CN112403481B - Modified coke oven gas hydrodesulfurization catalyst and preparation method thereof - Google Patents

Modified coke oven gas hydrodesulfurization catalyst and preparation method thereof Download PDF

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CN112403481B
CN112403481B CN202011249917.7A CN202011249917A CN112403481B CN 112403481 B CN112403481 B CN 112403481B CN 202011249917 A CN202011249917 A CN 202011249917A CN 112403481 B CN112403481 B CN 112403481B
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catalyst
femo
coke oven
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oven gas
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陈嘉梁
岑旭江
郭利鑫
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Ningbo Fareasttech Catalyst Engineering Co ltd
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    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J23/85—Chromium, molybdenum or tungsten
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract

The invention discloses a modified coke oven gas hydrodesulfurization catalyst and a preparation method thereof. The catalyst comprises FeMo catalyst and [ DETA]Ac, wherein: the FeMo catalyst comprises the following raw materials in percentage by mass: fe2O3：2‑10%，MoO3: 5-20%, doped element oxide: 0.1-5%, and the balance of gamma-Al2O3(ii) a The doped element oxide is V2O5、Cr2O3Or CuO; said FeMo catalyst and said [ DETA]The mass ratio of Ac is (1-3) to 1. The modified coke oven gas hydrodesulfurization catalyst can realize the thiophene conversion rate of more than or equal to 43 percent at the temperature of 150-180 ℃, the reaction temperature is low, and the thiophene conversion rate is obviously improved.

Description

Modified coke oven gas hydrodesulfurization catalyst and preparation method thereof
Technical Field
The invention relates to a modified coke oven gas hydrodesulfurization catalyst and a preparation method thereof.
Background
During the coking process, coking coal forms coke in a coking chamber, and raw coke gas is discharged firstly. The raw coke oven gas is cooled and condensed, and the coal gas obtained by recovering coal tar, ammonia, crude benzene, hydrogen sulfide and hydrogen cyanide by using various absorbents is the purified coke oven gas (the coke oven gas for short).
The hydrogen, methane, carbon monoxide and the like in the coke oven gas are all recyclable chemical substances. Before recycling, harmful impurities contained in the coke oven gas must be removed. The impurities being predominantly H2S、COS、CS2Thiophene, thiol, thioether, HCN, NH3Naphthalene, benzene, tar, and the like. These impurities not only pollute the environment, but also can corrode equipment and block pipelines, which can lead to poisoning and deactivation of catalysts and adsorbents and influence the subsequent recycling process, especially sulfides in the catalysts and the adsorbents. The sulfide in the coke oven gas has very complex form and mainly contains H2S、COS、CS2And RSH, among which thiophene has high chemical stability and is one of the most difficult sulfides to be removed. Therefore, the problem of the desulfurization of the coke oven gas is the bottleneck of resource utilization andone of the research subjects.
The coke oven gas desulfurization technology comprises wet desulfurization and dry desulfurization, and the dry desulfurization commonly used in industry comprises an absorption method, a pyrolysis method, a hydrolysis method and a hydroconversion method. The hydro-conversion method has high conversion rate of organic sulfur, and particularly has better conversion capability on thiophene organic sulfur to convert the thiophene organic sulfur into H which is easy to remove2S, and then absorbing by using an adsorption desulfurizing agent.
The desulfurizer commonly used in the dry desulfurization process of the coke oven gas at present is Fe-Mo/gamma-Al2O3The hydrodesulfurization rate of the hydrogenation catalyst is only about 60 percent in the desulfurization process of the coke-oven gas, the use temperature is high (350-.
By the p-Fe-Mo/gamma-Al in the prior art2O3The hydrogenation catalyst is doped and modified to obtain a catalyst with better catalytic performance, and although the doping of Mn, Zn, Co and Ni can improve the activity of the catalyst, the doping of V, Cr, Cu and other elements can reduce the activity of the catalyst.
Therefore, how to further expand Fe-Mo/γ -Al2O3The kind of hydrogenation catalyst can effectively improve the efficiency of removing organic sulfur in coke oven gas when V, Cr and Cu are doped, and is a technical problem to be solved in the field.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art that the elements such as V, Cr, Cu and the like are doped with Fe-Mo/gamma-Al2O3Hydrogenation catalyst thiophene low conversion rate, and provides a modified coke oven gas hydrodesulfurization catalyst and a preparation method thereof.
The invention provides a modified coke oven gas hydrodesulfurization catalyst, which comprises a FeMo catalyst and [ DETA ] Ac, wherein:
the FeMo catalyst comprises the following raw materials in percentage by mass:
Fe2O3：2-10％，MoO3: 5-20%, doped element oxide: 0.1-5%, and the balance of gamma-Al2O3(ii) a The doped element oxide isV2O5、Cr2O3Or CuO;
the mass ratio of the FeMo catalyst to the [ DETA ] Ac is (1-3) to 1.
In the present invention, preferably, the Fe2O3Is in the range of 2.0 to 5.0%, for example 3.0%, percent referring to mass percent in the FeMo catalyst.
In the present invention, preferably, the MoO3Is in the range of 5.0 to 10.0%, for example 9.0%, by mass in the FeMo catalyst.
In the present invention, it is preferable that the content of the doping element oxide is 0.1 to 1.0%, for example, 0.3%, 0.6% or 0.9%, which means a mass percentage in the FeMo catalyst.
In the present invention, preferably, the doping element oxide is V2O5Or CuO.
In the present invention, preferably, the FeMo catalyst comprises the following raw materials: fe2O3：2.0-5.0％，MoO3: 5.0-10.0%, doped element oxide: 0.1 to 1.0 percent of the total weight of the alloy, and the balance of gamma-Al2O3The percentage refers to the mass percentage in the FeMo catalyst.
In the present invention, preferably, the FeMo catalyst is prepared by the following method:
(1) subjecting said Fe to2O3The precursor raw material of (1), the MoO3Dissolving the precursor raw material of (A) and the precursor raw material of the doped element oxide in water to obtain a mixed solution A;
(2) mixing the mixed solution A and gamma-Al2O3Mixing, soaking, oven drying, and calcining.
In the step (1), the Fe2O3The precursor starting material of (b) may be any material conventional in the art capable of being converted to Fe2O3For example, ferric nitrate.
In step (1), the MoO3The precursor feedstock of (a) may be any conventional in the art capable of being converted to MoO3For example ammonium molybdate.
In the step (1), when the doped element oxide is V2O5When said V is2O5The precursor material of (b) may be ammonium metavanadate.
In the step (1), when the doped element oxide is Cr2O3When said Cr is present2O3The precursor raw material of (b) may be chromium nitrate.
In the step (1), when the doping element oxide is CuO, a precursor material of the CuO may be copper nitrate.
In step (1), the dissolution of each precursor raw material may be promoted by adding a pH adjuster, for example, an acid. The acid may be an inorganic acid such as one or more of sulphuric acid, nitric acid, phosphoric acid, hydrochloric acid, oxalic acid, citric acid and boric acid, for example citric acid.
In the step (2), the mixed solution A can be aged for 2-4h and then is mixed with gamma-Al2O3And (4) mixing and dipping.
In step (2), the time for the impregnation may be 5 to 15 hours, for example 10 hours.
In the step (2), the temperature for drying may be 100-150 ℃, for example, 120 ℃.
In the step (2), the drying time may be 1 to 5 hours, for example, 2 hours.
In step (2), the temperature of the calcination may be 350-500 ℃, for example, 500 ℃.
In step (2), the calcination time may be 2 to 5 hours, for example, 3 hours.
In the present invention, preferably, the mass ratio of the FeMo catalyst to the [ DETA ] Ac is 3:1, 1:1 or 2: 1.
In the present invention, preferably, the [ DETA ] Ac is prepared by the following method:
1) reacting diethylenetriamine with acid to obtain diethylenetriamine salt;
2) reacting the diethylenetriamine salt in the step 1) with anhydrous acetate solid to obtain the [ DETA ] Ac.
In step 1), the acid may be hydrochloric acid.
In step 1), the acid may be added dropwise, for example, 0.5 mol/h.
In step 1), the temperature of the reaction may be 20 to 30 ℃, for example 25 ℃.
In step 1), the reaction time may be 5 to 8 hours, for example 4 hours.
In the step 2), the anhydrous acetate can be anhydrous sodium acetate.
In step 2), the temperature of the reaction may be 20 to 30 ℃, for example 25 ℃.
In step 2), the reaction time may be 12 to 36 hours, for example, 24 hours.
In step 2), the [ DETA ] Ac may be further subjected to post-treatment conventional in the art to remove moisture, for example, rotary steaming and drying the [ DETA ] Ac.
Wherein the time of the rotary evaporation can be 2-5 hours, such as 3 hours.
Wherein the drying temperature may be 50-80 ℃, e.g. 70 ℃.
Wherein the drying time may be 24-48 hours, such as 48 hours.
The invention also provides a preparation method of the modified coke oven gas hydrodesulfurization catalyst, which comprises the following steps: and mixing the FeMo catalyst and the [ DETA ] Ac.
Wherein the FeMo catalyst can be crushed and then mixed with the [ DETA ] Ac. The crushing can be to 20-40 mesh.
The positive progress effects of the invention are as follows:
the modified coke oven gas hydrodesulfurization catalyst can realize the thiophene conversion rate of more than or equal to 43 percent at the temperature of 150 ℃ and 180 ℃, the reaction temperature is low, and the thiophene conversion rate is obviously improved.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples and comparative examples:
ammonium molybdate (AR): chemical agents of the national drug group, ltd;
iron nitrate (AR): national chemical testing, ltd;
citric Acid (AR): shanghai reagent factory I;
ammonium metavanadate (AR): national chemical group chemical agents, ltd;
chromium nitrate (AR): national chemical group chemical agents, ltd;
cobalt nitrate (AR): national chemical group chemical agents, ltd;
copper nitrate (AR): beijing chemical plant;
spherical gamma-Al2O3(industrial grade): provided by Wuhan Kelin Fine chemical Co., Ltd;
carbon disulfide (AR): national chemical testing, ltd;
thiophene (AR): national chemical testing company;
H2、N2、O2(pureness): wuhan City Xiangyun industry and trade company Limited.
Example 1 FeVMo/γ -Al2O3Preparation of (2)
According to the proportion shown in table 1, ammonium molybdate and proper amount of citric acid (pH is adjusted to 3-5) are taken to be dissolved in deionized water, ammonium metavanadate is added, a certain amount of ferric nitrate is added after stirring and dissolving, the solution is aged for 2-4h, and then the dried spherical gamma-Al is added2O3Adding the carrier, soaking for 10h, drying at 120 ℃ for 2h, and roasting at 500 ℃ for 3h to obtain the catalyst FeVMo/gamma-Al2O3. Catalyst FeVMo/gamma-Al2O3The compositions of (A) are shown in Table 1 below.
TABLE 1
Figure BDA0002769080850000051
Example 2 FeCrMo/gamma-Al2O3Preparation of
According to the proportion shown in table 2, ammonium molybdate and a proper amount of citric acid are taken to be dissolved in deionized water, chromium nitrate is added, a certain amount of ferric nitrate is added after stirring and dissolving, the solution is aged for 2-4h, and then the dried spherical iron nitrate is addedγ-Al2O3Adding a carrier, soaking for 10h, drying at 120 ℃ for 2h, and roasting at 500 ℃ for 3h to obtain a catalyst FeCrMo/gamma-Al2O3. Catalyst FeCrMo/gamma-Al2The composition of O is shown in Table 2 below.
TABLE 2
Figure BDA0002769080850000052
Example 3 FeCuMo/gamma-Al2O3Preparation of
According to the proportion shown in table 3, ammonium molybdate and a proper amount of citric acid are taken to be dissolved in deionized water, copper nitrate is added, a certain amount of ferric nitrate is added after stirring and dissolving, the solution is aged for 2-4h, and then dried spherical gamma-Al is added2O3Adding a carrier, soaking for 10h, drying at 120 ℃ for 2h, and roasting at 500 ℃ for 3h to obtain a catalyst FeCuMo/gamma-Al2O3. Catalyst FeCuMo/gamma-Al2The composition of O is shown in Table 3 below.
TABLE 3
Figure BDA0002769080850000061
Comparative example 1 FeCoMo/gamma-Al2O3Preparation of
According to the proportion shown in table 4, ammonium molybdate and a proper amount of citric acid are taken to be dissolved in deionized water, cobalt nitrate is added, a certain amount of ferric nitrate is added after stirring and dissolving, the solution is aged for 2-4h, and then dried spherical gamma-Al is added2O3Adding a carrier, soaking for 10h, drying at 120 ℃ for 2h, and roasting at 500 ℃ for 3h to obtain a catalyst FeCoMo/gamma-Al2O3. Catalyst FeCoMo/gamma-Al2The composition of O is shown in Table 4 below.
TABLE 4
Figure BDA0002769080850000062
Example 4 preparation of [ DETA ] Ac
Taking a three-neck flask, adding 0.5mol of diethylenetriamine, placing the flask in a constant-temperature water bath kettle, and magnetically stirring for 30min under the ice-water bath condition; the left side of the three-neck flask is filled with nitrogen for protection, the middle part is connected with a spherical condenser pipe, the right side is connected with a dropping funnel filled with 0.5mol of hydrochloric acid, and the hydrochloric acid is dropwise added into the three-neck flask. Controlling the dropping speed to ensure that the hydrochloric acid is dropped for about 1 hour; then the temperature of the constant temperature water bath kettle is raised to 25 ℃, and the mixture is condensed and refluxed for reaction for 4 hours to obtain light yellow liquid, namely diethylenetriamine hydrochloride [ DETA ] Cl.
After obtaining [ DETA ] Cl, [ DETA ] Ac was obtained by continuing the following steps:
adding 0.5mol of anhydrous sodium acetate solid into the ionic liquid [ DETA ] C1, and reacting at 25 ℃ for 24h to obtain colorless transparent liquid and generate white precipitate NaCl; filtering under reduced pressure to remove solid NaC1, and performing rotary evaporation on the filtrate for 3h to remove water: and then putting the obtained liquid into a vacuum drying oven, and drying for 48 hours at 70 ℃ to obtain the ionic liquid [ DETA ] Ac.
Comparative example 2 preparation of [ DEA ] Ac
Adding 0.5mol of diethanolamine into a three-mouth flask containing 50mL of absolute ethanol, introducing nitrogen into the left side of the three-mouth flask, and sealing the right outlet by a plastic packaging film; then 0.5mol of acetic acid solution is dripped into the three-neck flask through a dropping funnel, the dripping speed is controlled to ensure that the dripping is finished within about 1 hour, and the process is carried out under the condition of ice-water bath; then raising the temperature of the constant-temperature water bath kettle to 50 ℃, and magnetically stirring for 12 hours at the temperature; followed by rotary evaporation of the resulting liquid to remove ethanol and most of the water; and finally, drying the liquid in a vacuum drying oven at 70 ℃ for 48 hours to obtain the [ DEA ] Ac ionic liquid, wherein the obtained product is yellow viscous liquid.
Comparative example 3 TEAH. FeCl4Preparation of (2)
Weighing 0.5mol of triethylamine hydrochloride and 0.25mol of anhydrous ferric chloride solid, directly mixing in an open flask, stirring and reacting for 4 hours at 70 ℃ to obtain uniform brown viscous liquid, namely TEAH & FeCl4。
Example 5
The catalysts prepared in examples 1 to 3 and comparative example 1 were crushed to 20 to 40 mesh and mixed with the ionic liquids prepared in example 4 and comparative examples 2 to 3 in the proportions shown in Table 5 to obtain modified catalysts.
TABLE 5
Figure BDA0002769080850000081
Note: denotes a comparative catalyst; the dosage percentage refers to the mass percentage.
Effect example 1
The catalyst evaluation system comprises three parts, namely a gas source, a reactor and a detection device.
The gas source is prepared raw material gas, the target sulfide is thiophene, the steel cylinder is evacuated by using vacuum oil pump, a certain quantity of thiophene is injected by using microinjector, then H is added2、N2Rushing into the vessel to a certain pressure, wherein H2Is 58% by volume, N2The volume fraction of (2) is 42%, the prepared raw material gas is placed for 2-3 days, and then the content of thiophene in the raw material gas is measured. Taking a certain amount of raw material gas with an injector, injecting into an ultraviolet fluorescence sulfur determinator (TEA-600S, Jiangsu liter Tuo precision instruments Co., Ltd.), detecting, introducing the sample for at least 3 times, averaging the analysis results, and obtaining the content of thiophene in the prepared raw material gas of 101.5mg/m3。
The catalytic reaction is carried out in a fixed bed reactor, the reactor is cylindrical, the height of the reactor is 700mm, the diameter of the reactor is 10mm, the material is temperature-resistant hard glass, and a sand core in the middle is used as a reaction bed. The reactor is arranged in a heating furnace, the heating furnace is a ceramic tube wound by a resistance wire, a thermocouple is arranged on the upper part of a catalyst bed layer for measuring temperature, and a KSY-1 type electric furnace temperature controller is used for controlling the temperature. The gas flow rate is regulated by a needle valve in the reaction process, the flowmeter is a self-made throttling flowmeter, the gas flow is displayed according to the height of a liquid column generated by the pressure difference of an inner pipe and an outer pipe, and the gas flow is calibrated by a soap film flowmeter before use. And absorbing the reacted gas with alkali liquor.
And detecting the reacted gas by using a trace sulfur analyzer and a gas chromatograph. The micro sulfur analyzer is MCGC-1B gas chromatography, TDX-108 chromatographic column, FPD flame photometric detector, S detection, and is manufactured by Wuhanjing environmental protection technology research Limited companyThe limit of measurement is 0.02mg/m3. The data workstation N2010 chromatography of Zhida information engineering Limited company of Zhejiang university is used for online. Before use, the standard gas containing thiophene is used for calibration.
3mL of the catalyst obtained in example 5 was each measured and placed in the reactor bed, and a thermocouple was inserted into the reactor bed at a position close to the surface of the catalyst. Firstly, nitrogen is introduced into the gas circuit, and experiments can be carried out after no leakage is determined. Bubbling hydrogen (flow 30mL/min) into the CS2Presulfurizing a catalyst for 6 hours at 180 ℃, switching nitrogen to purge a bed layer, simultaneously cooling, switching a feed gas when the temperature is reduced to 150 ℃, in order to approach the condition that industrial coke oven gas contains a certain amount of water vapor, feeding the feed gas into a reactor through a water saturator, sampling by using an injector after the reaction is stabilized for 2 hours, and using N2Diluting, and injecting into a trace sulfur analyzer for analysis.
The catalytic reaction conditions are as follows: 150 ℃ and 180 ℃, normal pressure, 100mL/min of raw material gas flow and 2000h of corresponding volume space velocity-1。
The hydrogenation activity of the catalyst is expressed as the conversion x of thiophene:
Figure BDA0002769080850000091
wherein C isInlet port、CAn outletThe respective concentrations of thiophene in the inlet and outlet gases of the reactor (mg/m)3)。
The results of the relevant performance tests of the catalysts are shown in table 6.
TABLE 6
Figure BDA0002769080850000101

Claims (10)

1. The modified coke oven gas hydrodesulfurization catalyst is characterized by comprising a FeMo catalyst and [ DETA ] Ac, wherein:
the FeMo catalyst comprises the following raw materials in percentage by mass:
Fe2O3：2-10%，MoO3: 5-20%, doped element oxide: 0.1-5%, and the balance of gamma-Al2O3(ii) a The doped element oxide is V2O5、Cr2O3Or CuO;
the mass ratio of the FeMo catalyst to the [ DETA ] Ac is (1-3) to 1;
the [ DETA ] Ac is prepared by the following method:
1) reacting diethylenetriamine with acid to obtain diethylenetriamine salt;
2) reacting the diethylenetriamine salt in the step 1) with anhydrous acetate solid to obtain the [ DETA ] Ac.
2. The modified coke oven gas hydrodesulfurization catalyst of claim 1 wherein the Fe is2O3The content of (a) is 2.0-5.0%, and the percentage refers to the mass percentage in the FeMo catalyst;
and/or, said MoO3The content of (b) is 5.0-10.0%, and the percentage refers to the mass percentage in the FeMo catalyst;
and/or the content of the doped element oxide is 0.1-1.0%, and the percentage refers to the mass percentage in the FeMo catalyst;
and/or the doped element oxide is V2O5Or CuO;
and/or the mass ratio of the FeMo catalyst to the [ DETA ] Ac is 3:1, 1:1 or 2: 1.
3. The modified coke oven gas hydrodesulfurization catalyst of claim 2, wherein the Fe is Fe2O3The content of (b) is 3.0%, and the percentage refers to the mass percentage in the FeMo catalyst;
and/or, the MoO3The content of (b) is 9.0%, and the percentage refers to the mass percentage in the FeMo catalyst;
and/or the content of the doped element oxide is 0.3%, 0.6% or 0.9%, and the percentage refers to the mass percentage in the FeMo catalyst;
and/or the doped element oxide is V2O5Or CuO;
and/or the mass ratio of the FeMo catalyst to the [ DETA ] Ac is 3:1, 1:1 or 2: 1.
4. The modified coke oven gas hydrodesulfurization catalyst of claim 1 wherein the FeMo catalyst comprises the following feed stocks: fe2O3：2.0-5.0%，MoO3: 5.0-10.0%, doped element oxide: 0.1 to 1.0 percent of the total weight of the alloy, and the balance of gamma-Al2O3The percentage refers to the mass percentage in the FeMo catalyst.
5. The modified coke oven gas hydrodesulfurization catalyst of any one of claims 1 to 4 wherein the FeMo catalyst is prepared by the following method:
(1) subjecting said Fe to2O3The precursor raw material of (1), the MoO3Dissolving the precursor raw material of (2) and the precursor raw material of the doped element oxide in water to obtain a mixed solution A;
(2) mixing the mixed solution A and gamma-Al2O3Mixing, soaking, oven drying, and calcining.
6. The modified coke oven gas hydrodesulfurization catalyst of claim 5 wherein in step (1) the Fe is2O3The precursor raw material of (1) is ferric nitrate;
and/or, in step (1), the MoO3The precursor raw material of (A) is ammonium molybdate;
and/or, in the step (1), when the doped element oxide is V2O5When said V is2O5The precursor raw material of (A) is ammonium metavanadate;
and/or, in the step (1), when the doping element oxide is Cr2O3When is, the Cr is2O3The precursor raw material of (A) is chromium nitrate;
and/or, in the step (1), when the doping element oxide is CuO, the precursor raw material of the CuO is copper nitrate;
and/or in the step (2), after the mixed solution A is aged for 2-4h, the mixed solution A is mixed with gamma-Al2O3Mixing and dipping;
and/or, in the step (2), the immersion time is 5-15 hours;
and/or, in the step (2), the temperature for drying is 100-150 ℃;
and/or in the step (2), the drying time is 1-5 hours;
and/or, in the step (2), the calcining temperature is 350-500 ℃;
and/or in the step (2), the calcining time is 2-5 hours.
7. The modified coke oven gas hydrodesulfurization catalyst of claim 6 wherein in step (2) the impregnation time is 10 hours;
and/or in the step (2), the drying temperature is 120 ℃;
and/or in the step (2), the drying time is 2 hours;
and/or, in the step (2), the calcining temperature is 500 ℃;
and/or in the step (2), the calcining time is 3 hours.
8. The modified coke oven gas hydrodesulfurization catalyst of claim 1 wherein in step 1) the acid is hydrochloric acid;
and/or, in the step 1), the acid is added dropwise at a dropping speed of 0.5 mol/h;
and/or, in the step 1), the temperature of the reaction is 20-30 ℃;
and/or, in the step 1), the reaction time is 5-8 hours;
and/or, in the step 2), the anhydrous acetate is anhydrous sodium acetate;
and/or, in the step 2), the temperature of the reaction is 20-30 ℃;
and/or, in the step 2), the reaction time is 12-36 hours;
and/or in the step 2), carrying out rotary steaming and drying treatment on the [ DETA ] Ac.
9. The modified coke oven gas hydrodesulfurization catalyst of claim 8 wherein the temperature of the reaction in step 1) is 25 ℃;
and/or, in step 2), the temperature of the reaction is 25 ℃;
and/or, in the step 2), the reaction time is 24 hours;
and/or, in the step 2), when the [ DETA ] Ac is further subjected to rotary steaming and drying treatment, wherein the rotary steaming time is 2-5 hours, the drying temperature is 50-80 ℃, and the drying time is 24-48 hours.
10. A method for preparing the modified coke oven gas hydrodesulfurization catalyst according to any one of claims 1 to 9, comprising the following steps: and mixing the FeMo catalyst and the [ DETA ] Ac.
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