CN105289454A - Method for preparing TiO2 liquid phase desulfurization adsorbents through photocatalysis - Google Patents

Abstract

The invention relates to a method for preparing TiO2 liquid phase desulfurization adsorbents through photocatalysis, a method for preparing TiO2, metal oxides with TiO2 being carriers and Ag/TiO2 liquid phase desulfurization adsorbents through photocatalysis, and particularly relates to an ultraviolet and solar photocatalytic preparation method. The TiO2 adsorption principle is utilized by the method, free hydroxyl radical groups on the surface of TiO2 are excited through photocatalysis, then the TiO2 adsorption principle is combind with the TiO2 adsorption and desulfurization principle, the TiO2 desulfurization adsorbents prepared through the photocatalysis mode are formed, and the efficiency of the TiO2 desulfurization adsorbents is improved. A low-power ultraviolet device is adopted for the method, ultraviolet in sunlight can also be utilized, the active groups of the adsorbents can be excited, energy consumption is reduced, and the industrial photocatalysis preparation technology can be achieved. The adsorbents prepared through photocatalysis stably exist under the high-temperature condition, and thus the adsorbents can be regenerated and reused while original desulfurization performance is maintained.

Description

TiO is prepared in photocatalysis 2the method of liquid-like phase desulfuration adsorbent

Technical field

The present invention relates to the preparation method of gasoline liquid adsorption desulfurization agent, particularly TiO ₂the gasoline liquid adsorption desulfurization agent of class, comprises TiO ₂, with TiO ₂for the TiO of carrier ₂-metal oxide support material and Ag/TiO ₂the preparation method of gasoline liquid adsorption desulfurization agent, belong to desulfur technology or the technology field of crude oil.

Background technology

Titanium dioxide (TiO ₂) be widely used in every field as a kind of special light sensitivity semi-conducting material.TiO ₂and be used for solving problem of environmental pollution with its photochemical catalyst being carrier, such as useless water purification, the process of the harmful chemical in air and soil.For this reason, people are for titanium dioxide (TiO ₂) surface active groups and photocatalytic mechanism carried out large quantifier elimination.

Photocatalysis technology also has a wide range of applications in liquid desulfuration research field.Photochemical catalytic oxidation desulfur technology is then rely on TiO ₂deng the characteristic of photosensitive material, utilize ultraviolet light or sunshine by the organic sulfur compound exhaustive oxidation in liquid phase fuel, thus reach the object separated from liquid phase crude oil by organic sulfur compound.Such as, but photochemical catalytic oxidation desulfur technology needs to use multiple strong oxidizer, H ₂o ₂or O ₃, in production, they not only have high safety requirements to reaction system, also may cause secondary pollution to environment.

In recent years, adsorption desulfurize field starts to carry out large quantity research to this type of light sensitivity semi-conducting material, and achieves certain achievement.TiO ₂the hydroxyl activity desulfurization group had due to its surface and by people's extensive concern.Utilize TiO ₂or with TiO ₂for the metal desulfurization adsorbent of carrier, can by organic sulfur compound (such as thiophene or benzene thiophene) deep removal from liquid fuel.Phenyl ring on organic sulfur compound, thiophene carbocyclic ring or element sulphur can with TiO ₂the free hydroxyl on surface forms Hydrogenbond, thus organic sulfur compound is separated from liquid phase organic-fuel.Ag/TiO ₂adsorbent is except utilizing surface hydroxyl, Ag and Ti-OH active group can also form special Ag-O-Ti key, and the S element in organic sulfur compound then can form π bond with this specific groups and close, thus realizes removing of organic sulfur compound.Therefore, for TiO ₂for the desulfuration adsorbent of carrier, TiO ₂the hydrogen-oxygen active group quantity on surface directly determines the desulphurizing ability of this type of adsorbent.

Organic sulfur compound is modal impurity in crude oil, is prevalent in Multi liquid fuel, as gasoline, diesel oil and aviation fuel.Can generate sulfur dioxide and metal sulfur granules after organic sulfur compound burning in fuel oil, these materials can cause serious problem of environmental pollution.For this reason, developed country and environmental administration of most developing country have formulated extremely harsh standard to the sulfur content in commercial fuel.In recent years, crude quality declines, and for the demand of clean fuel in continuous increase, these factors are had higher requirement to desulfur technology.Wherein, adsorption desulfurize technology is a kind of method utilizing adsorbent deep sulfide removing from fuel oil at normal temperatures and pressures, because its reaction condition is gentle, operating process is simple and be widely studied.

Adsorbent is the core of adsorption desulfurize technology, and the adsorbent of high-quality must possess high absorption property and certain selective, can regenerate and repetitive cycling use simultaneously.This just proposes new requirement to the preparation of adsorbent.Up to the present, a lot of adsorbent is all used in adsorption desulfurize research.Wherein Ag/TiO ₂adsorbent due to its manufacturing process simple, desulfurization performance is superior, and regeneration properties is stable and show one's talent.But the preparation method of present stage can not activate more TiO ₂surface Hydrogen oxygen groups, thus the usefulness limiting this type of adsorbent.

Summary of the invention

The present invention is directed to the deficiency that the usefulness that exists for the adsorbent of organic sulfide removal compound from liquid fuel is at present low, utilize TiO ₂photocatalysis performance, a class TiO is provided ₂high-efficiency desulfurization adsorbent, comprise TiO ₂, TiO ₂-metal oxide support material, Ag/TiO ₂deng preparation method, from liquid fuel, more effectively can be adsorbed with machine sulfide.

For achieving the above object, the technical solution used in the present invention is to provide photocatalysis and prepares TiO ₂the method of liquid-like phase desulfuration adsorbent, comprises following content:

1, a kind of photocatalysis is provided to prepare TiO ₂the method of gasoline liquid adsorption desulfurization agent, comprises the steps:

(1) TiO is determined ₂pore volume, by TiO ₂particulate abrasive, screening to particle diameter is 850 ~ 1400 μm, is that under the condition of 100 ~ 150 DEG C, drying processes 6 ~ 12 hours in temperature;

(2) under the condition constantly stirred, deionized water is dropped in TiO ₂on, fully moistening to TiO ₂upper formation liquid film;

(3) by fully moistening TiO ₂evenly spread out, under ultraviolet catalytic condition, process 2 ~ 4 hours, then drying process 6 ~ 12 hours;

(4) product step (3) obtained is calcine 2 ~ 3 hours in the dry air of 400 ~ 450 DEG C in temperature, after being cooled to room temperature, obtains a kind of TiO ₂desulfuration adsorbent.

2, a kind of photocatalysis is provided to prepare TiO ₂the method of-carrier material gasoline liquid adsorption desulfurization agent, comprises the steps:

(1) organic titanium solution is pressed TiO ₂the weight of the Ti that the agent of-carrier material gasoline liquid adsorption desulfurization is carried is 2 ~ 20wt%, is configured to organic titanium mixed impregnant liquor;

(2) by " equi-volume impregnating ", mixed impregnant liquor is instilled on metal oxide support material, under the condition constantly stirred, tentatively obtain TiO ₂-carrier material head product;

(3) head product obtained in step (2) drips deionized water, constantly stirs, occur supersaturation to surface;

(4) product that step (3) obtains evenly is spread out, under ultraviolet catalytic condition, process 2 ~ 4 hours, then drying process 6 ~ 12 hours;

(5) product step (4) obtained is calcine 2 ~ 3 hours in the dry air of 500 ~ 550 DEG C in temperature, after being cooled to room temperature, obtains TiO ₂-carrier material desulfuration adsorbent.

In the technical program, described organic titanium solution is C ₁₂h ₂₈o ₄ti; Described metal oxide support material is Al ₂o ₃.

3, a kind of photocatalysis is provided to prepare Ag/TiO ₂the method of gasoline liquid adsorption desulfurization agent, comprises the steps:

(1) TiO is determined ₂pore volume, by TiO ₂particulate abrasive, screening to particle diameter is 850 ~ 1400 μm, is that under the condition of 100 ~ 150 DEG C, drying processes 6 ~ 12 hours in temperature;

(2) by Ag/TiO ₂the metal A g weight that gasoline liquid adsorption desulfurization agent is carried is 2 ~ 10wt%, preparation AgNO ₃maceration extract, by " equi-volume impregnating ", at TiO ₂carrier drips AgNO ₃maceration extract, under continuous stirring condition, obtains Ag/TiO ₂;

(3) under constant agitation deionized water drop is added in Ag/TiO prepared by step (2) ₂on, to Ag/TiO ₂surface produces liquid film or occurs supersaturation, obtains fully moistening Ag/TiO ₂;

(4) by fully moistening Ag/TiO ₂evenly spread out, under ultraviolet catalytic condition, process 2 ~ 4 hours, then be dry process 6 ~ 12 hours under the condition of 100 ~ 150 DEG C in temperature;

(5) product step (4) obtained is calcine 2 ~ 3 hours in the dry air of 400 ~ 450 DEG C in temperature, after being cooled to room temperature, obtains a kind of Ag/TiO ₂gasoline liquid adsorption desulfurization agent.

The present invention adopts photocatalysis to prepare TiO ₂the desulfuration adsorbent of class, its principle is: utilize ultraviolet lighting device to carry out ultraviolet lighting process, thus fully excite TiO ₂the hydroxyl reactive group on surface.The present invention is based on TiO ₂desulphurization mechanism, due to TiO ₂surface has a large amount of with the hydroxyl of Hydrogenbond, therefore can realize chemisorbed hydrone and Lacking oxygen.For with the hydroxyl of Hydrogenbond, the energy that ultraviolet light provides can interrupt hydrogen bond, thus the hydroxyl reactive group that gains freedom.Ultraviolet luminous energy excitation electron and hole simultaneously, makes TiO simultaneously ₂the hydrone of adsorption and Lacking oxygen combine generation hydroxide groups.By TiO ₂be loaded in high surface area carrier, hydroxyl reactive group can be made more to be evenly distributed in adsorbent surface, increase the contact probability of active group and organic sulfur, thus improve desulfurization performance.And for Ag/TiO ₂, photocatalysis preparation process not only can excite more free hydroxyl group, produces more-OH, also can form more Ag-O-Ti active group.Therefore, the TiO after process of the present invention is utilized ₂the desulfuration adsorbent of class, the hydrogen-oxygen active group had is more, and the desulphurizing ability of adsorbent is stronger, and efficiency is higher, better effects if.

Compared with existing absorbent preparation technology, advantage of the present invention is:

1, the present invention utilizes TiO ₂adsorption mechanism, excites TiO by photocatalysis ₂the hydroxy radical group on surface, then this mechanism is combined with the adsorption desulfurize mechanism of titanium dioxide, formed and prepare TiO by photocatalysis mode ₂class desulfuration adsorbent, substantially increases existing TiO ₂the usefulness of class adsorption desulfurizing agent.

2, adopt low-power ultraviolet device, also can utilize the ultraviolet light in sunshine, realize the active group exciting adsorbent, reduce energy resource consumption, and the industrialization of photocatalysis preparation technology can be realized.

3, the desulphurizing activated group energy stable existence excited by photocatalysis is in adsorbent surface, the adsorbent prepared through photocatalysis is appointed under the high temperature conditions can stable existence, adsorbent prepared by this type of photocatalysis can regenerate and reuse, and keeps original desulfurization performance simultaneously.

Accompanying drawing explanation

Fig. 1 is a kind of photocatalysis Ag/TiO provided by the invention ₂preparation flow schematic diagram.

Fig. 2 is the schematic flow sheet of a kind of adsorption desulfurize fixed bed reaction technique provided by the invention and adsorbent reactivation technique.

Fig. 3 prepares for tradition and adsorbent TiO is prepared in photocatalysis of the present invention ₂performance comparison figure.

Fig. 4 prepares for tradition and adsorbent TiO is prepared in photocatalysis ₂be loaded in Al ₂o ₃(TiO ₂-Al ₂o ₃) on performance comparison figure.

Fig. 5 prepares for tradition and prepares adsorbent A g/TiO with embodiment of the present invention photocatalysis ₂performance comparison figure.

Fig. 6 prepares Ag/TiO for using the preparation of aviation fuel test tradition with embodiment of the present invention photocatalysis ₂performance comparison figure.

Detailed description of the invention

Below in conjunction with drawings and Examples, technical solution of the present invention is described further.

Embodiment 1:

The present embodiment adopts following steps to prepare photocatalysis TiO ₂adsorbent:

(1) TiO ₂absorbent preparation

The titania support (commercially available) provided by SaintGobainNorpro is provided in the present embodiment, utilizes BET method to measure its pore volume for 0.44mL/g.By TiO ₂particulate abrasive and screening to 850 ~ 1400 μm of sizes, in an oven about 100 DEG C drying more than 6 hours for subsequent use.

(2) photocatalysis preparation process

1. remove ionized water with dropper, drop in TiO ₂on, constantly stir, until naked eyes are seen, and adsorbent has a large amount of liquid film, now stop dripping.This step does not limit the number of deionized water, makes TiO as far as possible ₂adsorbent is moistening, awash.

2. the ultraviolet catalytic treatment process of the present embodiment employing, its device is low-power (4watt) Portable ultraviolet lamp, and wavelength is 365nm, is about 2mW/cm in the UV intensity of distance fluorescent tube 10cm ².Oversaturated adsorbent is evenly spread out in evaporating dish, irradiates 2 hours under being placed in ultraviolet light.About 100 DEG C, baking oven is put into again dry 6 hours again after putting into afterwards.

3. the TiO prepared by photocatalysis ₂adsorbent in dry air 450 DEG C calcining 2 hours, until its cooling after namely can be used for adsorption desulfurize process.

(3) adsorbent desulfurization performance is tested

See accompanying drawing 2, it is the schematic flow sheet of a kind of adsorption desulfurize fixed bed reaction technique provided by the invention and adsorbent reactivation technique.Utilize desulfurization breakthrough experiment, use standard sample fuel to test respectively adsorbent prepared by traditional handicraft and TiO prepared by photocatalysis ₂performance of the adsorbent.Concrete steps are as follows:

1. be dissolved in normal octane by benzene thiophene, configuration sulfur-bearing standard sample fuel, in the present embodiment, the organic sulfur content of fuel standard sample is 3500ppmw;

2. the TiO that prepared by traditional handicraft and prepared by photocatalysis is taken ₂the each 10.0g of adsorbent, is packed into fixed bed desulfurization reactor respectively;

3. utilize the reaction unit in accompanying drawing 2, carry out breakthrough experiment.Within every 5 to 10 minutes, get fluid sample, with the organic sulfur content in liquid phase GC analyzing liquid sample.

4. draw breakthrough curve, calculate break through volume and the saturated adsorption capacity of adsorbent thus.Finally the adsorbent capacity data that two kinds of methods prepare are contrasted.Comparing result lists see accompanying drawing 3. table 1 to be prepared and the two kinds of TiO inventing preparation thus by conventional method ₂adsorbent this experiment in penetration performance and saturated performance value for contrast.

Embodiment 2:

The present embodiment adopts following steps to prepare photocatalysis TiO ₂be loaded in high surface area carrier materials A l ₂o ₃(TiO ₂-Al ₂o ₃) adsorbent:

(1) Al ₂o ₃the preparation of carrier

(commercially available) alundum (Al2O3) Al provided by AlfaAesar is provided in the present embodiment ₂o ₃carrier, utilizes BET method to measure its pore volume for 1.0mL/g.By Al ₂o ₃particulate abrasive and screening to 850 ~ 1400 μm of sizes, in an oven about 100 DEG C drying more than 6 hours for subsequent use.

(2) use " equi-volume impregnating ", the metal Ti weight of carrying as required, (the present embodiment is C to calculate required organic titanium ₁₂h ₂₈o ₄ti) solution concentration and prepare TiO ₂-Al ₂o ₃adsorbent:

1. determine to need the Ti weight of carrying to be whole TiO ₂-Al ₂o ₃the 10wt% of adsorbent weight, namely

$\frac{m_{\mathrm{Ti}}}{m_{\mathrm{Ti}{O}_2}-{\mathrm{Al}}_2{O}_3}=0.10.$

2. the Al of 10.0g is taken ₂o ₃carrier, according to " equi-volume impregnating ", total pore volume of carrier is the volume of required organic Ti solution:

V _Ti＝10.0g×1.0mL/g＝10mL。

3. the Ti molal weight n that following formulae discovery needs is utilized _ti;

Wherein MW _tifor the molecular weight of titanium, for the molecular weight of titanium dioxide, for Al ₂o ₃quality.

Above-mentioned formulae discovery is utilized to draw Ti molal weight n _tifor 0.025mol.

4. the molar concentration of corresponding solution is drawn according to calculated Ti molal weight and liquor capacity:

$C_{Ti}=\frac{n_{Ti}}{V_{Ti}}=\frac{0.025mol}{10mL}=2.5\×{10}^{-3}mol/mL.$

5. dropper is utilized to get the C of the certain concentration of 10mL ₁₂h ₂₈o ₄ti maceration extract dropwise instills Al ₂o ₃carrier, constantly stirs simultaneously, carrier is fully contacted with maceration extract, tentatively obtains the TiO of 10wt% ₂-Al ₂o ₃.

(3) photocatalysis preparation process

1. remove ionized water by drip irrigation, drop in 10wt%TiO ₂-Al ₂o ₃on, constantly stir, until naked eyes are seen, and adsorbent has a large amount of liquid film, now stop dripping.This step does not limit the number of deionized water, is that adsorbent is moistening as far as possible, awash.

2. the ultraviolet generation device in the present embodiment is low-power (4watt) Portable ultraviolet lamp, and wavelength is 365nm, is about 2mW/cm in the UV intensity of distance fluorescent tube 10cm ².Oversaturated adsorbent is evenly spread out in evaporating dish, irradiates 2 hours under being placed in ultraviolet light.About 100 DEG C, baking oven is put into again dry 6 hours again after putting into afterwards.

3. the adsorbent prepared by photocatalysis in dry air 550 DEG C calcining 2 hours, until its cooling after namely can be used for adsorption desulfurize process.

(4) adsorbent desulfurization performance is tested

Utilize desulfurization breakthrough experiment, use standard sample fuel to test respectively adsorbent prepared by traditional handicraft and TiO prepared by photocatalysis ₂-Al ₂o ₃performance of the adsorbent.Concrete steps are as follows:

1. be dissolved in normal octane by benzene thiophene, configuration sulfur-bearing standard sample fuel, in the present embodiment, the organic sulfur content of fuel standard sample is 3500ppmw.

2. the 10wt%TiO that prepared by traditional handicraft and prepared by photocatalysis is taken ₂-Al ₂o ₃the each 10.0g of adsorbent, is packed into fixed bed desulfurization reactor respectively.

3. utilize the reaction unit in Fig. 2, carry out breakthrough experiment.Within every 5 to 10 minutes, get fluid sample, with the organic sulfur content in liquid phase GC analyzing liquid sample.

4. draw breakthrough curve, calculate break through volume and the saturated adsorption capacity of adsorbent thus.Finally the adsorbent capacity data that two kinds of methods prepare are contrasted.Comparing result is see accompanying drawing 4.Table 1 lists to be prepared and the two kinds of TiO inventing preparation thus by conventional method ₂-Al ₂o ₃adsorbent this experiment in penetration performance and saturated performance value for contrast.

Embodiment 3:

See accompanying drawing 1, it is a kind of photocatalysis Ag/TiO provided by the invention ₂preparation flow schematic diagram, the present embodiment adopt following steps prepare Ag/TiO ₂adsorbent:

(1) TiO ₂the preparation of carrier

In the present embodiment, select the titania support that SaintGobainNorpro provides, utilize BET method to measure its pore volume for 0.44mL/g.By TiO ₂particulate abrasive and screening to particle diameter be 850 ~ 1400 μm, in an oven about 100 DEG C drying more than 6 hours for subsequent use.

(2) use " equi-volume impregnating ", the weight metal carried as required, calculate required AgNO ₃the concentration of solution and prepare AgNO ₃adsorbent.

1. first determine to need the argent weight of carrying to be whole Ag/TiO ₂the 4wt% of adsorbent weight, that is:

$\frac{m_{Ag}}{m_{\frac{Ag}{{\mathrm{TiO}}_2}}}=\mathrm{0.04.}$

2. the TiO of 10.0g is taken ₂carrier, according to " equi-volume impregnating ", total pore volume of carrier is required AgNO ₃the volume of liquid:

3. the AgNO that following formulae discovery needs is utilized ₃molal weight

$\frac{{\mathrm{MW}}_{Ag}\×n_{{\mathrm{AgNO}}_2}}{{\mathrm{MW}}_{Ag}\×n_{{\mathrm{AgNO}}_2}+m_{{\mathrm{TiO}}_2}}=0.04,$

Wherein MW _agfor the molecular weight of silver, for the weight of titanium dioxide.Above-mentioned formulae discovery is utilized to draw AgNO ₃molal weight is 3.858 × 10 ^-3mol.

4. according to calculated AgNO ₃molal weight and liquor capacity draw the molar concentration of corresponding solution:

5. dropper is utilized to get the AgNO of the certain concentration of 4.4mL ₃maceration extract dropwise instills TiO ₂carrier, constantly stirs simultaneously, carrier is fully contacted with maceration extract, tentatively obtains the Ag/TiO that Ag content is 4wt% ₂.

(3) photocatalysis preparation process

1. remove ionized water by drip irrigation, drop in Ag/TiO ₂on, constantly stir, until naked eyes are seen, and adsorbent has a large amount of liquid film, now stop dripping.This step does not limit the number of deionized water, is that adsorbent is moistening as far as possible, awash.

2. the ultraviolet generation device in the present embodiment is low-power (4watt) Portable ultraviolet lamp, and wavelength is 365nm, is about 2mW/cm in the UV intensity of distance fluorescent tube 10cm ².Oversaturated adsorbent is evenly spread out in evaporating dish, irradiates 2 hours under being placed in ultraviolet light.About 100 DEG C, baking oven is put into again dry 6 hours again after putting into afterwards.

3. the adsorbent prepared by photocatalysis in dry air 450 DEG C calcining 2 hours, until its cooling after namely can be used for adsorption desulfurize process.

(4) adsorbent desulfurization performance is tested

Performance of the adsorbent prepared by the adsorbent utilizing desulfurization breakthrough experiment test traditional handicraft to prepare and photocatalysis.Concrete steps are as follows:

1. be dissolved in normal octane by benzene thiophene, configuration sulfur-bearing standard sample fuel, in the present embodiment, the organic sulfur content of fuel standard sample is 3500ppmw.

2. the 4wt%Ag/TiO that prepared by traditional handicraft and the present invention adopts photocatalysis to prepare is taken ₂the each 10.0g of adsorbent, is packed in fixed bed desulfurization reactor respectively.

3. see accompanying drawing 2, it is the schematic flow sheet of adsorption desulfurize fixed bed reaction technique and adsorbent reactivation technique, and the present embodiment carries out breakthrough experiment by this technological process.Within every 5 to 10 minutes, get fluid sample, with the organic sulfur content in liquid phase GC analyzing liquid sample.

4. draw breakthrough curve, calculate break through volume and the saturated adsorption capacity of adsorbent thus.Finally the adsorbent capacity data that two kinds of methods prepare are contrasted.Comparing result is see Fig. 5.

Table 1 summarizes the three kinds of TiO being prepared by conventional method and prepared by the present invention ₂class adsorbent this experiment in penetration performance and saturated performance value for contrast.

Table 1

5. for Ag/TiO prepared by traditional handicraft preparation and the present embodiment photocatalysis ₂, again test with military aviation fuel JP5, comparing result is see Fig. 6 and table 2.

Table 2

Preparation method's simple possible provided by the invention, can not only improve the desulfurization performance of titanium dioxide, can also effectively improve with acid hydroxide groups be desulphurizing activated in the desulfurization absorption property of all adsorbents, thus promote the development of adsorption desulfurize technology.

Claims (4)

1. TiO is prepared in a photocatalysis ₂the method of gasoline liquid adsorption desulfurization agent, is characterized in that comprising the steps:

(1) TiO is determined ₂pore volume, by TiO ₂particulate abrasive, screening to particle diameter is 850 ~ 1400 μm, is that under the condition of 100 ~ 150 DEG C, drying processes 6 ~ 12 hours in temperature;

(2) under the condition constantly stirred, deionized water is dropped in TiO ₂on, fully moistening to TiO ₂upper formation liquid film;

(3) by fully moistening TiO ₂evenly spread out, under ultraviolet catalytic condition, process 2 ~ 4 hours, then drying process 6 ~ 12 hours;

(4) product step (3) obtained is calcine 2 ~ 3 hours in the dry air of 400 ~ 450 DEG C in temperature, after being cooled to room temperature, obtains a kind of TiO ₂desulfuration adsorbent.

2. TiO is prepared in a photocatalysis ₂the method of-carrier material gasoline liquid adsorption desulfurization agent, is characterized in that comprising the steps:

(1) organic titanium solution is pressed TiO ₂the weight of the Ti that the agent of-carrier material gasoline liquid adsorption desulfurization is carried is 2 ~ 20wt%, is configured to organic titanium mixed impregnant liquor;

(2) by " equi-volume impregnating ", mixed impregnant liquor is instilled on metal oxide support material, under the condition constantly stirred, tentatively obtain TiO ₂-carrier material head product;

(3) head product obtained in step (2) drips deionized water, constantly stirs, occur supersaturation to surface;

(4) product that step (3) obtains evenly is spread out, under ultraviolet catalytic condition, process 2 ~ 4 hours, then drying process 6 ~ 12 hours;

(5) product step (4) obtained is calcine 2 ~ 3 hours in the dry air of 500 ~ 550 DEG C in temperature, after being cooled to room temperature, obtains TiO ₂-carrier material desulfuration adsorbent.

3. TiO is prepared in a kind of photocatalysis according to claim 2 ₂the method of-carrier material gasoline liquid adsorption desulfurization agent, is characterized in that: described organic titanium solution is C ₁₂h ₂₈o ₄ti; Described metal oxide support material is Al ₂o ₃.

4. Ag/TiO is prepared in a photocatalysis ₂the method of gasoline liquid adsorption desulfurization agent, is characterized in that comprising the steps:

(1) TiO is determined ₂pore volume, by TiO ₂particulate abrasive, screening to particle diameter is 850 ~ 1400 μm, is that under the condition of 100 ~ 150 DEG C, drying processes 6 ~ 12 hours in temperature;

(2) by Ag/TiO ₂the metal A g weight that gasoline liquid adsorption desulfurization agent is carried is 2 ~ 10wt%, preparation AgNO ₃maceration extract, by " equi-volume impregnating ", at TiO ₂carrier drips AgNO ₃maceration extract, under continuous stirring condition, obtains Ag/TiO ₂;

(3) under constant agitation deionized water drop is added in Ag/TiO prepared by step (2) ₂on, to Ag/TiO ₂surface produces liquid film or occurs supersaturation, obtains fully moistening Ag/TiO ₂;

(4) by fully moistening Ag/TiO ₂evenly spread out, under ultraviolet catalytic condition, process 2 ~ 4 hours, then be dry process 6 ~ 12 hours under the condition of 100 ~ 150 DEG C in temperature;

(5) product step (4) obtained is calcine 2 ~ 3 hours in the dry air of 400 ~ 450 DEG C in temperature, after being cooled to room temperature, obtains a kind of Ag/TiO ₂gasoline liquid adsorption desulfurization agent.