurizer according to claim 2, characterized in that: The solid ferrous salt in step (2) is one or both of ferrous sulfate heptahydrate and ferrous chloride.

4. The resin-based iron oxyhydroxide desulfurizer according to claim 2, characterized in that: The drying in step (4) is air-drying or drying at 60-90°C.

5. The resin-based iron oxyhydroxide desulfurizer according to claim 1, characterized in that: The resin is prepared according to the following method: 1) In parts by weight, 1 part of p-aminophenol, 0.55-0.7 parts of formaldehyde aqueous solution and 0.01 parts of sulfuric acid are added to a reactor, heated under reflux for reaction for 1.5 hours, 2-3 parts of water are added after the reaction is completed, the aqueous phase is separated, the temperature is continued to be raised to 150° C., vacuumized to 0.05-0.1 MPa, and reacted for 1-2 hours to obtain a phenolic resin; 2) In parts by weight, 0.3-0.5 parts of the phenolic resin obtained in step 1), 1 part of terephthalic acid alcohol, 3.8-4.5 parts of triphenylphosphine and 3-3.5 parts of diisopropyl azodicarboxylate are added to 10-15 parts of tetrahydrofuran, stirred to dissolve, and then heated to 60-80° C. to react for 4-8 hours. After the reaction is completed, the solvent is removed by distillation under reduced pressure, and the obtained solid is washed with ethanol 2-3 times to obtain a resin.

6. The resin-based iron oxyhydroxide desulfurizer according to claim 5, characterized in that: The mass concentration of the formaldehyde aqueous solution in step 1) is 35-40%.

7. The method for preparing the resin-based iron oxyhydroxide desulfurizer according to claim 1, characterized in that: The following steps are involved: In parts by weight, 40 to 80 parts of oxyhydroxide iron and 5 to 10 parts of resin are put into a reactor, 150 to 250 parts of water are added thereto, the mixture is heated to 50 to 60°C, and stirred for 2 to 3 hours. After the stirring is completed, the obtained mixed liquid is filtered, and the obtained filter cake is dried at 90°C for 3 to 5 hours to obtain a resin-based oxyhydroxide iron desulfurizer.

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