CN103007873A - Adsorbent for gasoline desulfurization and preparation method as well as application thereof - Google Patents

Adsorbent for gasoline desulfurization and preparation method as well as application thereof Download PDF

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CN103007873A
CN103007873A CN2013100138784A CN201310013878A CN103007873A CN 103007873 A CN103007873 A CN 103007873A CN 2013100138784 A CN2013100138784 A CN 2013100138784A CN 201310013878 A CN201310013878 A CN 201310013878A CN 103007873 A CN103007873 A CN 103007873A
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adsorbent
copper
gasoline
mesoporous
room temperature
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单佳慧
曹宇锋
丁欣宇
喻红梅
华平
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Nantong University
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Nantong University
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Abstract

The invention belongs to the technical field of fuel oil processing and discloses an adsorbent for gasoline desulfurization and a preparation method as well as application of the adsorbent. The adsorbent is characterized in that copper element doping mesoporous gamma-A12O is in contact with fuel oil containing sulfur, and desulphurization is realized by an adsorption method. The adsorption operation can be carried out at normal temperatures and pressures, and the operation cost is low. The adsorbent has great adsorption capacity on thiophenic sulfur and good desulfurization effect, is convenient to regenerate and still has better desulfurization effect after being regenerated.

Description

A kind of adsorbent for gasoline desulfur and its preparation method and application
Technical field
The invention belongs to the fuel oil processing technique field, relate to mesoporous that a kind of copper mixes γ-Al 2O 3Adsorbent and preparation method thereof and the application in gasoline desulfur.
Background technology
World's crude oil heaviness, in poor quality have the trend of increasingly sharpening, and the sulfur content in the crude oil constantly increases.Sulphides burn in gasoline, the diesel oil generates SO xOne of major pollutants of vehicle exhaust.SO xBe discharged in the atmosphere and can cause acid rain, that main is SO xBe the mortifier of cleaning catalyst for tail gases of automobiles, can significantly reduce automobile exhaust purifier to NO x, imperfect combustion hydro carbons purifying rate.Therefore, along with the increasingly stringent of environmental legislation, countries in the world are more and more stricter to the requirement of Sulfur content in Fuel Oil content.Although traditional hydrodesulfurization can remove most of sulfide effectively, and is undesirable to the removal effect of thiophene-type sulfide.In many super degree of depth desulfurization of fuel oil technology, the absorption method desulfurization has that operating condition gentleness, desulfurized effect are good, investment and operating cost is low, alkene the advantage such as is not reduced by the octane number in saturated, the fuel oil, is one of the most promising method.
Document (Ind. Eng. Chem. Res., 2006, reported CuCl has been loaded on the SBA-15 45:7892) that remove thiophene in the analog fuel oil as adsorbent, the result shows that SBA-15/Cu (I) improves a lot to the adsorbance of thiophene.
Document (Chem. Eng. Sci., 2008,63:356) reported CuCl, PdCl 2Load on MCM-41 and the SBA-15 by hot dispersion method, remove the sulfide among the Aviation Fuel JP-5, show good adsorption desulfurize performance.
Document (Ind. Eng. Chem. Res., 2009,48: 142) reported (NO with Cu 3) 22H 2O loads on SBA-15 and the MCM-41 by infusion process, makes adsorbent Cu 2O/SBA-15 and Cu 2O/MCM-41.The result shows that this adsorbent has preferably adsorption effect to the sulfide among the Aviation Fuel JP-5.
Up to now, there is not yet utilize copper to mix mesoporous γ-Al 2O 3As adsorbent, the report of deep removal sulfide in petrol.
Summary of the invention
The object of the present invention is to provide a kind of adsorbent, adsorbent for removing the gasoline thiophene-type sulfide the preparation method, utilize described adsorbent that gasoline is carried out the method for adsorbing and removing thiophene-type sulfide, the renovation process of described adsorbent, this adsorbent adopts mesoporous that copper mixes γ-Al 2O 3Adsorbent carries out adsorbing and removing to the sulfide in the gasoline under temperate condition.
The objective of the invention is to realize by following technical proposal:
A kind of adsorbent for gasoline desulfur, this adsorbent are the mesoporous of copper doping γ-Al 2O 3
Described adsorbent, wherein mantoquita is one or more in copper nitrate, copper sulphate, copper chloride, the Schweinfurt green.
It is mesoporous that copper mixes γ-Al 2O 3Prepare by the synthetic method of following Direct Hydrothermal: with the Al (NO of 39wt% 3) 39H 2O, template P123 and distilled water mix, and add subsequently mantoquita, the solution that then obtains clarifying at 30 ~ 45 ℃ of lower stirring 36 h; Stop this moment stirring static ageing 6 ~ 8 h.After ageing finishes, slowly dropwise adding respectively precipitating reagent under the stirring, precipitating reagent is for containing 10 wt% NaOH, 13 wt% Na 2CO 3With 40 wt% K 2CO 3Solution, percentage refers to respectively NaOH, Na in each solution 2CO 3And K 2CO 3Mass content, be incorporated with in the teflon-lined stainless steel cauldron after ageing 6 ~ 8 h under the room temperature, 100 ℃ of lower ageing 24 h that continue, the hole wall of gained mesoporous material is by the AlOOH(boehmite at this moment) consist of, with deionized water the gained sample is washed fully, behind the suction filtration, at room temperature naturally dry and namely get former powder, former powder be the copper of not removed template method P123 mix mesoporous γ-Al 2O 3At air atmosphere, 500 ~ 550 ℃ of lower roasting 4 ~ 6 h, in roasting process, the hole wall of mesoporous material is converted into by AlOOH with former powder γ-Al 2O 3Again with the sample after the roasting in inert gas atmosphere, 550 ~ 650 ℃ of lower autoreduction 12 ~ 24 h, be cooled to mesoporous that room temperature obtains namely that copper mixes γ-Al 2O 3What wherein synthetic copper mixed is mesoporous γ-Al 2O 3Quantity of reaction mass than the mol ratio that is scaled respective substance be: 1.0Al 3+: 0.011P123:3OH -: (0.01 ~ 0.3) Cu 2+
Described preparation method, wherein copper and mesoporous γ-Al 2O 3In the mol ratio of aluminium element be 0.01 ~ 0.3; Inert gas is He, Ar or N 2
A kind of sulfur method of gasoline, the method adopt above-mentioned adsorbent to contact with the gasoline of sulfur-bearing, utilize absorption method to realize the desulfurization of gasoline.
Described gasolene desulfurizing method by adsorption, wherein the condition that contacts with adsorbent of gasoline is that temperature is: room temperature ~ 50 ℃ are preferably room temperature; Adsorbent is 1:35 ~ 100 with the quality of gasoline ratio; Pressure is the pressure of normal pressure ~ 0.5MPa, is preferably normal pressure.
Described gasolene desulfurizing method by adsorption, the sulphur impurity that wherein contains are generally thiophene, benzothiophene, dibenzothiophenes and their a series of organic sulfur compounds such as derivative.
The renovation process of described adsorbent, the method are with the adsorbent behind the saturated adsorption, purge 4 ~ 6 h in 300 ~ 500 ℃ air atmosphere, then at inert gas atmosphere, 550 ~ 650 ℃ of lower autoreduction 12 ~ 24 h.Adsorbent after the regeneration is reusable.
It is mesoporous that copper mixes γ-Al 2O 3During adsorbent performance suction-operated, copper is take monovalence copper as main.Cupric can the spontaneous monovalence copper that is reduced under proper temperature, inert atmosphere.
Adsorbent does not add the finished product that explanation all refers to removed template method.It is mesoporous that copper mixes γ-Al 2O 3It is mesoporous that former powder refers to that the copper of removed template method P123 not mixes γ-Al 2O 3
Gasoline desulfating method provided by the invention it is characterized in that the method comprise with the gasoline of sulfur-bearing and a kind of copper mix mesoporous γ-Al 2O 3Adsorbent contacts, and the stirring reaction certain hour filters at a certain temperature, utilizes absorption method to realize the deep desulfuration of gasoline.Liquid product is measured its sulfur content with ANTK-9000 Sulfur Analysis instrument.
Beneficial effect of the present invention:
Novel desulphurization adsorbent provided by the invention is owing to adopt the mesoporous of copper doping γ-Al 2O 3As adsorbent, large to the adsorption capacity of thiophene and derivatives, desulfurization degree is high; Adsorption operations can carry out at normal temperatures and pressures, and running cost reduces; Adsorbent reactivation is convenient, still can keep preferably desulfurized effect after the regeneration.Novelty of the present invention is mainly reflected in two aspects: the one, and the innovation on the carrier is namely with mesoporous γ-Al 2O 3As carrier; The 2nd, the innovation on the absorbent preparation method, document is generally introduced copper compound by the method for " load ", and the degree of scatter of copper is not high; And the present invention is incorporated into copper mesoporous by the synthetic method of original position γ-Al 2O 3In, can realize the high degree of dispersion of copper.
The specific embodiment
In order to deepen the understanding of the present invention, the invention will be further described below in conjunction with embodiment, and following examples only are used for explaining the present invention, do not consist of the restriction to protection domain of the present invention.
The adsorbent that is used for gasoline desulfur is mesoporous γ-Al2O3 that copper mixes; It is mesoporous that copper mixes γ-Al 2O 3Middle copper and mesoporous γ-Al 2O 3In the mol ratio of aluminium element be 0.01 ~ 0.3; The mantoquita of copper is one or more in copper nitrate, copper sulphate, copper chloride, the Schweinfurt green.
The adsorbent that is used for gasoline desulfur is the mesoporous of copper doping γ-Al 2O 3, it is mesoporous that copper mixes γ-Al 2O 3The method synthetic by following Direct Hydrothermal prepares: with the Al (NO of 39wt% 3) 39H 2O, template P123 and distilled water mix, and add subsequently mantoquita, the solution that then obtains clarifying at 30 ~ 45 ℃ of lower stirring 36 h; Stop this moment stirring static ageing 6 ~ 8 h.After ageing finishes, slowly dropwise adding respectively precipitating reagent under the stirring, precipitating reagent is for containing 10 wt% NaOH, 13 wt% Na 2CO 3With 40 wt% K 2CO 3Solution, percentage refers to respectively NaOH, Na in each solution 2CO 3And K 2CO 3Mass content, be incorporated with in the teflon-lined stainless steel cauldron after ageing 6 ~ 8 h under the room temperature, 100 ℃ of lower ageing 24 h that continue, the hole wall of gained mesoporous material is by the AlOOH(boehmite at this moment) consist of, with deionized water the gained sample is washed fully, behind the suction filtration, at room temperature naturally dry and namely get former powder, former powder be the copper of not removed template method P123 mix mesoporous γ-Al 2O 3At air atmosphere, 500 ~ 550 ℃ of lower roasting 4 ~ 6 h, in roasting process, the hole wall of mesoporous material is converted into by AlOOH with former powder γ-Al 2O 3Again with the sample after the roasting in inert gas atmosphere, 550 ~ 650 ℃ of lower autoreduction 12 ~ 24 h, be cooled to mesoporous that room temperature obtains namely that copper mixes γ-Al 2O 3What wherein synthetic copper mixed is mesoporous γ-Al 2O 3Quantity of reaction mass than the mol ratio that is scaled respective substance be: 1.0Al 3+: 0.011P123:3OH -: (0.01 ~ 0.3) Cu 2+The consumption of mantoquita is copper and mesoporous in copper γ-Al 2O 3In the mol ratio of aluminium element be 0.01 ~ 0.3, described inert gas is He, Ar or N 2
Adopt the method for the gasoline desulfur of the adsorbent that is used for gasoline desulfur, adsorbent contacts with the gasoline of sulfur-bearing, utilizes absorption method to realize the desulfurization of gasoline; Gasoline is the gasoline that contains thiophene-type sulfide; Gasoline with the condition that described adsorbent contacts is: temperature is room temperature to 50 ℃, is preferably room temperature, and adsorbent and quality of gasoline are than being 1:35 ~ 100, and pressure is normal pressure ~ 0.5MPa, is preferably normal pressure.
Be used for the renovation process of the adsorbent of gasoline desulfur, the adsorbent behind the saturated adsorption purged 4 ~ 6 h in 300 ~ 500 ℃ air atmosphere, then at inert gas atmosphere, 550 ~ 650 ℃ of lower autoreduction 12 ~ 24 h.
Embodiment describes respectively adsorbent to the desulfurized effect of thiophene-type sulfide, because dibenzothiophenes and 4, the 6-dimethyl Dibenzothiophene is for thiophene, it is the relatively more difficult large molecule organic sulfur compound that removes, so although what all be made into is that sulfur content is the analog gasoline of 500 ppm, adsorbent is to dibenzothiophenes and 4, the desulfurized effect of 6-dimethyl Dibenzothiophene is compared with thiophene, still has some gaps.
Following example will be further described the present invention, but content of the present invention is not limited to this fully.
Embodiment 1
Al (NO with 0.1 mol 3) 39H 2O adds in the 18.0 g water, adds until completely dissolved 6.38 g template P123, adds subsequently the Cu (NO of 0.005 mol 3) 33H 2O, the solution that then obtains clarifying at 40 ℃ of lower stirring 36 h.Stop this moment stirring static ageing 8 h.After ageing finishes, the precipitating reagent NaOH(10 wt% that under slow stirring, dropwise adds respectively 0.3 mol), be incorporated with in the teflon-lined stainless steel cauldron after ageing 8 h under the room temperature, 100 ℃ of lower ageing 24 h that continue, the hole wall of gained mesoporous material is by the AlOOH(boehmite at this moment) consist of.With a large amount of deionized waters the gained sample is washed fully, behind the suction filtration, at room temperature naturally dry and namely get former powder.At air atmosphere, 550 ℃ of lower roasting 4 h, in roasting process, the hole wall of mesoporous material is converted into by AlOOH with former powder γ-Al 2O 3Again with the sample after the roasting in inert gas atmosphere, 550 ℃ of lower autoreduction 24 h, be cooled to mesoporous that room temperature obtains namely that copper mixes γ-Al 2O 3The content that ICP measures copper is 4.8 % of adsorbent gross mass.0.1815 g thiophene is dissolved in the analog gasoline that is made into sulfur content 500 ppm in the 200 mL isooctane.Get this analog gasoline of 20 mL, to wherein adding mesoporous that the above-mentioned copper of 0.3101 g mixes γ-Al 2O 3, stirring reaction 6 h under the room temperature normal pressure filter.Liquid product is measured its sulfur content with ANTK-9000 Sulfur Analysis instrument.Sulfur content is down to 386 ppm from 500 ppm.Desulfurization amount is 163.6 μ mol sulphur/g adsorbents.
Embodiment 2
Al (NO with 0.1 mol 3) 39H 2O adds in the 18.0 g water, adds until completely dissolved 6.38 g template P123, adds subsequently the Cu (NO of 0.01 mol 3) 33H 2O, the solution that then obtains clarifying at 40 ℃ of lower stirring 36 h.Stop this moment stirring static ageing 8 h.After ageing finishes, the precipitating reagent NaOH(10 wt% that under slow stirring, dropwise adds respectively 0.3 mol), after ageing 8 h sample is incorporated with in the teflon-lined stainless steel cauldron under the room temperature, 100 ℃ of lower ageing 24 h that continue, the hole wall of gained mesoporous material is by the AlOOH(boehmite at this moment) consist of.With a large amount of deionized waters the gained sample is washed fully, behind the suction filtration, at room temperature naturally dry and namely get former powder.At air atmosphere, 550 ℃ of lower roasting 4 h, in roasting process, the hole wall of mesoporous material is converted into by AlOOH with former powder γ-Al 2O 3Again with the sample after the roasting in inert gas atmosphere, 550 ℃ of lower autoreduction 24 h, be cooled to mesoporous that room temperature obtains namely that copper mixes γ-Al 2O 3The content that ICP measures copper is 10.1 % of adsorbent gross mass.0.1815 g thiophene is dissolved in the analog gasoline that is made into sulfur content 500 ppm in the 200 mL isooctane.Get this analog gasoline of 20 mL, to wherein adding mesoporous that the above-mentioned copper of 0.3015 g mixes γ-Al 2O 3, stirring reaction 6 h under the room temperature normal pressure filter.Liquid product is measured its sulfur content with ANTK-9000 Sulfur Analysis instrument.Sulfur content is down to 199 ppm from 500 ppm.Desulfurization amount is 431.2 μ mol sulphur/g adsorbents.
Embodiment 3
Al (NO with 0.1 mol 3) 39H 2O adds in the 18.0 g water, adds until completely dissolved 6.38 g template P123, adds subsequently the Cu (NO of 0.018 mol 3) 33H 2O, the solution that then obtains clarifying at 40 ℃ of lower stirring 36 h.Stop this moment stirring static ageing 8 h.After ageing finishes, the precipitating reagent NaOH(10 wt% that under slow stirring, dropwise adds respectively 0.3 mol), after ageing 8 h sample is incorporated with in the teflon-lined stainless steel cauldron under the room temperature, 100 ℃ of lower ageing 24 h that continue, the hole wall of gained mesoporous material is by the AlOOH(boehmite at this moment) consist of.With a large amount of deionized waters the gained sample is washed fully, behind the suction filtration, at room temperature naturally dry and namely get former powder.At air atmosphere, 550 ℃ of lower roasting 4 h, in roasting process, the hole wall of mesoporous material is converted into by AlOOH with former powder γ-Al 2O 3Again with the sample after the roasting in inert gas atmosphere, 550 ℃ of lower autoreduction 24 h, be cooled to mesoporous that room temperature obtains namely that copper mixes γ-Al 2O 3The content that ICP measures copper is 13.1 % of adsorbent gross mass.0.1815 g thiophene is dissolved in the analog gasoline that is made into sulfur content 500 ppm in the 200 mL isooctane.Get this analog gasoline of 20 mL, to wherein adding mesoporous that the above-mentioned copper of 0.3005 g mixes γ-Al 2O 3, stirring reaction 6 h under the room temperature normal pressure filter.Liquid product is measured its sulfur content with ANTK-9000 Sulfur Analysis instrument.Sulfur content is down to 112 ppm from 500 ppm.Desulfurization amount is 557.6 μ mol sulphur/g adsorbents.
Embodiment 4
Al (NO with 0.1 mol 3) 39H 2O adds in the 18.0 g water, adds until completely dissolved 6.38 g template P123, adds subsequently the Cu (NO of 0.027 mol 3) 33H 2O, the solution that then obtains clarifying at 40 ℃ of lower stirring 36 h.Stop this moment stirring static ageing 8 h.After ageing finishes, the precipitating reagent NaOH(10 wt% that under slow stirring, dropwise adds respectively 0.3 mol), after ageing 8 h sample is incorporated with in the teflon-lined stainless steel cauldron under the room temperature, 100 ℃ of lower ageing 24 h that continue, the hole wall of gained mesoporous material is by the AlOOH(boehmite at this moment) consist of.With a large amount of deionized waters the gained sample is washed fully, behind the suction filtration, at room temperature naturally dry and namely get former powder.At air atmosphere, 550 ℃ of lower roasting 4 h, in roasting process, the hole wall of mesoporous material is converted into by AlOOH with former powder γ-Al 2O 3Again with the sample after the roasting in inert gas atmosphere, 550 ℃ of lower autoreduction 24 h, be cooled to mesoporous that room temperature obtains namely that copper mixes γ-Al 2O 3The content that ICP measures copper is 18.2 % of adsorbent gross mass.0.1815 g thiophene is dissolved in the analog gasoline that is made into sulfur content 500 ppm in the 200 mL isooctane.Get this analog gasoline of 20 mL, to wherein adding mesoporous that the above-mentioned copper of 0.3001 g mixes γ-Al 2O 3, stirring reaction 6 h under the room temperature normal pressure filter.Liquid product is measured its sulfur content with ANTK-9000 Sulfur Analysis instrument.Sulfur content is down to 11ppm from 500 ppm.Desulfurization amount is 703.7 μ mol sulphur/g adsorbents.
Embodiment 5
Al (NO with 0.1 mol 3) 39H 2O adds in the 18.0 g water, adds until completely dissolved 6.38 g template P123, adds subsequently the Cu (NO of 0.01 mol 3) 33H 2O, the solution that then obtains clarifying at 40 ℃ of lower stirring 36 h.Stop this moment stirring static ageing 8 h.After ageing finishes, under slow stirring, dropwise add respectively the precipitating reagent K of 0.15 mol 2CO 3(40 wt%) is incorporated with sample in the teflon-lined stainless steel cauldron after ageing 8 h under the room temperature, 100 ℃ of lower ageing 24 h that continue, the hole wall of gained mesoporous material is by the AlOOH(boehmite at this moment) consist of.With a large amount of deionized waters the gained sample is washed fully, behind the suction filtration, at room temperature naturally dry and namely get former powder.At air atmosphere, 550 ℃ of lower roasting 4 h, in roasting process, the hole wall of mesoporous material is converted into by AlOOH with former powder γ-Al 2O 3Again with the sample after the roasting in inert gas atmosphere, 550 ℃ of lower autoreduction 24 h, be cooled to mesoporous that room temperature obtains namely that copper mixes γ-Al 2O 3The content that ICP measures copper is 9.3 % of adsorbent gross mass.0.1815 g thiophene is dissolved in the analog gasoline that is made into sulfur content 500 ppm in the 200 mL isooctane.Get this analog gasoline of 20 mL, to wherein adding mesoporous that the above-mentioned copper of 0.3128 g mixes γ-Al 2O 3, stirring reaction 6 h under the room temperature normal pressure filter.Liquid product is measured its sulfur content with ANTK-9000 Sulfur Analysis instrument.Sulfur content is down to 231 ppm from 500 ppm.Desulfurization amount is 371.4 μ mol sulphur/g adsorbents.
Embodiment 6
Al (NO with 0.1 mol 3) 39H 2O adds in the 18.0 g water, adds until completely dissolved 6.38 g template P123, adds subsequently the Cu (NO of 0.01 mol 3) 33H 2O, the solution that then obtains clarifying at 40 ℃ of lower stirring 36 h.Stop this moment stirring static ageing 8 h.After ageing finishes, under slow stirring, dropwise add respectively the precipitating reagent Na of 0.15 mol 2CO 3(13 wt%) is incorporated with sample in the teflon-lined stainless steel cauldron after ageing 8 h under the room temperature, 100 ℃ of lower ageing 24 h that continue, the hole wall of gained mesoporous material is by the AlOOH(boehmite at this moment) consist of.With a large amount of deionized waters the gained sample is washed fully, behind the suction filtration, at room temperature naturally dry and namely get former powder.At air atmosphere, 550 ℃ of lower roasting 4 h, in roasting process, the hole wall of mesoporous material is converted into by AlOOH with former powder γ-Al 2O 3Again with the sample after the roasting in inert gas atmosphere, 550 ℃ of lower autoreduction 24 h, be cooled to mesoporous that room temperature obtains namely that copper mixes γ-Al 2O 3The content that ICP measures copper is 9.5 % of adsorbent gross mass.0.1815 g thiophene is dissolved in the analog gasoline that is made into sulfur content 500 ppm in the 200 mL isooctane.Get this analog gasoline of 20 mL, to wherein adding mesoporous that the above-mentioned copper of 0.3109 g mixes γ-Al 2O 3, stirring reaction 6 h under the room temperature normal pressure filter.Liquid product is measured its sulfur content with ANTK-9000 Sulfur Analysis instrument.Sulfur content is down to 224 ppm from 500 ppm.Desulfurization amount is 383.4 μ mol sulphur/g adsorbents.
Embodiment 7
Al (NO with 0.1 mol 3) 39H 2O adds in the 18.0 g water, adds until completely dissolved 6.38 g template P123, adds subsequently the CuSO of 0.01 mol 45H 2O, the solution that then obtains clarifying at 40 ℃ of lower stirring 36 h.Stop this moment stirring static ageing 8 h.After ageing finishes, the precipitating reagent NaOH(10 wt% that under slow stirring, dropwise adds respectively 0.3 mol), after ageing 8 h sample is incorporated with in the teflon-lined stainless steel cauldron under the room temperature, 100 ℃ of lower ageing 24 h that continue, the hole wall of gained mesoporous material is by the AlOOH(boehmite at this moment) consist of.With a large amount of deionized waters the gained sample is washed fully, behind the suction filtration, at room temperature naturally dry and namely get former powder.At air atmosphere, 550 ℃ of lower roasting 4 h, in roasting process, the hole wall of mesoporous material is converted into by AlOOH with former powder γ-Al 2O 3Again with the sample after the roasting in inert gas atmosphere, 550 ℃ of lower autoreduction 24 h, be cooled to mesoporous that room temperature obtains namely that copper mixes γ-Al 2O 3The content that ICP measures copper is 9.2 % of adsorbent gross mass.0.1815 g thiophene is dissolved in the analog gasoline that is made into sulfur content 500 ppm in the 200 mL isooctane.Get this analog gasoline of 20 mL, to wherein adding mesoporous that the above-mentioned copper of 0.3007 g mixes γ-Al 2O 3, stirring reaction 6 h under the room temperature normal pressure filter.Liquid product is measured its sulfur content with ANTK-9000 Sulfur Analysis instrument.Sulfur content is down to 223 ppm from 500 ppm.Desulfurization amount is 397.8 μ mol sulphur/g adsorbents.
Embodiment 8
Al (NO with 0.1 mol 3) 39H 2O adds in the 18.0 g water, adds until completely dissolved 6.38 g template P123, adds subsequently the Cu (CH of 0.01 mol 3COO) H 2O, the solution that then obtains clarifying at 40 ℃ of lower stirring 36 h.Stop this moment stirring static ageing 8 h.After ageing finishes, the precipitating reagent NaOH(10 wt% that under slow stirring, dropwise adds respectively 0.3 mol), after ageing 8 h sample is incorporated with in the teflon-lined stainless steel cauldron under the room temperature, 100 ℃ of lower ageing 24 h that continue, the hole wall of gained mesoporous material is by the AlOOH(boehmite at this moment) consist of.With a large amount of deionized waters the gained sample is washed fully, behind the suction filtration, at room temperature naturally dry and namely get former powder.At air atmosphere, 550 ℃ of lower roasting 4 h, in roasting process, the hole wall of mesoporous material is converted into by AlOOH with former powder γ-Al 2O 3Again with the sample after the roasting in inert gas atmosphere, 550 ℃ of lower autoreduction 24 h, be cooled to mesoporous that room temperature obtains namely that copper mixes γ-Al 2O 3The content that ICP measures copper is 9.5 % of adsorbent gross mass.0.1815 g thiophene is dissolved in the analog gasoline that is made into sulfur content 500 ppm in the 200 mL isooctane.Get this analog gasoline of 20 mL, to wherein adding mesoporous that the above-mentioned copper of 0.3011 g mixes γ-Al 2O 3, stirring reaction 6 h under the room temperature normal pressure filter.Liquid product is measured its sulfur content with ANTK-9000 Sulfur Analysis instrument.Sulfur content is down to 233 ppm from 500 ppm.Desulfurization amount is 382.9 μ mol sulphur/g adsorbents.
Embodiment 9
Al (NO with 0.1 mol 3) 39H 2O adds in the 18.0 g water, adds until completely dissolved 6.38 g template P123, adds subsequently the CuCl of 0.01 mol 22H 2O, the solution that then obtains clarifying at 40 ℃ of lower stirring 36 h.Stop this moment stirring static ageing 8 h.After ageing finishes, the precipitating reagent NaOH(10 wt% that under slow stirring, dropwise adds respectively 0.3 mol), after ageing 8 h sample is incorporated with in the teflon-lined stainless steel cauldron under the room temperature, 100 ℃ of lower ageing 24 h that continue, the hole wall of gained mesoporous material is by the AlOOH(boehmite at this moment) consist of.With a large amount of deionized waters the gained sample is washed fully, behind the suction filtration, at room temperature naturally dry and namely get former powder.At air atmosphere, 550 ℃ of lower roasting 4 h, in roasting process, the hole wall of mesoporous material is converted into by AlOOH with former powder γ-Al 2O 3Again with the sample after the roasting in inert gas atmosphere, 550 ℃ of lower autoreduction 24 h, be cooled to mesoporous that room temperature obtains namely that copper mixes γ-Al 2O 3The content that ICP measures copper is 8.6 % of adsorbent gross mass.0.1815 g thiophene is dissolved in the analog gasoline that is made into sulfur content 500 ppm in the 200 mL isooctane.Get this analog gasoline of 20 mL, to wherein adding mesoporous that the above-mentioned copper of 0.3012 g mixes γ-Al 2O 3, stirring reaction 6 h under the room temperature normal pressure filter.Liquid product is measured its sulfur content with ANTK-9000 Sulfur Analysis instrument.Sulfur content is down to 269 ppm from 500 ppm.Desulfurization amount is 331.2 μ mol sulphur/g adsorbents.
Embodiment 10
Al (NO with 0.1 mol 3) 39H 2O adds in the 18.0 g water, adds until completely dissolved 6.38 g template P123, adds subsequently the Cu (NO of 0.01 mol 3) 33H 2O, the solution that then obtains clarifying at 40 ℃ of lower stirring 36 h.Stop this moment stirring static ageing 8 h.After ageing finishes, the precipitating reagent NaOH(10 wt% that under slow stirring, dropwise adds respectively 0.3 mol), after ageing 8 h sample is incorporated with in the teflon-lined stainless steel cauldron under the room temperature, 100 ℃ of lower ageing 24 h that continue, the hole wall of gained mesoporous material is by the AlOOH(boehmite at this moment) consist of.With a large amount of deionized waters the gained sample is washed fully, behind the suction filtration, at room temperature naturally dry and namely get former powder.At air atmosphere, 550 ℃ of lower roasting 4 h, in roasting process, the hole wall of mesoporous material is converted into by AlOOH with former powder γ-Al 2O 3Again with the sample after the roasting in inert gas atmosphere, 550 ℃ of lower autoreduction 24 h, be cooled to mesoporous that room temperature obtains namely that copper mixes γ-Al 2O 3The content that ICP measures copper is 10.1 % of adsorbent gross mass.0.4021 g dibenzothiophenes is dissolved in the analog gasoline that is made into sulfur content 500 ppm in the 200 mL isooctane.Get this analog gasoline of 20 mL, to wherein adding mesoporous that the above-mentioned copper of 0.3010 g mixes γ-Al 2O 3, stirring reaction 6 h under the room temperature normal pressure filter.Liquid product is measured its sulfur content with ANTK-9000 Sulfur Analysis instrument.Sulfur content is down to 230 ppm from 500 ppm.Desulfurization amount is 387.4 μ mol sulphur/g adsorbents.
Embodiment 11
Al (NO with 0.1 mol 3) 39H 2O adds in the 18.0 g water, adds until completely dissolved 6.38 g template P123, adds subsequently the Cu (NO of 0.01 mol 3) 33H 2O, the solution that then obtains clarifying at 40 ℃ of lower stirring 36 h.Stop this moment stirring static ageing 8 h.After ageing finishes, the precipitating reagent NaOH(10 wt% that under slow stirring, dropwise adds respectively 0.3 mol), after ageing 8 h sample is incorporated with in the teflon-lined stainless steel cauldron under the room temperature, 100 ℃ of lower ageing 24 h that continue, the hole wall of gained mesoporous material is by the AlOOH(boehmite at this moment) consist of.With a large amount of deionized waters the gained sample is washed fully, behind the suction filtration, at room temperature naturally dry and namely get former powder.At air atmosphere, 550 ℃ of lower roasting 4 h, in roasting process, the hole wall of mesoporous material is converted into by AlOOH with former powder γ-Al 2O 3Again with the sample after the roasting in inert gas atmosphere, 550 ℃ of lower autoreduction 24 h, be cooled to mesoporous that room temperature obtains namely that copper mixes γ-Al 2O 3The content that ICP measures copper is 10.1 % of adsorbent gross mass.With 0.4829g 4, the 6-dimethyl Dibenzothiophene is dissolved in the analog gasoline that is made into sulfur content 500 ppm in the 200 mL isooctane.Get this analog gasoline of 20 mL, to wherein adding mesoporous that the above-mentioned copper of 0.3009 g mixes γ-Al 2O 3, stirring reaction 6 h under the room temperature normal pressure filter.Liquid product is measured its sulfur content with ANTK-9000 Sulfur Analysis instrument.Sulfur content is down to 302 ppm from 500 ppm.Desulfurization amount is 284.2 μ mol sulphur/g adsorbents.
Embodiment 12
Al (NO with 0.1 mol 3) 39H 2O adds in the 18.0 g water, adds until completely dissolved 6.38 g template P123, adds subsequently the Cu (NO of 0.01 mol 3) 33H 2O, the solution that then obtains clarifying at 40 ℃ of lower stirring 36 h.Stop this moment stirring static ageing 8 h.After ageing finishes, the precipitating reagent NaOH(10 wt% that under slow stirring, dropwise adds respectively 0.3 mol), after ageing 8 h sample is incorporated with in the teflon-lined stainless steel cauldron under the room temperature, 100 ℃ of lower ageing 24 h that continue, the hole wall of gained mesoporous material is by the AlOOH(boehmite at this moment) consist of.With a large amount of deionized waters the gained sample is washed fully, behind the suction filtration, at room temperature naturally dry and namely get former powder.At air atmosphere, 550 ℃ of lower roasting 4 h, in roasting process, the hole wall of mesoporous material is converted into by AlOOH with former powder γ-Al 2O 3Again with the sample after the roasting in inert gas atmosphere, 550 ℃ of lower autoreduction 24 h, be cooled to mesoporous that room temperature obtains namely that copper mixes γ-Al 2O 3The content that ICP measures copper is 10.1 % of adsorbent gross mass.Get the FCC gasoline that 20 mL sulfur contents are 493 ppm, to wherein adding mesoporous that the above-mentioned copper of 0.3013 g mixes γ-Al 2O 3, stirring reaction 6 h under the room temperature normal pressure filter.Liquid product is measured its sulfur content with ANTK-9000 Sulfur Analysis instrument.Sulfur content is down to 235 ppm from 500 ppm.Desulfurization amount is 379.8 μ mol sulphur/g adsorbents.
Embodiment 13
Adsorbent behind the saturated adsorption among the embodiment 3 is purged in air, and in 2 h, be warming up to 500 ℃, keep 500 ℃ and purge 4 ~ 6 h, naturally cool to room temperature.Then at N 2Atmosphere, 650 ℃ of lower autoreduction 12 h.After the regeneration, again carry out gasoline desulfur by the method for embodiment 3 again, the adsorption capacity of sulphur can reach 95 % of initial adsorption capacity.
Embodiment 14
Adsorbent behind the saturated adsorption among the embodiment 3 is purged in air, and in 2 h, be warming up to 500 ℃, keep 500 ℃ and purge 4 ~ 6 h, naturally cool to room temperature.Then at He atmosphere, 650 ℃ of lower autoreduction 12 h.After the regeneration, again carry out gasoline desulfur by the method for embodiment 3 again, the adsorption capacity of sulphur can reach 98 % of initial adsorption capacity.
Novel desulphurization adsorbent provided by the invention is owing to adopt the mesoporous of copper doping γ-Al 2O 3As adsorbent, large to the adsorption capacity of thiophene and derivatives, desulfurization degree is high; Adsorption operations can carry out at normal temperatures and pressures, and running cost reduces; Adsorbent reactivation is convenient, still can keep preferably desulfurized effect after the regeneration.Novelty of the present invention is mainly reflected in two aspects: the one, and the innovation on the carrier is namely with mesoporous γ-Al 2O 3As carrier; The 2nd, the innovation on the absorbent preparation method, document is generally introduced copper compound by the method for " load ", and the degree of scatter of copper is not high; And the present invention is incorporated into copper mesoporous by the synthetic method of original position γ-Al 2O 3In, can realize the high degree of dispersion of copper.

Claims (10)

1. adsorbent that is used for gasoline desulfur is characterized in that: this adsorbent be copper mix mesoporous γ-Al 2O 3
2. the adsorbent for gasoline desulfur according to claim 1 is characterized in that: it is mesoporous that described copper mixes γ-Al 2O 3Middle copper and mesoporous γ-Al 2O 3In the mol ratio of aluminium element be 0.01 ~ 0.3.
3. the adsorbent for gasoline desulfur according to claim 1, it is characterized in that: the mantoquita of described copper is one or more in copper nitrate, copper sulphate, copper chloride, the Schweinfurt green.
4. preparation method who is used for the adsorbent of gasoline desulfur is characterized in that: this adsorbent be copper mix mesoporous γ-Al 2O 3, it is mesoporous that described copper mixes γ-Al 2O 3The method synthetic by following Direct Hydrothermal prepares: with the Al (NO of 39wt% 3) 39H 2O, template P123 and distilled water mix, and add subsequently mantoquita, the solution that then obtains clarifying at 30 ~ 45 ℃ of lower stirring 36 h; Stop this moment stirring static ageing 6 ~ 8 h; After ageing finishes, slowly dropwise adding respectively precipitating reagent under the stirring, described precipitating reagent is for containing 10 wt% NaOH, 13 wt% Na 2CO 3With 40 wt% K 2CO 3Solution, be incorporated with in the teflon-lined stainless steel cauldron 100 ℃ of lower ageing 24 h that continue under the room temperature after ageing 6 ~ 8 h; This moment, the hole wall of gained mesoporous material was made of boehmite AlOOH, with deionized water the gained sample was washed fully, behind the suction filtration, at room temperature naturally dried and namely got former powder, and former powder is copper doping mesoporous of not removed template method P123 γ-Al 2O 3At air atmosphere, 500 ~ 550 ℃ of lower roasting 4 ~ 6 h, in roasting process, the hole wall of mesoporous material is converted into by AlOOH with former powder γ-Al 2O 3Again with the sample after the roasting in inert gas atmosphere, 550 ~ 650 ℃ of lower autoreduction 12 ~ 24 h, be cooled to mesoporous that room temperature obtains namely that copper mixes γ-Al 2O 3What wherein synthetic copper mixed is mesoporous γ-Al 2O 3Quantity of reaction mass than the mol ratio that is scaled respective substance be: 1.0Al 3+: 0.011P123:3OH -: (0.01 ~ 0.3) Cu 2+
5. the preparation method of the adsorbent for gasoline desulfur according to claim 4, it is characterized in that: the consumption of described mantoquita is copper and mesoporous in copper γ-Al 2O 3In the mol ratio of aluminium element be 0.01 ~ 0.3, described inert gas is He, Ar or N 2
6. adopt adsorbent claimed in claim 1 to carry out the method for gasoline desulfur, it is characterized in that: described adsorbent contacts with the gasoline of sulfur-bearing, utilizes absorption method to realize the desulfurization of gasoline.
7. described employing adsorbent carries out the method for gasoline desulfur according to claim 6, and it is characterized in that: described gasoline is the gasoline that contains thiophene-type sulfide.
8. described employing adsorbent carries out the method for gasoline desulfur according to claim 6, it is characterized in that: described gasoline with the condition that described adsorbent contacts is: temperature is room temperature to 50 ℃, adsorbent is 1:35 ~ 100 with the quality of gasoline ratio, and pressure is normal pressure ~ 0.5MPa.
9. described employing adsorbent carries out the method for gasoline desulfur according to claim 6, and it is characterized in that: described gasoline with the optimum condition that described adsorbent contacts is: temperature is room temperature, and pressure is normal pressure.
10. the renovation process of the adsorbent for gasoline desulfur according to claim 1, it is characterized in that: the adsorbent behind the saturated adsorption is purged 4 ~ 6 h in 300 ~ 500 ℃ air atmosphere, then at inert gas atmosphere, 550 ~ 650 ℃ of lower autoreduction 12 ~ 24 h.
CN2013100138784A 2013-01-15 2013-01-15 Adsorbent for gasoline desulfurization and preparation method as well as application thereof Pending CN103007873A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106111054A (en) * 2016-07-07 2016-11-16 浙江工业大学 A kind of with SiO2/ Cu2o composite aerogel is the method for thiophene sulphur in adsorbent removing fuel oil
CN106590728A (en) * 2016-12-15 2017-04-26 浙江工业大学 Method or removing thiophenic sulfur from fuel oil by taking Cu2O/SiO2-Al2O3 composite aerogel as adsorbent
CN110538645A (en) * 2018-05-28 2019-12-06 中国石油化工股份有限公司 treatment method of agglomerated regenerated adsorbent and desulfurization method of sulfur-containing hydrocarbon oil

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005330305A (en) * 2004-05-18 2005-12-02 Sekiyu Combinat Kodo Togo Unei Gijutsu Kenkyu Kumiai Method for adsorptive desulfurization of hydrocarbon oil
CN101314727A (en) * 2008-06-25 2008-12-03 南京工业大学 Desulfurization method for gasoline

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005330305A (en) * 2004-05-18 2005-12-02 Sekiyu Combinat Kodo Togo Unei Gijutsu Kenkyu Kumiai Method for adsorptive desulfurization of hydrocarbon oil
CN101314727A (en) * 2008-06-25 2008-12-03 南京工业大学 Desulfurization method for gasoline

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
单佳慧: ""Ce改性介孔γ-Al2O3的一步水热合成及其对噻吩的吸附性能"", 《化工新型材料》 *
单佳慧: ""吸附法深度脱除燃料油中硫化物的研究进展"", 《化工进展》 *
李武: ""有序介孔材料SBA-15/Cu(I)分离噻吩的研究"", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106111054A (en) * 2016-07-07 2016-11-16 浙江工业大学 A kind of with SiO2/ Cu2o composite aerogel is the method for thiophene sulphur in adsorbent removing fuel oil
CN106590728A (en) * 2016-12-15 2017-04-26 浙江工业大学 Method or removing thiophenic sulfur from fuel oil by taking Cu2O/SiO2-Al2O3 composite aerogel as adsorbent
CN106590728B (en) * 2016-12-15 2018-06-29 浙江工业大学 One kind is with Cu2O/SiO2-Al2O3The method that composite aerogel removes thiophene sulphur in fuel oil for adsorbent
CN110538645A (en) * 2018-05-28 2019-12-06 中国石油化工股份有限公司 treatment method of agglomerated regenerated adsorbent and desulfurization method of sulfur-containing hydrocarbon oil
CN110538645B (en) * 2018-05-28 2022-05-03 中国石油化工股份有限公司 Treatment method of agglomerated regenerated adsorbent and desulfurization method of sulfur-containing hydrocarbon oil

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