CN102773072A - Cerium element-modified mesoporous silica adsorbent and preparation method for adsorbent and application in gasoline desulfurization - Google Patents
Cerium element-modified mesoporous silica adsorbent and preparation method for adsorbent and application in gasoline desulfurization Download PDFInfo
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Abstract
The invention belongs to the field of fuel desulfurization and discloses a cerium element-modified mesoporous silica adsorbent and a preparation method for the adsorbent and application in gasoline desulfurization. The adsorbent is cerium element-modified mesoporous silica. The adsorbent is the cerium element-modified mesoporous silica SBA-15 and MCM-48 prepared by adopting an in situ synthesis method, an immersion method and a solid phase grinding or raw powder grinding method. The adsorbent is good in desulfurization effect, and moreover, better desulfurization performance still can be kept after the adsorbent is regenerated. By adopting the desulfurization adsorbent, the defects that an adsorbent adopting silver and copper to serve as active components can be easily decomposed under light and can be easily oxidized during the storage and transportation process are overcome.
Description
Technical field
The invention belongs to the gasoline desulfur field, relate to a kind of Ce elements modification mesopore silicon oxide adsorbent and preparation method thereof and the application in gasoline desulfur.
Background technology
Contained mercaptan, thioether, oxysulfide and thiophene-type sulfide is one of principal element that causes environmental pollution in the fuel oil (gasoline, diesel oil and kerosene etc.).These sulfur compounds can generate oxysulfide behind the fuel oil combustion, are discharged into and form acid rain in the atmosphere, contaminated air, the catalyst poisoning that vehicle exhaust is handled.Therefore, removing these sulfur-containing compounds is the urgent tasks that improve environment.Can reduce the sulfur content in the fuel oil though use general hydrodesulfurization technology now, need higher energy consumption if reach the purpose of deep desulfuration, also will increase the loss of hydrogen, running cost is high, difficulty is big.Therefore, desirable scheme is that the development of new adsorbent is realized deep desulfuration under the condition of gentleness.The adsorption desulfurize operating condition is gentle, and technology is simple, becomes present research focus.
The emphasis of adsorption desulfurize process is the adsorbent of development of new, improves the adsorption capacity of adsorbent.Document (Chem.Eng.Sci., 2008, reported CuCl has been loaded on SBA-15 and the MCM-41 63:356) that remove the sulfide in the JP-5 fuel oil light component as adsorbent, the result shows that adsorption desulfurize is satisfactory for result.
Document (Chem.Eng.Sci., 2009,64:5240) reported AgNO
3Load on MCM-41 and the SBA-15, remove the sulfide in the JP-5 fuel oil light component, show the good adsorption performance.
Research to the desulfuration adsorbent active specy in recent years all concentrates on silver and copper, does not see as yet with Ce elements and modifies mesopore silicon oxide SBA-15 and the MCM-48 report as desulfuration adsorbent.
Summary of the invention
The objective of the invention is to be to provide a kind of adsorbent that is used for removing the gasoline thiophene-type sulfide, this adsorbent adopts Ce elements to modify mesopore silicon oxide.
Another object of the present invention provides above-mentioned preparation of adsorbent method.
Of the present invention also have a purpose to provide above-mentioned adsorbent carries out the adsorbing and removing thiophene-type sulfide to gasoline method.
Of the present invention have a purpose to provide the renovation process of above-mentioned adsorbent again.
The objective of the invention is to realize through following technical proposal:
A kind of adsorbent that is used for gasoline desulfur, this adsorbent are the mesopore silicon oxides that Ce elements is modified.
Described adsorbent, wherein the mol ratio of the element silicon in Ce elements and the mesopore silicon oxide is 0.005～0.25.
The compound that Ce elements is provided is cerous nitrate, cerium chloride, cerous sulfate, cerous acetate; Mesoporous silicon oxide molecular sieve is SBA-15, MCM-48.
Molecular sieve SBA-15, MCM-48 are through silicon source TEOS (positive tetraethyl orthosilicate) hydrolysis, and respectively with surfactant P123 (EO
20PO
70EO
20), CTAB (softex kw) is the mesoporous silicon based material that template is synthetic, its template 550 ℃ of roasting 5h under air atmosphere remove.
The mesopore silicon oxide that the synthetic Ce elements of in-situ synthesis is modified may further comprise the steps: in the building-up process of mesoporous molecular sieve SBA-15 or MCM-48; Add Ce elements and element silicon mol ratio in the silicon source before the TEOS hydrolysis and be 0.005～0.25 cerium salt dissolving, just can obtain the mesopore molecular sieve of Ce elements modification;
The mesopore silicon oxide that the synthetic Ce elements of infusion process is modified may further comprise the steps: the cerium salt of getting 0.00005～0.0025mol is dissolved in the water; Add 0.6g SBA-15 or MCM-48 again and stir 24h; At 80 ℃ of following evaporates to dryness; At 100 ℃ of following dry 4h, 400～600 ℃ of following roasting 3～10h under air atmosphere obtain the mesoporous silicon oxide molecular sieve that Ce elements is modified afterwards then.
The mesopore silicon oxide that the synthetic Ce elements of solid-phase grinding method is modified may further comprise the steps: the cerium salt that takes by weighing 0.00005～0.0025mol; At room temperature levigate; Fully grind with 0.6gSBA-15 or MCM-48 then; Again under air atmosphere at 400～600 ℃ of following roasting 3～10h, obtain the mesoporous silicon oxide molecular sieve that Ce elements is modified.
The mesopore silicon oxide that the synthetic Ce elements of former powder polishing is modified may further comprise the steps: the cerium salt that takes by weighing 0.00005～0.0025mol; At room temperature levigate; Fully grind with former powder SBA-15 of 1.2g or former powder MCM-48 then; Again under air atmosphere at 400～600 ℃ of following roasting 3～10h, obtain the mesoporous silicon oxide molecular sieve that Ce elements is modified.
A kind of gasolene desulfurizing method by adsorption, this method adopt above-mentioned adsorbent to contact with the gasoline of sulfur-bearing, utilize absorption method to realize the desulfurization of gasoline.The condition that gasoline contacts with adsorbent is: temperature is room temperature～50 ℃, and pressure is normal pressure～0.5MPa; Preferred temperature is a room temperature, and pressure is normal pressure; The desulfurization object is the gasoline that contains thiophene-type sulfide.
The renovation process of said adsorbent of molecular sieve, this method are at air atmosphere, 400～600 ℃ of following roasting 3～10h with the adsorbent of molecular sieve of absorption after saturated.
The sulfide that gasoline contains described in the gasoline desulfating method provided by the invention is generally thiophene, benzothiophene, dibenzothiophenes and their a series of organic sulfur compounds such as derivative.
Molecular sieve does not add the finished product that specified otherwise all is meant removed template method.Former powder SBA-15, former powder MCM-48 are meant the not mesopore silicon oxide of removed template method P123, CTAB respectively.
Beneficial effect of the present invention:
The present invention adopts the mesopore silicon oxide of Ce elements modification as desulfuration adsorbent.Adsorption desulfurize carries out (like normal temperature and pressure) under the condition of gentleness, running cost is low, desulfurization effect, and still can keep desulfurization performance preferably after the regeneration.Novelty of the present invention is mainly reflected in two aspects: the one, and the innovation of adsorption desulfurize active specy; Promptly adopt Ce elements as the active specy that removes thiophene-type sulfide; Because the cerium species are stable under normal conditions, the meso pore silicon oxide material that therefore this cerium is modified has overcome and adopts silver and the adsorbent of copper as active specy in storage and transportation, to be prone to see the light decomposition, to be prone to oxidized shortcoming.The 2nd, the innovation on the adsorbent preparation method adopts that original position is synthetic, infusion process, solid-phase grinding and former powder polishing introduce mesopore silicon oxide with the cerium species.
Solid-phase grinding method and former powder polishing operational difference be molecular sieve whether be former powder, yet the effect of the formation principle of sample, finished product character and adsorption desulfurize but is diverse.The sample of former powder polishing preparation has obviously demonstrated the effect of adsorption desulfurize preferably; This will give the credit to the ultra micro space that exists between the template and silicon wall among the former powder SBA-15, and the confinement effect that this space forms more helps the jewelry kind and in the duct of SBA-15, becomes the individual layer dispersity.The solid-phase grinding method is owing to removed template, and effect is just good not as former powder polishing.
The specific embodiment
Below through embodiment the present invention is further described, but content of the present invention is not limited thereto fully.
Embodiment 1
It is at room temperature levigate to take by weighing the 0.0216g cerous nitrate, adds the former powder SBA-15 of 1.2020g then and fully grinds the back at 500 ℃ of following roasting 5h of air atmosphere, makes the cerium silicon mol ratio and be 0.005 adsorbent, is labeled as 0.5CeAS.
The 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog gasoline that sulfur content is 550ppm.Adsorbent mass is 0.2g in the adsorption column; Model gasoline is got into by the adsorption column bottom; Flow velocity with 3mL/h passes through whole adsorption column; Liquid product is measured its sulfur content with Varian 3800 gas chromatographs, and desulfurization amount is 147 μ mol sulphur/g adsorbents (desulfurization amount of explaining among the application is the adsorbance when adsorbent is saturated to be adsorbed, down together).
Embodiment 2
Take by weighing the 0.0438g cerous nitrate with at room temperature levigate, add the former powder SBA-15 of 1.2020g then and fully grind the back, make the cerium silicon mol ratio and be 0.01 adsorbent, be labeled as 1.0CeAS at 500 ℃ of following roasting 5h of air atmosphere.
The 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog gasoline that sulfur content is 550ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 167 μ mol sulphur/g adsorbents.
Embodiment 3
It is at room temperature levigate to take by weighing the 0.0655g cerous nitrate, adds the former powder SBA-15 of 1.2020g then and fully grinds the back at 500 ℃ of following roasting 5h of air atmosphere, makes the cerium silicon mol ratio and be 0.015 adsorbent, is labeled as 1.5CeAS.
The 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog gasoline that sulfur content is 550ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 180 μ mol sulphur/g adsorbents.
Embodiment 4
It is at room temperature levigate to take by weighing the 0.0868g cerous nitrate, adds the former powder SBA-15 of 1.2020g then and fully grinds the back at 500 ℃ of following roasting 5h of air atmosphere, makes the cerium silicon mol ratio and be 0.02 adsorbent, is labeled as 2.0CeAS.
The 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog gasoline that sulfur content is 550ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 160 μ mol sulphur/g adsorbents.
Embodiment 5
It is at room temperature levigate to take by weighing the 0.1302g cerous nitrate, adds the former powder SBA-15 of 1.2020g then and fully grinds the back at 500 ℃ of following roasting 5h of air atmosphere, makes the cerium silicon mol ratio and be 0.03 adsorbent, is labeled as 3.0CeAS.
The 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog gasoline that sulfur content is 550ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 144 μ mol sulphur/g adsorbents.
Embodiment 6
It is at room temperature levigate to take by weighing the 0.0216g cerous nitrate, and the SBA-15 that adds 0.6010g removed template method P123 then fully grinds the back at 500 ℃ of following roasting 5h of air atmosphere, makes the cerium silicon mol ratio and be 0.005 adsorbent, is labeled as 0.5CeCS.
The 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog gasoline that sulfur content is 550ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 107 μ mol sulphur/g adsorbents.
Embodiment 7
It is at room temperature levigate to take by weighing the 0.0434g cerous nitrate, and the SBA-15 that adds 0.6010g removed template method P123 then fully grinds the back at 500 ℃ of following roasting 5h of air atmosphere, makes the cerium silicon mol ratio and be 0.01 adsorbent, is labeled as 1.0CeCS.
The 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog gasoline that sulfur content is 550ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 103 μ mol sulphur/g adsorbents.
Embodiment 8
It is at room temperature levigate to take by weighing the 0.0665g cerous nitrate, and the SBA-15 that adds 0.6010g removed template method P123 then fully grinds the back at 500 ℃ of following roasting 5h of air atmosphere, makes the cerium silicon mol ratio and be 0.015 adsorbent, is labeled as 1.5CeCS.
The 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog gasoline that sulfur content is 550ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 110 μ mol sulphur/g adsorbents.
Embodiment 9
It is at room temperature levigate to take by weighing the 0.0873g cerous nitrate, and the SBA-15 that adds 0.6010g removed template method P123 then fully grinds the back at 500 ℃ of following roasting 5h of air atmosphere, makes the cerium silicon mol ratio and be 0.02 adsorbent, is labeled as 2.0CeCS.
The 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog gasoline that sulfur content is 550ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 97 μ mol sulphur/g adsorbents.
Embodiment 10
It is at room temperature levigate to take by weighing the 0.1308g cerous nitrate, and the SBA-15 that adds 0.6010g removed template method P123 then fully grinds the back at 500 ℃ of following roasting 5h of air atmosphere, makes the cerium silicon mol ratio and be 0.03 adsorbent, is labeled as 3.0CeCS.
The 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog gasoline that sulfur content is 550ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 97 μ mol sulphur/g adsorbents.
Embodiment 11
The mesoporous molecular sieve adsorbent that absorption among the embodiment 3 is saturated is at air atmosphere, 500 ℃ of following roasting 5h.After the regeneration, carry out gasoline desulfur once more by the method for embodiment 3, desulfurization amount is 164 μ mol sulphur/g adsorbents.
Embodiment 12
It is at room temperature levigate to take by weighing the 0.2171g cerous nitrate, adds the former powder SBA-15 of 1.2020g then and fully grinds the back at 500 ℃ of following roasting 5h of air atmosphere, makes the cerium silicon mol ratio and be 0.05 adsorbent, is labeled as 5.0CeAS.
The 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog gasoline that sulfur content is 550ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 131 μ mol sulphur/g adsorbents.
Embodiment 13
It is at room temperature levigate to take by weighing the 0.8684g cerous nitrate, adds the former powder SBA-15 of 1.2020g then and fully grinds the back at 500 ℃ of following roasting 5h of air atmosphere, makes the cerium silicon mol ratio and be 0.2 adsorbent, is labeled as 20CeAS.
The 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog gasoline that sulfur content is 550ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 165 μ mol sulphur/g adsorbents.
Embodiment 14
It is at room temperature levigate to take by weighing the 1.7368g cerous nitrate, adds the former powder SBA-15 of 1.2020g then and fully grinds the back at 500 ℃ of following roasting 5h of air atmosphere, makes the cerium silicon mol ratio and be 0.4 adsorbent, is labeled as 40CeAS.
The 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog gasoline that sulfur content is 550ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 82 μ mol sulphur/g adsorbents.
Embodiment 15
It is at room temperature levigate to take by weighing the 0.0655g cerous nitrate, adds the former powder MCM-48 of 1.2020g then and fully grinds the back at 500 ℃ of following roasting 5h of air atmosphere, makes the cerium silicon mol ratio and be 0.015 adsorbent, is labeled as 1.5CeAM.
The 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog gasoline that sulfur content is 550ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 165 μ mol sulphur/g adsorbents.
Embodiment 16
It is at room temperature levigate to take by weighing the 0.0655g cerous nitrate, and the MCM-48 that adds 1.2020g removed template method CTAB then fully grinds the back at 500 ℃ of following roasting 5h of air atmosphere, makes the cerium silicon mol ratio and be 0.015 adsorbent, is labeled as 1.5CeCM.
The 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog gasoline that sulfur content is 550ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 129 μ mol sulphur/g adsorbents.
Embodiment 17
Take by weighing the 0.0655g cerous nitrate and be dissolved in the 10g deionized water; The SBA-15 that adds 0.6g removed template method P123 then fully stirs 24h; Steam down at 80 ℃, 100 ℃ down behind the dry 4h; Again at 500 ℃ of following roasting 5h of air atmosphere, make cerium, silicon mol ratio and be 0.015 adsorbent, be labeled as 1.5CeS-J.
The 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog gasoline that sulfur content is 550ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 118 μ mol sulphur/g adsorbents.
Embodiment 18
Take by weighing the 0.0655g cerous nitrate and be dissolved in the 10g deionized water; The MCM-48 that adds 0.6g removed template method CTAB then fully stirs 24h; Steam down at 80 ℃, 100 ℃ down behind the dry 4h; Again at 500 ℃ of following roasting 5h of air atmosphere, make cerium, silicon mol ratio and be 0.015 adsorbent, be labeled as 1.5CeM-J.
The 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog gasoline that sulfur content is 550ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 103 μ mol sulphur/g adsorbents.
Embodiment 19
Take by weighing 3g P123 (EO
20PO
20EO
20) template is dissolved in the mixed solution of 2mol/L hydrochloric acid, 0.2009g cerous nitrate and 22.5g deionized water of 90g, stir clarification after, put into 40 ℃ of waters bath with thermostatic control and stir 0.5h; Add 6.38gTEOS then; Keep the permanent rotating speeds of 40 ℃ of constant temperature, 600 rev/mins to stir 24h, then system is warming up to 100 ℃ and at this warm ageing crystallization 24h, take out sample; Spend deionised water, suction filtration; Dry under the last room temperature, it is 0.015 adsorbent that the sample after drying makes cerium, silicon mol ratio at 550 ℃ of following bubbling air roasting 5h, is labeled as 1.5CeS-Y.
The 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog gasoline that sulfur content is 550ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 125 μ mol sulphur/g adsorbents.
Embodiment 20
0.192g NaOH is dissolved in the deionized water of 10g, then 2.04g softex kw and 0.0651g cerous nitrate is joined in the solution, 35 ℃ of following 600 rev/mins of permanent rotating speed stirring and dissolving; When treating the solution clarification, slowly add the positive tetraethyl orthosilicate of 2.08g, continue to keep 35 ℃ of constant temperature stir about 0.5h; Obtain milky colloidal sol, system is warming up to 100 ℃ and at this warm ageing crystallization 3d, take out sample; Spend deionised water, suction filtration; Dry under the last room temperature, it is 0.015 adsorbent that the sample after drying obtains cerium, silicon mol ratio at 550 ℃ of following bubbling air roasting 4h, is labeled as 1.5CeM-Y.
The 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog gasoline that sulfur content is 550ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 108 μ mol sulphur/g adsorbents.
Embodiment 21
It is at room temperature levigate to take by weighing the 0.0655g cerous nitrate, adds the former powder SBA-15 of 1.2020g then and fully grinds the back at 500 ℃ of following roasting 5h of air atmosphere, makes the cerium silicon mol ratio and be 0.015 adsorbent, is labeled as 1.5CeAS.
The 0.1603g benzothiophene is dissolved in the 100mL isooctane, and dilution is made into the analog gasoline that sulfur content is 500ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 158 μ mol sulphur/g adsorbents.
Embodiment 22
It is at room temperature levigate to take by weighing the 0.0655g cerous nitrate, adds the former powder SBA-15 of 1.2020g then and fully grinds the back at 500 ℃ of following roasting 5h of air atmosphere, makes the cerium silicon mol ratio and be 0.015 adsorbent, is labeled as 1.5CeAS.
With 0.2303g 4, the 6-dimethyl Dibenzothiophene is dissolved in the 100mL isooctane, and dilution is made into the analog gasoline that sulfur content is 500ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 135 μ mol sulphur/g adsorbents.
Embodiment 23
It is at room temperature levigate to take by weighing the 0.0655g cerous nitrate, adds the former powder SBA-15 of 1.2020g then and fully grinds the back at 500 ℃ of following roasting 5h of air atmosphere, makes cerium, silicon mol ratio and be 0.015 adsorbent, places under normal conditions one month, is labeled as 1.5CeAS-1.
The 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog gasoline that sulfur content is 550ppm.Adsorbent mass is 0.2g in the adsorption column, and model gasoline is got into by the adsorption column bottom, through whole adsorption column, liquid product is measured its sulfur content with Varian 3800 gas chromatographs with the flow velocity of 3mL/h, and desulfurization amount is 179 μ mol sulphur/g adsorbents.
Claims (10)
1. an adsorbent that is used for gasoline desulfur is characterized in that this adsorbent is the mesopore silicon oxide that Ce elements is modified.
2. adsorbent according to claim 1, the Ce elements that it is characterized in that modifying and the mol ratio of the element silicon in the mesopore silicon oxide are 0.005～0.25.
3. adsorbent according to claim 1 is characterized in that it is cerous nitrate, cerium chloride, cerous sulfate, cerous acetate that the compound of Ce elements is provided; Mesoporous silicon oxide molecular sieve is SBA-15, MCM-48.
4. adsorbent according to claim 1, the mesopore silicon oxide of it is characterized in that adopting that original position is synthetic, dipping, solid-phase grinding or the synthetic Ce elements of former powder abrasive method being modified.
5. adsorbent according to claim 1 is characterized in that molecular sieve SBA-15, MCM-48 are through silicon source TEOS (positive tetraethyl orthosilicate) hydrolysis, and respectively with surfactant P123 (EO
20PO
70EO
20), CTAB (softex kw) is the mesoporous silicon based material that template is synthetic, its template 550 ℃ of roasting 5h under air atmosphere remove.
6. the preparation method of adsorbent of molecular sieve according to claim 1 is characterized in that the mesopore silicon oxide that this method adopts the synthetic Ce elements of method of in-situ synthesis, infusion process, solid-phase grinding method or former powder polishing to modify respectively:
The mesopore silicon oxide that the synthetic Ce elements of in-situ synthesis is modified may further comprise the steps: in the building-up process of mesoporous molecular sieve SBA-15 or MCM-48; Add Ce elements and element silicon mol ratio in the silicon source before the TEOS hydrolysis and be 0.005～0.25 cerium salt dissolving, just can obtain the mesopore molecular sieve of Ce elements modification;
The mesopore silicon oxide that the synthetic Ce elements of infusion process is modified may further comprise the steps: the cerium salt that takes by weighing 0.00005～0.0025mol is dissolved in the water; The SBA-15 or the MCM-48 that add 0.6g again stir 24h; At 80 ℃ of following evaporates to dryness; At 100 ℃ of following dry 4h, 400～600 ℃ of following roasting 3～10h under air atmosphere obtain the mesoporous silicon oxide molecular sieve that Ce elements is modified afterwards then;
The mesopore silicon oxide that the synthetic Ce elements of solid-phase grinding method is modified may further comprise the steps: the cerium salt that takes by weighing 0.00005～0.0025mol; At room temperature levigate; SBA-15 or MCM-48 with 0.6g fully grinds then; Again under air atmosphere at 400～600 ℃ of following roasting 3～10h, obtain the mesoporous silicon oxide molecular sieve that Ce elements is modified;
The mesopore silicon oxide that the synthetic Ce elements of former powder polishing is modified may further comprise the steps: the cerium salt that takes by weighing 0.00005～0.0025mol; At room temperature levigate; Former powder SBA-15 or former powder MCM-48 with 1.2g fully grinds then; Again under air atmosphere at 400～600 ℃ of following roasting 3～10h, obtain the mesoporous silicon oxide molecular sieve that Ce elements is modified.
7. method according to claim 6, former powder SBA-15, former powder MCM-48 are meant the not mesopore silicon oxide of removed template method P123, CTAB respectively.
8. a gasolene desulfurizing method by adsorption is characterized in that this method adopts the described adsorbent of claim 1 to contact with the gasoline of sulfur-bearing, utilizes absorption method to realize the desulfurization of gasoline.
9. method according to claim 8 is characterized in that the condition that gasoline contacts with adsorbent is: temperature is room temperature～50 ℃, and pressure is normal pressure～0.5MPa; Preferred temperature is a room temperature, and pressure is normal pressure; The desulfurization object is the gasoline that contains thiophene-type sulfide.
10. according to the renovation process of the said adsorbent of molecular sieve of claim 1, it is characterized in that with absorption adsorbent of molecular sieve after saturated is at air atmosphere, 400～600 ℃ of following roasting 3～10h.
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