Photocatalytic real-time liquid-phase adsorption desulfurization method

Technical field of photocatalytic real-time liquid phase adsorption desulfurization method

[0001] The present invention relates to a liquid phase adsorption desulfurization method, in particular to a dynamic real-time adsorption desulfurization process using ultraviolet photocatalysis, which is suitable for the desulfurization treatment of organic sulfur compounds in liquid fuels, and belongs to the desulfurization process technology of crude oil. field.

Background technique

[0002] Organic sulfur compounds are the most common impurities in crude oil. It is ubiquitous in a variety of liquid fuels, such as gasoline, diesel and aviation fuel. Organic sulfur compounds will generate sulfur dioxide and metal sulfur particles after the liquid fuel is burned, which will cause serious environmental pollution. In recent years, as the quality of crude oil continues to decline, the content of organic sulfur in liquid fuels has increased year by year. For this reason, developed countries and most developing countries have set extremely stringent standards for the sulfur content in commercially available liquid fuels. In addition, the supply of deep desulfurization fuel also restricts the development of fuel cells, an advanced technology.

[0003] Hydrodesulfurization technology is a desulfurization method commonly used in the industry at this stage. Under high temperature and high pressure, organic sulfides are reduced to H2S by hydrogen on the surface of the catalyst and separated from the liquid fuel. However, most of the organic sulfur compounds present in gasoline, diesel and aviation fuel are benzene and benzene ring-containing organic sulfide derivatives. Such organic sulfides have stable properties and are difficult to undergo traditional hydrogenation reactions. Therefore, the existing hydrodesulfurization process cannot remove these organic sulfur compounds from the liquid fuel. Therefore, it is difficult for hydrodesulfurization technology to meet the requirements of deep desulfurization. In summary, these factors have promoted the rapid development of various desulfurization technologies.

[0004] Adsorption desulfurization technology is a deep desulfurization method that can be operated at normal temperature and pressure. The reaction conditions are mild, the operation process is simple, and the adsorbent used can be regenerated and reused repeatedly. Refer to Figure 1, which is a flow chart of the traditional adsorption desulfurization and high temperature regeneration process. Adsorption desulfurization technology uses a fixed-bed reactor to adsorb organic sulfur compounds in liquid fuels on a solid desulfurizer to achieve the purpose of liquid desulfurization. The adsorbent bed used can be regenerated and recycled under high temperature conditions. Adsorption desulfurization has been studied a lot, and it is also considered to be the most potential desulfurization technology, which can cooperate with hydrodesulfurization technology or even replace the existing hydrodesulfurization process. In recent years, a large number of researches on photosensitive semiconductor materials have been carried out in the field of adsorption desulfurization, and certain results have been achieved. Among them, titanium dioxide adsorbents are widely used in the study of adsorption desulfurization because of their non-toxic and stable properties. A large number of studies have shown that the active center of adsorption and desulfurization of Ti02 is the acidic hydroxide group (-0H) on its surface. The sulfur atoms or benzene rings of macromolecular organic sulfides can be combined with hydroxide radicals through hydrogen bonds, thereby adsorbing on the surface of titanium dioxide, further achieving the purpose of adsorption and desulfurization. The use of TiO2 or a metal desulfurization adsorbent with TiO2 as a carrier can also deeply remove organic sulfides (such as thiophene or benzophene) from the liquid fuel. Benzene ring on organic sulfide, Both the phenocarbocyclic ring or the sulfur element can form a hydrogen bond with the free urn group on the surface of Ti02, so that the organic sulfide can be separated from the liquid organic fuel oAg/Ti0₂In addition to the use of surface vat groups in the adsorbent, Ag and Ti-OH active groups can also form special Ag-0-Ti bonds, and the S element in the organic sulfide can form a "bond bond with this special group, thereby To achieve the removal of organic sulfur compounds. Therefore, the number of acid urns directly determines the desulfurization performance of the adsorbent. Studies have shown that water molecules in the fuel will greatly affect the adsorption performance of such desulfurizers containing acidic desulfurization active centers. The trace water molecules in the fuel will combine with acidic hydroxide groups before the organic sulfur molecules, thereby reducing the desulfurization ability of the adsorbent. When the fuel contains a large amount of water molecules, a further layer will be formed on the surface of the adsorbent. Water molecule film, water molecule film can completely block the reaction of organic sulfur molecules and hydroxide groups. In summary, the water molecules in the fuel will have a great negative impact on the original desulfurization performance of the adsorbent. At this stage, the traditional adsorption desulfurization process cannot solve such problems caused by water molecules.

Summary of the invention

[0005] In view of the shortcomings in the prior art in the adsorption and desulfurization of liquid fuels containing organic sulfides, the present invention provides a method that can effectively improve the real-time adsorption performance of a liquid-phase desulfurization adsorbent, and at the same time solves the problem of liquid fuel Photocatalytic real-time liquid phase adsorption desulfurization method based on the negative effect of moisture on the adsorbent.

[0006] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present invention includes the following three photocatalytic real-time liquid phase adsorption desulfurization methods.

[0007] The first photocatalytic real-time liquid phase adsorption desulfurization method uses TiO2 as an adsorbent and includes the following steps:

[0008] (1) The Ti02 adsorbent is packed into the adsorption desulfurization quartz fixed bed reactor, and dried N2 is passed into the fixed bed pretreatment at normal temperature and pressure for 1 hour;

[0009] (2) The ultraviolet light generating device is placed next to the adsorption desulfurization quartz fixed bed, and the bed is uniformly exposed to ultraviolet light radiation to obtain a photocatalytic desulfurization fixed bed reactor;

[0010] (3) Use a rotary pump to feed the liquid fuel from the bottom into the photocatalytic desulfurization fixed bed reactor obtained in step (2), so that the liquid fuel infiltrates all the beds from bottom to top;

[0011] (4) When the liquid fuel contacts the bottom of the bed, turn on the ultraviolet light generating device to perform the photocatalytic real-time liquid phase adsorption desulfurization process;

[0012] (5) After the adsorption desulfurization process is completed, the adsorption desulfurization quartz fixed-bed reactor is moved to a high-temperature regeneration device, regenerated in dry air at a temperature of 450° C., and the regenerated TiO 2 adsorbent is reused.

[0013] Another photocatalytic real-time liquid phase adsorption desulfurization method uses TiO2-support material as an adsorbent, and includes the following steps:

[0014] (1) The organic Ti is dissolved in a solvent, and the weight of Ti on the Ti02-support material liquid-phase desulfurization adsorbent is 2-20wt%, and a mixed impregnation liquid is configured;

[0015] (2) According to the "equal volume impregnation method", drop the mixed impregnation liquid onto the porous carrier material, and obtain the initial product of TiO2-carrier material under the condition of constant stirring;

[0016] (3) Drying the initial product obtained in step (2) for 6-12 hours, then fumigating in dry air at a temperature of 500-550° C. for 2 to 3 hours, and cooling to room temperature to obtain Ti02-support Material adsorbent

[0017] (4) The TiO2-support material adsorbent obtained in step (3) is filled into the adsorption desulfurization quartz fixed bed reactor, and dried N2 is passed into the fixed bed pretreatment at normal temperature and pressure for 1 hour;

[0018] (5) The ultraviolet light generating device is placed beside the fixed bed of adsorption desulfurization quartz, and the bed is uniformly exposed to ultraviolet light radiation to obtain a photocatalytic desulfurization fixed bed reactor;

[0019] (6) A rotary pump is used to feed the liquid fuel from the bottom into the photocatalytic desulfurization fixed bed reactor obtained in step (5), so that the liquid fuel infiltrates all the beds from bottom to top;

[0020] (7) When the liquid fuel contacts the bottom of the bed, turn on the ultraviolet light generating device to perform the photocatalytic real-time liquid phase adsorption desulfurization process;

[0021] (8) After the adsorption desulfurization process is completed, the adsorption desulfurization quartz fixed bed reactor is moved to a high-temperature regeneration device, and regenerated in dry air at a temperature of 450° C. The regenerated Ti02-support material adsorbent repeats use.

[0022] In this technical solution, the organic Ti is Ci₂H₂80₄Ti; the solvent is isopropanol; the carrier material is AI2O3.

[0023] Another photocatalytic real-time liquid phase adsorption desulfurization method is based on Ag/Ti0₂As an adsorbent, it includes the following steps:

[0024] (1) Determine the pore volume of Ti02, grind the Ti02 particles, screen them to a particle size of 850~1400wn, and dry them for 6~12 hours at a temperature of 100~150°C;

[0025] (2) Press Ag/Ti0₂The weight of metallic Ag on the liquid-phase desulfurization adsorbent is 2~10wt%. Prepare the AgNOs impregnation solution. According to the "equal volume impregnation method", add AgN03 impregnation solution dropwise on the Ti02 carrier to obtain Ag/ TiO₂ [0026] (3) The product obtained in step (2) is calcined in dry air at a temperature of 400 to 450 ° C for 2 to 3 hours and cooled to room temperature to obtain an Ag/TiO₂Adsorbent

[0027] (4) The Ag/TiO obtained in step (3)₂The adsorbent is packed into the adsorption desulfurization quartz fixed bed reactor, and dried N2 is passed into the fixed bed pretreatment under normal temperature and pressure for 1 hour;

[0028] (5) The ultraviolet light generating device is placed next to the fixed bed of adsorption desulfurization quartz, and the bed is uniformly exposed to ultraviolet light radiation to obtain a photocatalytic desulfurization fixed bed reactor;

[0029] (6) Use a rotary pump to feed the liquid fuel from the bottom into the photocatalytic desulfurization fixed bed reactor obtained in step (5), so that the liquid fuel infiltrates all the beds from bottom to top;

[0030] (7) When the liquid fuel contacts the bottom of the bed, turn on the ultraviolet light generating device to perform the photocatalytic real-time liquid phase adsorption desulfurization process;

[0031] (8) After the adsorption desulfurization process is completed, the adsorption desulfurization quartz fixed-bed reactor is moved to a high-temperature regeneration device, and regenerated in dry air at a temperature of 450 °C. The regenerated Ag/TiO₂The adsorbent is reused.

[0032] In the ultraviolet light generating device of the present invention, a preferred solution is to use an ultraviolet lamp with a wavelength of 365 nm and a power of 4 to 8 watts, and the intensity of ultraviolet light radiation at the bed is 2 to 4 mW/cm²_o

[0033] The present invention adopts a real-time photocatalytic adsorption desulfurization method, the principle of which is: using ultraviolet light for ultraviolet light treatment, and real-time excitation of acidic vat-based active groups on the surface of TiO2. The invention is based on the adsorption and desulfurization mechanism of TiO2. Since the surface of TiO2 has a large number of urn groups bonded by hydrogen bonds, the energy provided by ultraviolet light can break the hydrogen bonds, thereby obtaining free urn group active groups. In addition, ultraviolet light can simultaneously excite electrons and holes, so that the water molecules adsorbed on the surface of TiO2 and the oxygen vacancies on the surface of TiO2 combine to undergo a photocatalytic reaction to produce more active light groups. Loading TiO2 on a porous carrier with a high specific surface area can make the vat groups more evenly distributed on the surface of the carrier, greatly increasing the probability of contact between the desulfurization active groups and the organic sulfur molecules. For Ag/TiO₂The adsorbent, silver ions can reduce the band gap of Ti02, which can excite more electrons and holes, and generate more free vat groups. In addition, the water molecules in the fuel can stably maintain the oxidation state of silver ions under photocatalysis, ensuring that the Ag-0-Ti active groups are not destroyed by ultraviolet light. Therefore, the adsorption desulfurization performed by the device of the present invention can effectively solve the problem of water molecules in the fuel, and at the same time make the adsorbent have stronger desulfurization capacity, higher efficiency, and better effect.

[0034] The technical solution provided by the present invention can effectively improve the real-time adsorption performance of the liquid-phase desulfurization adsorbent, and at the same time solve the negative impact of the moisture in the liquid fuel on the adsorbent. The photocatalytic adsorption desulfurization process uses ultraviolet light to directly act on the adsorption desulfurization fixed-bed reaction device. During the adsorption desulfurization process, the hydroxide active groups on the surface of the Ti02 adsorbent are excited in real time, which directly improves the desulfurization performance of the adsorbent. Since the present invention only needs to use a low-power output ultraviolet light device, the temperature will not increase significantly during the adsorption process, so there is no need to consider the negative impact of high temperature on the adsorption desulfurization process. In addition, the present invention also utilizes the photocatalytic decomposition reaction of water molecules on the surface of titanium dioxide under the catalysis of ultraviolet rays to fully stimulate the generation of more desulfurizing active acid hydroxide groups, thereby well solving the desulfurization effect of water molecules in the fuel. Adsorbent brings negative influence, and according to this reaction mechanism to further improve the desulfurization performance of titanium dioxide adsorbent.

[0035] Compared with the existing adsorption desulfurization device, the advantages of the present invention are:

[0036] 1. The present invention utilizes the TiO2 adsorption desulfurization mechanism to directly introduce ultraviolet light into the dynamic adsorption desulfurization process, and the active vat groups on the surface of TiO2 are excited in real time by photocatalysis. Greatly improve the real-time adsorption desulfurization performance of Ti02 adsorption desulfurization materials

can;

[0037] 2. The short-time ultraviolet light adsorption desulfurization process will not damage the surface structure of the material, and the adsorbent after photocatalytic desulfurization can be regenerated and reused, while stably maintaining the original desulfurization performance.

[0038] 3. Use a low-power ultraviolet device to excite the surface active groups of the adsorbent in real time, or simply use sunlight to excite the desulfurization active groups, reduce energy consumption, and realize the industrialization of the photocatalytic adsorption desulfurization process;

[0039] 4. The negative impact of water molecules in the fuel on the adsorbent is eliminated, and the photocatalytic reaction of water molecules on the surface of TiO2 is used to further improve its adsorption and desulfurization performance.

Description of the drawings

[0040] Figure 1 is a flow chart of the traditional adsorption desulfurization and high temperature regeneration process;

[0041] FIG. 2 is a process flow diagram of the photocatalytic fixed bed real-time adsorption desulfurization and high-temperature regeneration provided by the present invention;

[0042] FIG. 3 is a performance comparison diagram of TiO2 desulfurization adsorbent using traditional desulfurization process and photocatalytic desulfurization process;

[0043] Figure 4 shows the influence of water molecules on the TiO2 adsorbent in the traditional desulfurization and photocatalytic desulfurization processes;

[0044] FIG. 5 is Τΐθ2-Α1₂The performance comparison chart of θ3 desulfurization adsorbent using traditional desulfurization process and photocatalytic desulfurization process;

[0045] Figure 6 shows the effect of water molecules on TiO₂-Al₂The influence of O3 adsorbent in traditional desulfurization and photocatalytic desulfurization process;

[0046] FIG. 7 shows the effect of water molecules in fuel on Ag/Ti0₂Influence in the traditional desulfurization and photocatalytic desulfurization process.

Detailed ways

[0047] The technical solution of the present invention will be further described below with reference to the drawings and embodiments.

[0048] Embodiment 1:

[0049] In this embodiment, the following steps are used to perform TiO2 photocatalytic real-time liquid phase adsorption desulfurization:

[0050] (1) Preparation of TiO2 adsorbent

[0051] In this embodiment, titanium dioxide particles (commercially available) provided by Saint Gobain Norpro were selected, and the TiO2 particles were ground and sieved to 850~1400wn, dried in an oven at 100°C for 6 hours, and then at a high temperature of 450° in dry air. Boil for 2 hours, and wait until TiO2 is cooled in dry air for later use.

[0052] (2) Photocatalytic real-time adsorption desulfurization process

[0053] Refer to Figure 2, which is a process flow diagram of the photocatalytic fixed bed real-time adsorption desulfurization and high temperature regeneration provided by this embodiment; compared with the traditional process shown in Figure 1, this embodiment uses a rotary pump to remove liquid fuel From the bottom into the photocatalytic desulfurization fixed bed reactor, the liquid fuel infiltrates all the beds from bottom to top, and when the liquid fuel contacts the bottom of the bed, the photocatalytic real-time liquid phase adsorption desulfurization process is carried out by ultraviolet light. The ultraviolet light generating device is placed next to the adsorption desulfurization quartz fixed bed reactor, and the bed layer is uniformly exposed to ultraviolet light radiation to obtain a photocatalytic desulfurization fixed bed reactor.

[0054] In this embodiment, the realization of the ultraviolet photocatalysis process can be used in a specific solution: two low-power ultraviolet generating devices are symmetrically placed on both sides of the quartz reactor so that they are as close as possible to the reactor tube wall The outer edge is made into the ultraviolet adsorption reactor of the photocatalytic desulfurization reaction device. The entire ultraviolet adsorption reactor is placed in a dark box, and aluminum foil is used inside the dark box, so that the ultraviolet light can be uniformly irradiated on the entire reactor. The ultraviolet generating device used in this embodiment is a low-power (4watt) portable ultraviolet lamp with a wavelength of 365nm, and the ultraviolet intensity is 2mW/cm at a bed 10 cm away from the lamp.²_o

[0055] (3) Test the performance of the photocatalytic adsorption desulfurization process

[0056] The penetration experiment was used to test the desulfurization performance of TiO2 in traditional adsorption desulfurization and photocatalytic desulfurization processes using sample fuel prepared in the laboratory. Specific steps are as follows:

[0057] 1 Dissolve phenoxphene in n-octane and configure a sulfur-containing standard sample fuel. In this embodiment, the organic sulfur content of the fuel standard sample is 3500 ppmw;

[0058] 2 10.0 g of the prepared TiO2 adsorbent was respectively filled into the traditional fixed bed reactor and the photocatalytic desulfurization reaction device. At this time, first turn off the UV lamp in the photocatalytic desulfurization device, and then pass dry N2 into each bed to remove the gas-phase impurities mixed in when filling each bed, and stop the gas flow after pretreatment for 1 hour;

[0059] 3Using the photocatalytic desulfurization process provided in Figure 2: Pass the standard fuel sample prepared in step 1 from the photocatalytic desulfurization reactor into the adsorption bed, and turn on the ultraviolet when the liquid standard fuel sample contacts the bottom of the bed. At the same time, the photocatalytic adsorption desulfurization process started. The photocatalytic process in Figure 2 was used to carry out the desulfurization penetration experiment. Take liquid fuel samples every 5 to 10 minutes. After 2 hours, complete the penetration experiment and analyze the organic sulfur content in the samples by liquid phase infrared spectroscopy.

[0060] 4Using the traditional adsorption desulfurization provided in Figure 1: pass the standard fuel sample prepared in step 1 into the adsorption bed from the bottom of the traditional desulfurization reactor, and use the traditional adsorption desulfurization process provided in Figure 1 to perform Penetration experiment. Liquid fuel samples were taken every 5 to 10 minutes, and the penetration experiment was finished after 2 hours, and the organic sulfur content in the samples was analyzed by liquid phase infrared spectroscopy.

[0061] Draw a penetration curve, thereby calculating the penetration adsorption capacity and saturated adsorption capacity of the adsorbent. The horizontal axis of the penetration curve is time, and the vertical axis is C/Co. Where C is the organic sulfur content in the liquid sample, and Co is the original sulfur content in the fuel sample. Finally, the adsorption desulfurization performance data of TiO2 obtained in the two adsorption desulfurization devices were compared. Refer to Figure 3 for the comparison results. Table 1 lists the penetration performance and saturation performance values of the Ti02 adsorbent in the traditional adsorption desulfurization device and the photocatalytic adsorption desulfurization device for comparison.

[0062] (4) Test the effect of moisture on the performance of TiO2 in traditional and photocatalytic adsorption desulfurization devices

[0063] In the photocatalytic real-time adsorption desulfurization process, the penetration experiment was used to test the desulfurization performance of water molecules for TiO2 using the traditional adsorption desulfurization process and the photocatalytic desulfurization process using a sample fuel prepared in the laboratory. Specific steps are as follows:

[0064] 1 Dissolve phenothenin in n-octane to initially obtain a fuel sample with an organic sulfur content of 3500 ppmw. Deionized water was added to this liquid fuel sample to obtain a final water-containing fuel sample with a water content of 1000 ppmw.

[0065] 2 10.0 g of the prepared TiO2 adsorbent was respectively packed into the traditional fixed bed reactor and the photocatalytic desulfurization reactor. Turn off the UV lamp in the photocatalytic desulfurization device, and then pass dry N2 into each bed to remove the gas phase impurities mixed in when filling each bed. After pretreatment for 1 hour, stop the gas flow.

[0066] 3 The water-containing fuel sample prepared in step 1 is passed into the adsorption bed from the bottom of the photocatalytic desulfurization reactor, and the ultraviolet device is turned on when the liquid standard fuel sample contacts the bottom of the bed, and the photocatalytic adsorption desulfurization process is started at the same time. The photocatalytic process and device provided by the present invention are used to carry out desulfurization penetration experiments. Take liquid fuel samples every 5 to 10 minutes. After 2 hours, complete the penetration test and analyze the organic sulfur content in all liquid samples by liquid phase infrared spectroscopy.

[0067] 4 The water-containing fuel sample prepared in step 1 was passed into the adsorption bed from the bottom of the traditional desulfurization reactor, and the penetration experiment was carried out by using the traditional adsorption desulfurization device. Take liquid fuel samples every 5 to 10 minutes. After 2 hours, complete the penetration experiment and analyze the organic sulfur content in all liquid samples by liquid phase infrared spectroscopy.

[0068] Draw a penetration curve, thereby calculating the penetration capacity and saturated adsorption capacity of the adsorbent. The horizontal axis of the penetration curve is time, and the vertical axis is C/Co. Where C is the organic sulfur content in the liquid sample, and Co is the original sulfur content in the fuel sample. Finally, the desulfurization performance data of the adsorbent obtained by TiO2 in the two adsorption desulfurization devices were compared. See Figure 4 for the comparison results. Table 1 lists the comparison of the influence of water molecules in the fuel on the penetration and saturation performance of TiO2 adsorbents in traditional adsorption desulfurization devices and photocatalytic adsorption desulfurization devices.

[0069] Embodiment 2:

[0070] This embodiment uses the following steps to perform TiO₂-Al₂O3 photocatalytic real-time liquid phase adsorption desulfurization:

[0071] (1) Τίθ2-Α1₂Preparation of θ3

[0072] In this embodiment, the (commercially available) aluminum oxide AI2O3 carrier provided by Alfa Aesar is selected, and its pore volume is 1.0 mL/g_oGrind and sift AI2O3 particles to a size of 850~1400wn, and dry them in an oven at 100 °C for more than 6 hours for later use.

[0073] Using the "isovolume impregnation method", according to the weight of the metal Ti that needs to be loaded, calculate the concentration of the required organic titanium (C12H2804Ti in this embodiment) solution and prepare the Ti02-A1203 adsorbent.

[0074] 1 Determine the weight of Ti to be loaded as the entire TiO₂-Al₂O₃10wt% of adsorbent weight, namely: η^τϊ

[0075] ----------= 0. Work°.

^ΙΠΤϊθ2-Αΐ2θ3

[0076] 2 Weigh 10.0 g of the A1203 carrier, and according to the "isovolume impregnation method", the total pore volume of the carrier is the volume of the required organic Ti solution:

[0077] VTi=10.0g X 1.0mL/g=10mLo

[0078] 3 Use the following formula to calculate the required Ti molar mass rm:

MW_Ti X n_Ti

[0079] -~~~J ----=0.10, ^MWTiO2 ^{X n}Ti ^{+ m}A120g

[0080] Where MWTi is the molecular weight of titanium, Mr® is the molecular weight of titanium dioxide, and is the quality of AI2O3.

[0081] Using the above formula to calculate the molar mass of Ti nTi is 0.025mol_o

[0082] 4 The molar concentration of the corresponding solution is obtained according to the calculated molar mass of Ti and the volume of the solution: nj-i 0.025 mol _

[0083] C_ri = - =---------= 2.5 X 10^-3 mal/mL.

V_Ti 10 mL

[0084] 5 Use a dropper to take 10 mL of Ci at a specific concentration₂H₂80₄The Ti impregnating liquid is dropped into the AI2O3 carrier drop by drop, while continuously stirring, so that the carrier and the impregnating liquid are fully contacted, and 10wt% of Τίθ2-Α1 is initially obtained.₂θ3.

[0085] 6 Put the adsorbent obtained in step 5 into an oven at about 100° C. and dry it again for 6 hours, and then burn it in dry air at 550 Ό M for 2 hours. Finally, let it cool to room temperature in dry air for later use.

(2) Photocatalytic real-time adsorption desulfurization process

[0087] According to the technical scheme of Example 1, two low-power ultraviolet generating devices were symmetrically placed on both sides of the quartz reactor to make it as close as possible to the outer edge of the reactor tube wall. The entire ultraviolet adsorption reactor is placed in a dark box, and aluminum foil is used inside the dark box, so that the ultraviolet light can be uniformly irradiated on the entire reactor. The ultraviolet generating device used in this embodiment is a low-power (4watt) portable ultraviolet lamp with a wavelength of 365nm, and the ultraviolet intensity is 2mW/cm at a bed 10cm away from the tube.²。

[0088] (3) Test the effect of photocatalytic adsorption desulfurization process

[0089] The penetration experiment was used to test TiO with sample fuel prepared in the laboratory.₂-AbO3 desulfurization performance in traditional adsorption desulfurization equipment and photocatalytic desulfurization equipment. Specific steps are as follows:

[0090] 1 Dissolve phenoxphene in n-octane to obtain a standard fuel sample with an organic sulfur content of 3500 ppmw.

[0091] 2The prepared TiO₂-10.0g each of AbO3 adsorbents are respectively packed into the traditional fixed bed reactor and the photocatalytic desulfurization reactor. Turn off the UV lamp in the photocatalytic desulfurization device, and then pass dry N2 into each bed to remove the gas phase impurities mixed in when filling each bed. After pretreatment for 1 hour, stop the gas flow.

[0092] 3 The standard fuel sample prepared in step 1 is passed into the adsorption bed from the bottom of the photocatalytic desulfurization reactor, and when the liquid standard fuel sample contacts the bottom of the bed, the ultraviolet device is turned on, and the photocatalytic adsorption desulfurization process is started at the same time, Desulfurization

Penetration experiment. Liquid fuel samples were taken every 5 to 10 minutes, and the penetration experiment was ended after 2 hours, and the organic sulfur content in each sample was analyzed by liquid phase infrared spectroscopy.

[0093] 4 The standard fuel sample prepared in step 1 was passed into the adsorption bed from the bottom of the traditional desulfurization reactor, and the penetration experiment was carried out by using the traditional adsorption desulfurization device. Liquid fuel samples were taken every 5 to 10 minutes, and the penetration experiment was finished after 2 hours and the organic sulfur content in each sample was analyzed by liquid phase infrared spectroscopy.

[0094] Draw a penetration curve, thereby calculating the penetration capacity and saturated adsorption capacity of the adsorbent. The horizontal axis of the penetration curve is time, and the vertical axis is c/Co. Where C is the organic sulfur content in the liquid sample, and Co is the original sulfur content in the fuel sample. Finally, TiO₂-AbO3 compares the adsorption desulfurization performance data obtained in two adsorption desulfurization devices. Refer to Figure 5 for the comparison results. Table 2 lists TiO₂-The penetration performance and saturation performance value of AbO3 adsorbent in traditional adsorption desulfurization device and photocatalytic adsorption desulfurization device for comparison.

(4) Test moisture for TiO₂-Al₂Influence of O3 on the performance of traditional and photocatalytic adsorption desulfurization equipment

[0096] Using the penetration experiment, the sample fuel prepared in the laboratory was used to test the effect of water molecules on TTI₂-Α1₂θ3 Desulfurization performance when using traditional adsorption desulfurization process and photocatalytic desulfurization process. Specific steps are as follows:

[0097] 1 Dissolve phenyl thiophene in n-octane to initially obtain a fuel sample with an organic sulfur content of 3500 ppmw. Deionized water was added to this liquid fuel sample to obtain a final water-containing fuel sample with a water content of 1000 ppmw.

[0098] 2The prepared TiO₂-Al₂Each 10.0g of O3 adsorbent was packed into the traditional fixed-bed reactor and the photocatalytic desulfurization reactor. Turn off the UV lamp in the photocatalytic desulfurization device, and then pass dry N2 into each bed to remove the gas phase impurities mixed in when filling each bed. After pretreatment for 1 hour, stop the gas flow.

[0099] 3 The water-containing fuel sample prepared in step 1 is passed into the adsorption bed from the bottom of the photocatalytic desulfurization reactor, and the ultraviolet device is turned on when the liquid standard fuel sample contacts the bottom of the bed, and the photocatalytic adsorption desulfurization process is started at the same time. Use the photocatalytic device to carry out desulfurization penetration experiment. Take liquid fuel samples every 5 to 10 minutes. After 2 hours, complete the penetration experiment and analyze the organic sulfur content in all liquid samples by liquid phase infrared spectroscopy.

[0100] 4 The water-containing fuel sample prepared in step 1 was passed into the adsorption bed from the bottom of the traditional desulfurization reactor, and the penetration experiment was performed by using the traditional adsorption desulfurization device. Take liquid fuel samples every 5 to 10 minutes. After 2 hours, complete the penetration experiment and analyze the organic sulfur content in all liquid samples by liquid phase infrared spectroscopy.

[0101] Draw a penetration curve, thereby calculating the penetration capacity and saturated adsorption capacity of the adsorbent. The horizontal axis of the penetration curve is time, and the vertical axis is C/Co. Where C is the organic sulfur content in the liquid sample, and Co is the original sulfur content in the fuel sample. Finally, the desulfurization performance data of the adsorbent obtained by Ti02-A12O3 in the two adsorption desulfurization devices were compared. Refer to Figure 6 for the comparison results. Table 2 lists the influence of water molecules in the fuel on the penetration and saturation performance of the Ti02-AI2O3 adsorbent in the traditional adsorption desulfurization device and the photocatalytic adsorption desulfurization device.

Embodiment 3:

[0103] This embodiment uses the following steps to perform Ag/TiO₂Photocatalytic real-time liquid phase adsorption desulfurization:

(1) Preparation of Ag/TiO2 adsorbent

[0105] This example uses titanium dioxide particles (commercially available) provided by Saint Gobain Norpro, with a pore volume of 0.44 mL/g_oGrind and sift the TiO2 particles to a size of 850~1400um, and dry them in an oven at 100°C for 6 hours for later use.

[0106] Using the "Isometric Impregnation Method", according to the weight of the metal that needs to be loaded, calculate the concentration of the required AgN03 solution and prepare Ag/TiO₂Adsorbent.

[0107] 1 First determine that the mass percentage of metallic silver that needs to be loaded is 4wt%, namely:

<td>[0108]</td><td>m_Ae--- =0.04α^mAg/TiO₂</td>

<td>[0109]</td><td>2Weigh 10.Og Ti02 carrier, according to the "Isometric Impregnation Method", the total pore volume of the carrier is the required AgN03</td>

Volume of liquid:

<td>[0110]</td><td>V_AgN03 = 10.0 g X 0,44 mL/g = 4, 4 mLo</td>

<td>[0111]</td><td>3Use the following formula to calculate the required molar mass of AgN03ⁿAgNOj:</td>

<td>[0112]</td><td>Μ%ΧηΑΕ = .04,MW. Lu XⁿAgNO3 + ^mTiO2</td>

<td>[0113]</td><td>Where Μ% is the molecular weight of silver,^m-no₂Is the weight of titanium dioxide. Use the above formula to calculate AgN03</td>

The molar mass is 3.858 X ΙΟΛιοΙ.

<td>[0114]</td><td>4According to the calculated molar mass of AgN03 and the volume of the solution, the molar concentration of the corresponding solution is obtained: 3.858 X ΊΟ? Mol-</td>

<td>[0115]</td><td>%. Plant 5 is; =4.4_mL 877 Call</td>

<td>[0116]</td><td>5Using a dropper to take 4.4 mL of AgN03 immersion solution of a specific concentration drop by drop into the Ti02 carrier, while constantly stirring,</td>

Make the carrier and the immersion liquid fully contact, and initially obtain Ag/Ti0 with an Ag content of 4wt%_2o

<td>[0117]</td><td>6 Put the adsorbent obtained in step 5 into an oven at about 100°C to dry again for 6 hours, and then place it in dry air</td>

450 Ό Μ burned for 2 hours. Finally, let it cool to room temperature in dry air for later use.

<td>[0118][0119]</td><td>(2) According to the technical scheme of Example 1, the photocatalytic real-time adsorption desulfurization process has two low-power ultraviolet generators symmetrically placed on both sides of the quartz reactor to make</td>

It is as close as possible to the outer edge of the reactor tube wall. The entire ultraviolet adsorption reactor is placed in a dark box, and aluminum foil is used inside the dark box, so that the ultraviolet light can be uniformly irradiated on the entire reactor. The ultraviolet generator used in this example is a low-power (4watt) portable ultraviolet lamp with a wavelength of 365nm, and the ultraviolet intensity is 2mW/cm at a bed 10cm away from the lamp.²。

<td>[0120][0121]</td><td>(3) Test moisture for Ag/TiO₂The effect of performance in traditional and photocatalytic adsorption desulfurization devices. Use laboratory-prepared sample fuel to test the effect of water molecules on Ag/TiO.₂In the use of traditional adsorption desulfurization process</td>

The desulfurization performance of art and photocatalytic desulfurization process. Specific steps are as follows:

<td>[0122]</td><td>1 Dissolve phenothenin in n-octane to initially obtain a fuel sample with an organic sulfur content of 3500 ppmw. To this liquid</td>

Deionized water is added to the bulk fuel sample to obtain a final water-containing fuel sample with a water content of 1000 ppmw.

<td>[0123]</td><td>2The prepared Ag/TiO₂10.0g each of the adsorbents are respectively packed into the traditional fixed bed reactor and photocatalytic desorption</td>

Sulfur reactor. Turn off the UV lamp in the photocatalytic desulfurization device, and then pass dry N2 into each bed to remove the gas-phase impurities mixed in when filling each bed, and stop the gas flow after pretreatment for 1 hour.

<td>[0124]</td><td>3The water-containing fuel sample prepared in step 1 is passed into the adsorption bed from the bottom of the photocatalytic desulfurization reactor, when the liquid</td>

When the state standard fuel sample contacts the top of the bed, the ultraviolet device is turned on to start the photocatalytic adsorption desulfurization process. Take liquid fuel samples every 5 to 10 minutes. After 2 hours, complete the penetration experiment and analyze the organic sulfur content in all liquid samples by liquid phase infrared spectroscopy.

<td>[0125]</td><td>4 Pass the water-containing fuel sample prepared in step 1 into the adsorption bed from the bottom of the traditional desulfurization reactor, and use the transmission</td>

Penetration experiment was carried out with the integrated adsorption desulfurization device. Take liquid fuel samples every 5 to 10 minutes. After 2 hours, complete the penetration experiment and analyze the organic sulfur content in all liquid samples by liquid phase infrared spectroscopy.

<td>[0126]</td><td>5Draw a breakthrough curve, from which the breakthrough capacity and saturated adsorption capacity of the adsorbent are calculated. Penetration curve graph horizontal</td>

The axis is time, and the vertical axis is C/Coο where C is the organic sulfur content in the liquid sample, and Co is the original sulfur content in the fuel sample. Finally, compare the desulfurization performance data of the adsorbent obtained by TiO2 in the two adsorption desulfurization devices. Refer to Figure 7 for the comparison results. Table 3 lists the comparison of the influence of water molecules in the fuel on the penetration and saturation performance of the Ag/Ti02 adsorbent in the traditional adsorption desulfurization device and the photocatalytic adsorption desulfurization device.

[0127] Table 1 summarizes the penetration performance and saturation performance values of the TiO2 adsorbent in the traditional desulfurization device and the photocatalytic desulfurization device when different fuel samples are used for comparison.

[0128] Table 2 summarizes the TiO when using different fuel samples₂-Al₂O₃The penetration performance and saturation performance values of the adsorbent in the traditional desulfurization device and the photocatalytic desulfurization device are provided for comparison.

[0129] Table 3 summarizes the Ag/TiO₂The penetration performance and saturation performance values of the adsorbent in the traditional desulfurization device and the photocatalytic desulfurization device are provided for comparison.

[0130] The photocatalytic desulfurization device provided by the present invention is simple and feasible. It can not only improve the real-time desulfurization performance of titanium dioxide in a fixed bed reactor, but also effectively improve all adsorbents in the desulfurization activity with acidic hydroxide groups. At the same time, it can eliminate the negative impact of water molecules in the fuel on the adsorbent. The photocatalytic reaction of water molecules on the surface of TiO2 is used to further improve its adsorption and desulfurization performance, thereby promoting the development of adsorption desulfurization technology.

[0131] Table 1

[0132]

<td rowspan="2">Ti0₂</td><td colspan="2">Traditional desulfurization process</td><td colspan="2">Photocatalytic desulfurization process</td>

<td>Anhydrous fuel</td><td>Water-containing fuel</td><td>Anhydrous fuel</td><td>Water-containing fuel</td>

<td>Penetration adsorption force (mg S/g)</td><td>2. 45</td><td>1.59</td><td>4. 05</td><td>4.91</td>

<td>Saturated adsorption capacity (mg S/g)</td><td>3. 90</td><td>3. 27</td><td>5. 63</td><td>6. 20</td>

[0133] Table 2

[0134]

<td rowspan="2">TiO₂^_Al₂O₃</td><td colspan="2">Traditional desulfurization process</td><td colspan="2">Photocatalytic desulfurization process</td>

<td>Anhydrous fuel</td><td>Water-containing fuel</td><td>Anhydrous fuel</td><td>Water-containing fuel</td>

<td>Penetration adsorption force (mg S/g)</td><td>4.91</td><td>4. 29</td><td>6.13</td><td>6. 75</td>

<td>Saturated adsorption capacity (mg S/g)</td><td>6. 44</td><td>5. 61</td><td>7. 76</td><td>8.31</td>

[0135] Table 3

[0136]

<td>Ag/Ti0₂</td><td>Traditional desulfurization process</td><td>Photocatalytic desulfurization process</td>

<td>Penetration adsorption force (mg S/g)</td><td>3. 07</td><td>4.91</td>

<td>Saturated adsorption capacity (mg S/g)</td><td>4・63</td><td>6. 35</td>