CN108854953B - Method for adsorption and removal of thiophene sulfur in fuel oil by Ag2O/SiO2-TiO2-graphene oxide composite aerogel - Google Patents
Method for adsorption and removal of thiophene sulfur in fuel oil by Ag2O/SiO2-TiO2-graphene oxide composite aerogel Download PDFInfo
- Publication number
- CN108854953B CN108854953B CN201810601512.1A CN201810601512A CN108854953B CN 108854953 B CN108854953 B CN 108854953B CN 201810601512 A CN201810601512 A CN 201810601512A CN 108854953 B CN108854953 B CN 108854953B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- sio
- tio
- oxide composite
- composite aerogel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明公开了Ag2O/SiO2‑TiO2‑氧化石墨烯复合气凝胶吸附脱除燃料油中噻吩类硫的方法，属于燃料油加工技术领域。该方法以正硅酸甲酯、正硅酸乙酯、硅溶胶或水玻璃为硅源，以醋酸银或硝酸银为银源，以钛酸四丁酯为钛源，采用溶胶凝胶—常压干燥法制得Ag2O/SiO2‑TiO2‑氧化石墨烯复合气凝胶，然后将其定量填装于固定床吸附装置中，在一定温度与空速下，注入含噻吩类硫化物的模拟汽油，在反应装置的下端出口处收集吸附后的模拟汽油。本发明提供的方法吸附反应在常压下进行，吸附条件温和，对吸附设备的要求低、操作方便，吸附容量大，该吸附剂可多次重复使用、经济效益高、环境友好。The invention discloses a method for adsorbing and removing thiophene sulfur in fuel oil by Ag 2 O/SiO 2 -TiO 2 -graphene oxide composite aerogel, and belongs to the technical field of fuel oil processing. The method uses methyl orthosilicate, ethyl orthosilicate, silica sol or water glass as the silicon source, silver acetate or silver nitrate as the silver source, tetrabutyl titanate as the titanium source, and a sol-gel-normal Ag 2 O/SiO 2 ‑TiO 2 ‑graphene oxide composite aerogel was prepared by pressing drying method, and then it was quantitatively filled in a fixed bed adsorption device. Simulate gasoline, and collect the adsorbed simulated gasoline at the outlet at the lower end of the reaction device. The adsorption reaction of the method provided by the invention is carried out under normal pressure, the adsorption conditions are mild, the requirements for adsorption equipment are low, the operation is convenient, and the adsorption capacity is large.
Description
Technical Field
The invention belongs to the technical field of fuel oil processing, and particularly relates to Ag2O/SiO2-TiO2A method for adsorbing and removing thiophene sulfur in fuel oil by using-graphene oxide composite aerogel.
Background
With the rapid development of the automobile industry, the emission of a large amount of sulfides in the automobile exhaust not only makes the environmental pollution problem become serious, but also threatens the human health. Fuel cells also have a relatively high demand for sulfur content in fuel oil, and the presence of organic sulfides poisons the catalyst in the fuel cell electrodes, rendering the fuel cell ineffective at converting the chemical energy in diesel and gasoline into electrical energy. Therefore, deep desulfurization of fuel oil has become a focus of global attention.
At present, the desulfurization process of fuel oil mainly comprises hydrodesulfurization technology, alkylation desulfurization technology, biological desulfurization technology, extraction desulfurization technology, oxidation desulfurization technology, adsorption desulfurization technology and the like. In the existing industrial production, the main process of desulfurization is still the traditional hydrodesulfurization, but the main process has the defects of higher operation cost, large hydrogen consumption, harsh operation conditions, octane number reduction in gasoline and the like. And the hydrodesulfurization only has good effect on mercaptan, thioether, inorganic sulfur and the like, and has poor desulfurization effect on thiophene sulfides with extremely high thermal stability. The adsorption desulfurization has low cost, mild operation condition, good desulfurization effect and no environmental pollution, wherein the pi-complex adsorption desulfurization is selective relative to physical adsorption desulfurization, is easier for desorption regeneration of chemical adsorption desulfurization and is the most promising desulfurization method at present.
The key of the pi-complex adsorption desulfurization lies in preparing a high-efficiency pi-complex adsorbent. The metal ion commonly used for preparing the pi-complexation desulfurization adsorbent is Cu2+、Ag+、Ni2+、Co2+And the like. And the preparation of the pi-complex desulfurization adsorbent needs to disperse the metal ions on a carrier with high specific surface area. The pi-complex desulfurization adsorbent can be classified into molecular sieves, activated carbons and metal oxides according to the difference of carriers.
Pi complex desulfurizing adsorbent with molecular sieve as carrier. The Shenyang chemical industry university (publication No. CN 103170305A) uses a 13X molecular sieve loaded with Ag ions as a desulfurization adsorbent and is used for deeply removing thiophene and derivatives thereof and benzothiophene in gasoline. Wherein, the content of silver element accounts for 3 percent to 5 percent of the total weight of the adsorbent, and the silver element is in an ionic state. A molecular sieve adsorbent for deeply removing sulfide is prepared by Chinese academy of sciences (publication No. CN 1511629A) and is composed of Y-type molecular sieve loaded with metal salts. The pi complex adsorbent has low carrier cost, simple preparation process and capacity of being regenerated circularly. However, the transition metal ions exchanged by the microporous molecular sieve desulfurization adsorbent are limited in number, the adsorption capacity to sulfide is not large, and the microporous molecular sieve has a microporous structure, so that large-molecular thiophene sulfides cannot enter a pore channel due to the molecular size effect to form pi complexation with metal ions, namely deep desulfurization cannot be achieved.
Pi-complex desulfurizing adsorbent with active carbon as carrier. Shenyang chemical industry university (publication No. CN 103143322A) prepares an active carbon adsorbent loaded with Fe ions, has larger adsorption capacity and selectivity on thiophene and derivatives thereof in gasoline, and has the advantages of simple preparation method, easy regeneration and long service life of the adsorbent. The method is implemented by adopting salt containing Al, Zn, Ni and other metals and H (publication No. CN 104549143A)3PO4The modified active carbon is used as an auxiliary agent to modify and modify the active carbon, so that the problems that a single adsorbent cannot simultaneously and effectively remove various sulfides, the removal rate of sulfur is low, the penetrating sulfur capacity of a desulfurizer is low and the like in the gas raw material adsorption, purification and desulfurization technology are solved. However, the pore structure of the activated carbon is mainly microporous, and the adsorption capacity of the modified activated carbon to thiophene macromolecular sulfides is still very small, so that the requirements of industrial production are difficult to meet.
Pi complex desulfurizing adsorbent with metal oxide as carrier. Nantong university (publication No. CN 10300787A) mesoporous gamma-Al doped with copper element2O3The catalyst is contacted with sulfur-containing fuel oil, and desulfurization is realized by using an adsorption method, so that the catalyst is low in operation cost, large in adsorption capacity and convenient to regenerate. China petrochemical company Limited (publication No. CN 10161923A) prepares a desulfurization adsorbent, which comprises alumina as binder and zinc oxide as carrier, and contacts with complexing agent solution, and then carries metal promoter. It is used for desulfurizing fuel oil, and has high activity and great sulfur adsorbing capacity. However, in the preparation process, metal ions easily block metal oxide pore channels, so that loaded active components are accumulated on the surface and cannot enter the pore channels to provide active sites, and the adsorption desulfurization performance is reduced.
Disclosure of Invention
Aiming at the problems of the existing pi complex adsorbent in removing thiophene sulfur in fuel oil, the invention aims to provide the Ag-containing composite adsorbent which has large adsorption capacity and is easy to regenerate2O/SiO2-TiO2And (3) removing thiophene sulfur in the fuel oil by taking the-graphene oxide composite aerogel as an adsorbent through the synergistic effect of pi complex adsorption and acid-base action.
The Ag is2O/SiO2-TiO2The method for adsorbing and removing thiophene sulfur in fuel oil by using-graphene oxide composite aerogel is characterized in that Ag is used2O/SiO2-TiO2The graphene oxide composite aerogel is used as an adsorbent, and the adsorbent is filled into a fixed bed adsorption device at the temperature of 0-100 ℃ for 1-10 h-1The simulated gasoline containing thiophene sulfur is introduced into the reactor at the airspeed, and the simulated gasoline with the sulfur concentration of less than 1ppm is obtained after adsorption.
The Ag is2O/SiO2-TiO2The method for adsorbing and removing the thiophene sulfur in the fuel oil by the graphene oxide composite aerogel is characterized in that the adsorbed thiophene sulfur is thiophene or benzothiophene.
The Ag is2O/SiO2-TiO2The method for adsorbing and removing thiophene sulfur in fuel oil by using-graphene oxide composite aerogel is characterized in that Ag2O/SiO2-TiO2The-graphene oxide composite aerogel is prepared by taking a silver source, a silicon source and a titanium source as raw materials and adopting a sol-gel-normal pressure drying method.
The Ag is2O/SiO2-TiO2The method for adsorbing and removing thiophene sulfur in fuel oil by using the graphene oxide composite aerogel is characterized in that a silicon source is methyl orthosilicate, ethyl orthosilicate, silica sol or water glass, a silver source is silver acetate or silver nitrate, and a titanium source is tetrabutyl titanate; preferably, the silicon source is ethyl orthosilicate and the silver source is silver nitrate.
The Ag is2O/SiO2-TiO2The method for adsorbing and removing thiophene sulfur in fuel oil by using-graphene oxide composite aerogel is characterized in that Ag2O/SiO2-TiO2The molar ratio of silicon to titanium in the graphene oxide composite aerogel adsorbent is 1-250: 1, preferably 25-50: 1; the molar ratio of silicon to silver is 10-50: 1, preferably 25-50: 1.
The Ag is2O/SiO2-TiO2The method for adsorbing and removing thiophene sulfur in fuel oil by using-graphene oxide composite aerogel is characterized in that Ag is used2O/SiO2-TiO2The mass percentage of the graphene oxide is 0.30-1.52 wt%, based on the total mass of the graphene oxide composite aerogel adsorbent.
The Ag is2O/SiO2-TiO2The method for adsorbing and removing the thiophene sulfur in the fuel oil by using the-graphene oxide composite aerogel is characterized in that the space velocity of introducing simulated gasoline containing the thiophene sulfur is 1-5 h-1。
The Ag is2O/SiO2-TiO2The method for adsorbing and removing the thiophene sulfur in the fuel oil by using the graphene oxide composite aerogel is characterized in that the adsorption temperature is 0-60 ℃.
The Ag is2O/SiO2-TiO2The method for adsorbing and removing thiophene sulfur in fuel oil by using the graphene oxide composite aerogel is characterized in that the concentration of thiophene or benzothiophene sulfur in simulated gasoline is 0.1 mgS/g-10 mgS/g.
The Ag is2O/SiO2-TiO2The method for adsorbing and removing thiophene sulfur in fuel oil by using-graphene oxide composite aerogel is characterized in that Ag2O/SiO2-TiO2The graphene oxide composite aerogel can be regenerated and utilized, and the solvent used for regeneration is cyclohexene, diethyl ether, benzene or toluene.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
(1) ag of the present invention2O/SiO2-TiO2The graphene oxide composite aerogel has a typical mesoporous characteristic pore diameter (5-20 nm), high porosity (85-99%), and a high specific surface area (600-1500 m)2The material has unique physical and chemical properties such as/g), so the thiophene sulfides can enter the pore channels of the aerogel without obstruction, and the active components can fully contact with the sulfides;
(2) ag of the present invention2O/SiO2-TiO2-graphene oxide composite aerogel as pi-complex desulfurization adsorbentCompared with other pi complex adsorbents, the structure of the pi complex adsorbent is formed by nanometer skeleton particles, so that active components in the skeleton can be fully exposed, and transition metal salt with the pi complexation effect can be added into the nanometer skeleton particles in the synthesis process of the aerogel, so that the amount of the active components can be adjusted;
(3) ag of the present invention2O/SiO2-TiO2-graphene oxide composite aerogel, with Ag2O/SiO2Compared with the aerogel, the titanium-doped aerogel introduces Ti into the silicon skeleton structure of the aerogel4+Generating L acid, the lone pair electrons on the S atom in the thiophene compound have alkalinity, and the aerogel matrix Ag2O/SiO2-TiO2The L acid center in the graphene oxide can adsorb the thiophene sulfur compounds through the acid-base action, and the synergistic effect of the pi complexation and the acid-base action can further improve the adsorption performance of the thiophene sulfur compounds on the thiophene sulfur;
(4) ag of the present invention2O/SiO2-TiO2-graphene oxide composite aerogel, with Ag2O/SiO2-TiO2Compared with the aerogel, the graphene oxide is introduced into the silicon skeleton structure of the aerogel, so that the strength of the aerogel skeleton is enhanced, and Ag is improved+The incorporation rate of the compound is high, and the surface of the introduced oxidized graphene has rich functional groups, so that the adsorption performance of the compound on thiophene sulfides is further improved.
(5) Ag of the present invention2O/SiO2-TiO2The oxidized graphene composite aerogel pi complex adsorbent has good adsorption performance on thiophene sulfides, can be regenerated by solvent washing, and still has good adsorption performance after regeneration;
(6) the adsorption reaction of the invention is carried out under normal pressure, the adsorption condition is mild, the requirement on adsorption equipment is low, the operation is convenient, and the invention has good adsorption effect on thiophene compounds.
Detailed Description
The invention is further described below with reference to specific examples:
Ag2O/SiO2-TiO2preparing the graphene oxide composite aerogel adsorbent from silicon,The molar ratio of silver is 50:1, the molar ratio of silicon to titanium is 50:1, and the molar ratio of graphene oxide is 2mg of Ag2O/SiO2-TiO2The graphene oxide composite aerogel adsorbent is prepared by the following steps:
15mL EtOH, 8mL TEOS, 1mL H2The mixed solution of O, 0.12g of silver nitrate and 0.243g of tetrabutyl titanate is stirred vigorously and mixed uniformly under an acidic condition and is marked as mixed solution A; then slowly dripping 2mg of graphene oxide dissolved in 1ml of distilled water into the solution A, adding ammonia water after half an hour to adjust the pH value to 6.5, and standing for about 15min at room temperature to obtain the Ag2O/SiO2-TiO2-graphene oxide composite aerogel; aging in absolute ethyl alcohol/n-silicon acetate with the volume ratio of 25:15 for 16h to enhance the skeleton structure of the gel; then using normal hexane to carry out solvent replacement on the gel, replacing the solvent twice within 24h, and removing ethanol, water, acid and other organic molecules in the gel; and finally drying for 2h at the temperature of 80-150 ℃ to obtain the silicon-silver molar ratio of 50:1, the molar ratio of silicon to titanium is 50:1, 0.61 wt% of Ag with graphene oxide2O/SiO2-TiO2-graphene oxide composite aerogel adsorbent.
Examples 1 to 5: ag of different silicon sources and silver sources2O/SiO2-TiO2Adsorption performance of graphene oxide composite aerogel on thiophene sulfur in simulated gasoline
In the preparation of Ag by sol-gel method2O/SiO2-TiO2In the graphene oxide composite aerogel, the silicon source used is methyl orthosilicate, ethyl orthosilicate and silica sol, the silver source is silver nitrate and silver acetate, and the titanium source is tetrabutyl titanate. Prepared Ag2O/SiO2-TiO2Carrying out a penetration adsorption desulfurization experiment on the graphene oxide composite aerogel, and specifically operating as follows: in a fixed bed reactor, the bottom layer is filled with appropriate amount of absorbent cotton, and then with 1g of Ag2O/SiO2-TiO2-graphene oxide composite aerogel with a suitable amount of quartz sand. Before the start of the adsorption experiment, the loaded adsorbent was thoroughly wetted with n-heptane. Introducing simulated gasoline, and collecting adsorbed simulated gasoline at the lower outlet of the reactorWhen the sulfur concentration in the effluent was 0.005mgS/g, the breakthrough point was determined by chromatography. In the experimental process: the airspeed is 1-5 h-1The adsorption temperature is 0-40 ℃, and the concentration of thiophene or benzothiophene sulfur in the simulated gasoline is 0.1-5 mgS/g. The breakthrough adsorption capacity results for thiophene and benzothiophene obtained are shown in table one and table two.
TABLE-Ag of different silicon sources2O/SiO2-TiO2Adsorption performance of graphene oxide composite aerogel on thiophene sulfur in simulated gasoline
Ag of two different silver sources2O/SiO2-TiO2Adsorption performance of graphene oxide composite aerogel on thiophene sulfur in simulated gasoline
As can be seen from tables I and II, Ag was synthesized2O/SiO2-TiO2A silicon source and a silver source used for the graphene oxide composite aerogel, wherein when the silicon source is ethyl orthosilicate and the silver source is silver nitrate, the synthesized Ag is2O/SiO2-TiO2In the breakthrough adsorption experiment, the graphene oxide composite aerogel has the largest breakthrough adsorption capacity on thiophene and benzothiophene, so that the preferred silicon source is tetraethoxysilane and the silver source is silver nitrate.
Examples 6 to 10: doping different graphene oxide pairs to Ag2O/SiO2-TiO2Adsorption performance of graphene oxide composite aerogel on thiophene sulfur in simulated gasoline
0.30 wt%, 0.61 wt%, 0.91 wt%, 1.21 wt%, 1.52 wt% Ag doped with graphene oxide2O/SiO2-TiO2Graphene oxide aerogel, performing a breakthrough adsorption experiment on thiophene sulfides in the simulated gasoline. Wherein the airspeed is 1-5 h-1Adsorption temperature ofThe concentration of thiophene or benzothiophene sulfur in the simulated gasoline is 0.1-5 mgS/g at 0-40 ℃. The operation of the breakthrough adsorption experiment is the same as that of examples 1-5, and the adsorption results are shown in Table III.
Ag with different graphene oxides doped in table III2O/SiO2-TiO2Adsorption performance of graphene oxide composite aerogel on thiophene sulfur in simulated gasoline
As can be seen from Table III, Ag2O/SiO2-TiO2The graphene oxide composite aerogel increases the penetrating adsorption capacity of thiophene and benzothiophene first and then decreases with the increase of the doping amount of graphene oxide. When the graphene oxide doping amount reaches 0.61 wt%, the penetrating adsorption capacity of thiophene and benzothiophene reaches the maximum, so that the Ag with the graphene oxide doping amount of 0.30 wt% to 0.91 wt% is preferred2O/SiO2-TiO2-graphene oxide composite aerogel.
Examples 11 to 16: ag of different Si/Ti molar ratios2O/SiO2-TiO2The adsorption performance of the graphene oxide composite aerogel on the thiophene sulfur in the simulated gasoline is that the Ag with the silicon-silver molar ratio of 50:1 and the graphene oxide molar ratio of 0.61 wt% and the silicon-titanium molar ratios of 5, 25, 50, 100, 150 and 200 respectively2O/SiO2-TiO2Graphene oxide aerogel, performing a breakthrough adsorption experiment on thiophene sulfides in the simulated gasoline. Wherein the airspeed is 1-5 h-1The adsorption temperature is 0-40 ℃, and the concentration of thiophene or benzothiophene sulfur in the simulated gasoline is 0.1-5 mgS/g. The operation of the breakthrough adsorption experiment was the same as in examples 1 to 5, and the adsorption results are shown in Table four.
TABLE IV Ag of different Si/Ti molar ratios2O/SiO2-TiO2Adsorption performance of graphene oxide composite aerogel on thiophene sulfur in simulated gasoline
As can be seen from table four, the molar ratio of silicon to silver is 50:1, 0.61 wt% of graphene oxide and Ag with different molar ratios of silicon to titanium2O/SiO2-TiO2The graphene oxide aerogel increases and then decreases the breakthrough adsorption capacity for thiophene and benzothiophene as the molar ratio of silicon to titanium decreases, i.e., the titanium content increases. When the silicon-titanium molar ratio is 50: when the molar ratio of the silicon to the titanium is 25-100: 1, Ag is preferred because the penetrating adsorption capacity of thiophene and benzothiophene is maximum at 12O/SiO2-TiO2-graphene oxide composite aerogel.
Examples 17 to 20: ag of different Si/Ag molar ratios2O/SiO2-TiO2Adsorption performance of graphene oxide composite aerogel on thiophene sulfur in simulated gasoline
Selecting Ag with the mol ratio of silicon to titanium of 50:1, the graphene oxide of 0.61wt per mill and the mol ratios of silicon to silver of 10, 20, 50 and 100 respectively2O/SiO2-TiO2And (3) carrying out a penetrating adsorption experiment on the thiophene sulfur in the simulated gasoline by using the graphene oxide composite aerogel. Wherein the airspeed is 1-5 h-1The adsorption temperature is 0-40 ℃, and the concentration of thiophene or benzothiophene sulfur in the simulated gasoline is 0.1-5 mgS/g. The operation of the breakthrough adsorption experiment was the same as in examples 1 to 5, and the adsorption results are shown in Table V.
TABLE five Ag of different Si/Ag molar ratios2O/SiO2-TiO2Adsorption performance of graphene oxide composite aerogel on thiophene sulfur in simulated gasoline
As can be seen from Table V, the molar ratio of Si to Ti is 50: 1. 0.61 wt% of graphene oxide and Ag2O/SiO2-TiO2The graphene oxide composite aerogel increases the penetrating adsorption capacity of thiophene and benzothiophene first and then decreases as the molar ratio of silicon to silver decreases, i.e., the silver content increases. The penetrating adsorption capacity of thiophene and benzothiophene is maximized after the molar ratio of silicon to silver is 50:1, and therefore silicon and silver are preferredAg with a molar ratio of 20-50: 12O/SiO2-TiO2-graphene oxide composite aerogel.
Examples 21 to 25: different space velocity pairs of Ag2O/SiO2-TiO2Adsorption performance of graphene oxide composite aerogel on thiophene sulfur in simulated gasoline
Selecting Ag with the molar ratio of silicon to silver of 50:1, the molar ratio of silicon to titanium of 50:1 and the graphene oxide of 2mg2O/SiO2-TiO2-graphene oxide composite aerogel. At a space velocity of 1h-1、3h-1、 5h-1、8h-1、10h-1Next, a breakthrough adsorption experiment was performed on the thiophene sulfur in the simulated gasoline. Wherein the adsorption temperature is 0-40 ℃, and the concentration of thiophene or benzothiophene sulfur in the simulated gasoline is 0.1-5 mgS/g. The operation of the breakthrough adsorption experiment is the same as that of examples 1-5, and the adsorption results are shown in Table six.
Table six different airspeeds Ag2O/SiO2-TiO2Adsorption performance of graphene oxide composite aerogel on thiophene sulfur in simulated gasoline
As can be seen from the sixth table, the penetration adsorption capacity of thiophene and benzothiophene is gradually increased when the space velocity is reduced, and when the space velocity is reduced to 5h-1Then, the penetrating adsorption capacity of the thiophene sulfides is not changed greatly, so that the preferred space velocity is 1-5 h-1。
Examples 26-30: different adsorption temperatures for Ag2O/SiO2-TiO2Adsorption performance of graphene oxide composite aerogel on thiophene sulfur in simulated gasoline
Selecting Ag with the mol ratio of silicon to silver of 50:1, the mol ratio of silicon to titanium of 50:1 and the graphene oxide of 0.61wt ‰2O/SiO2-TiO2-graphene oxide composite aerogel. The adsorption temperature is respectively selected to be 0 ℃, 25 ℃, 40 ℃, 80 ℃ and 100 ℃, and the penetration adsorption experiment is carried out on the thiophene sulfides in the simulated gasoline. Wherein the airspeed is 1-5 h-1The concentration of the thiophene or benzothiophene sulfur in the simulated gasoline is 0.1-5 mgS/g. The operation of the breakthrough adsorption experiment was the same as in examples 1 to 5, and the adsorption results are shown in Table seven.
TABLE seven Ag at different adsorption temperatures2O/SiO2-TiO2Adsorption performance of graphene oxide composite aerogel on thiophene sulfur in simulated gasoline
As can be seen from Table seven, the breakthrough adsorption capacities of thiophene and benzothiophene gradually decreased with the increase of adsorption temperature, and the adsorption breakthrough capacities of thiophene and benzothiophene were very small after 80 deg.C, indicating that at this temperature, the adsorbed ions were adsorbed by Ag2O/SiO2-TiO2The thiophene and benzothiophene adsorbed by the graphene oxide composite aerogel are desorbed. Therefore, the preferential adsorption temperature is 0 to 40 ℃.
Examples 31 to 36: simulating Ag in gasoline at different sulfur concentrations2O/SiO2-TiO2Adsorption performance of graphene oxide composite aerogel on thiophene sulfur
Selecting Ag with the mol ratio of silicon to silver of 50:1, the mol ratio of silicon to titanium of 50:1 and the graphene oxide of 0.61wt ‰2O/SiO2-TiO2-graphene oxide composite aerogel. The sulfur concentrations of thiophene and benzothiophene in the simulated gasoline were 0.1mgS/g, 0.5mgS/g, 1mgS/g, 2 mgS/g, 5mgS/g, and 10mgS/g, respectively, and the breakthrough adsorption experiments were performed. Wherein the airspeed is 1-5 h-1The adsorption temperature is 0-40 ℃. The breakthrough adsorption operation was the same as in examples 1 to 5, and the adsorption results are shown in Table eight.
Table eight simulates Ag in gasoline at different sulfur concentrations2O/SiO2-TiO2Adsorption performance of graphene oxide composite aerogel on thiophene sulfur
As can be seen from Table eight, the gasoline is simulatedIncrease in the sulfur concentration of thiophene or benzothiophene, Ag2O/SiO2-TiO2The penetration adsorption capacity of the graphene oxide composite aerogel on thiophene and benzothiophene is reduced, so that the concentration of thiophene or benzothiophene sulfur in the simulated gasoline is preferably 0.1-5 mgS/g.
Examples 37 to 40: different regeneration solvents for Ag2O/SiO2-TiO2Regeneration adsorption performance of graphene oxide composite aerogel on thiophene sulfur in simulated gasoline
Respectively using cyclohexene, ethyl ether, benzene and toluene to treat used Ag2O/SiO2-TiO2Eluting thiophene sulfur in the-graphene oxide composite aerogel, and then using n-heptane to carry out Ag2O/SiO2-TiO2And eluting the regenerated solvent in the graphene oxide composite aerogel, and then performing a penetrating adsorption experiment on thiophene sulfides in the simulated gasoline. Wherein the airspeed is 1-5 h-1The adsorption temperature is 0-40 ℃, and the concentration of thiophene or benzothiophene sulfur in the simulated gasoline is 0.1-5 mgS/g. The operation of the breakthrough adsorption experiment was the same as in examples 1 to 5, and the adsorption results are shown in Table nine.
TABLE nine different regeneration solvent pairs to Ag2O/SiO2-TiO2Adsorption performance of graphene oxide composite aerogel on thiophene sulfur in simulated gasoline
As can be seen from Table nine, regenerated Ag2O/SiO2-TiO2The solvent used for the graphene oxide composite aerogel is cyclohexene, diethyl ether, benzene and toluene. When benzene is selected, Ag2O/SiO2-TiO2The graphene oxide composite aerogel has the best regeneration effect on thiophene and benzothiophene. Thus, the preferred regeneration solvent is benzene.
Claims (8)
1.Ag2O/SiO2-TiO2The method for adsorbing and removing the thiophene sulfur in the fuel oil by using the graphene oxide composite aerogel is characterized in thatIn addition to Ag2O/SiO2-TiO2The graphene oxide composite aerogel is used as an adsorbent, and the adsorbent is filled into a fixed bed adsorption device at the temperature of 0-100 ℃ for 1-10 h-1Introducing simulated gasoline containing thiophene sulfur at the airspeed, and adsorbing to obtain the simulated gasoline with the sulfur concentration of less than 1 ppm; ag2O/SiO2-TiO2The graphene oxide composite aerogel is prepared by taking a silver source, a silicon source and a titanium source as raw materials and adopting a sol-gel-normal pressure drying method; ag2O/SiO2-TiO2The molar ratio of silicon to titanium in the graphene oxide composite aerogel adsorbent is 50-100: 1; the molar ratio of silicon to silver is 50:1, and the adsorption temperature is 25-40 ℃.
2. Ag according to claim 12O/SiO2-TiO2The method for adsorbing and removing the thiophene sulfur in the fuel oil by the graphene oxide composite aerogel is characterized in that the adsorbed thiophene sulfur is thiophene or benzothiophene.
3. Ag according to claim 12O/SiO2-TiO2The method for adsorbing and removing thiophene sulfur in fuel oil by using the graphene oxide composite aerogel is characterized in that a silicon source is methyl orthosilicate, ethyl orthosilicate, silica sol or water glass, a silver source is silver acetate or silver nitrate, and a titanium source is tetrabutyl titanate.
4. Ag according to claim 12O/SiO2-TiO2The method for adsorbing and removing thiophene sulfur in fuel oil by using the graphene oxide composite aerogel is characterized in that a silicon source is ethyl orthosilicate, and a silver source is silver nitrate.
5. Ag according to claim 12O/SiO2-TiO2The method for adsorbing and removing thiophene sulfur in fuel oil by using-graphene oxide composite aerogel is characterized in that Ag is used2O/SiO2-TiO2-the mass percent of graphene oxide based on the total mass of the graphene oxide composite aerogel adsorbentThe amount is 0.30 to 1.52 wt%.
6. Ag according to claim 12O/SiO2-TiO2The method for adsorbing and removing the thiophene sulfur in the fuel oil by using the-graphene oxide composite aerogel is characterized in that the space velocity of introducing simulated gasoline containing the thiophene sulfur is 1-5 h-1。
7. Ag according to claim 12O/SiO2-TiO2The method for adsorbing and removing thiophene sulfur in fuel oil by using the graphene oxide composite aerogel is characterized in that the concentration of thiophene or benzothiophene sulfur in simulated gasoline is 0.1 mgS/g-10 mgS/g.
8. Ag according to claim 12O/SiO2-TiO2The method for adsorbing and removing thiophene sulfur in fuel oil by using-graphene oxide composite aerogel is characterized in that Ag2O/SiO2-TiO2The graphene oxide composite aerogel can be regenerated and utilized, and the solvent used for regeneration is cyclohexene, diethyl ether, benzene or toluene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810601512.1A CN108854953B (en) | 2018-06-12 | 2018-06-12 | Method for adsorption and removal of thiophene sulfur in fuel oil by Ag2O/SiO2-TiO2-graphene oxide composite aerogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810601512.1A CN108854953B (en) | 2018-06-12 | 2018-06-12 | Method for adsorption and removal of thiophene sulfur in fuel oil by Ag2O/SiO2-TiO2-graphene oxide composite aerogel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108854953A CN108854953A (en) | 2018-11-23 |
| CN108854953B true CN108854953B (en) | 2022-03-01 |
Family
ID=64338868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810601512.1A Active CN108854953B (en) | 2018-06-12 | 2018-06-12 | Method for adsorption and removal of thiophene sulfur in fuel oil by Ag2O/SiO2-TiO2-graphene oxide composite aerogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108854953B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110354810B (en) * | 2019-07-18 | 2022-02-15 | 浙江工业大学 | Method for removing thiophene sulfides from fuel oil by using SiO2-MTES-APTES-Ag composite aerogel |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102191080A (en) * | 2010-03-11 | 2011-09-21 | 中国石油化工股份有限公司 | Method for lowering sulfur and olefin content in gasoline |
| CN105217640A (en) * | 2015-08-20 | 2016-01-06 | 西南交通大学 | The preparation method of a kind of graphene oxide/SiO 2 hybrid aerogel |
| CN106118717A (en) * | 2016-07-07 | 2016-11-16 | 浙江工业大学 | A Method for Removing Thiophene Sulfur from Fuel Oil Using Ag2O/SiO2 Composite Airgel as Adsorbent |
-
2018
- 2018-06-12 CN CN201810601512.1A patent/CN108854953B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102191080A (en) * | 2010-03-11 | 2011-09-21 | 中国石油化工股份有限公司 | Method for lowering sulfur and olefin content in gasoline |
| CN105217640A (en) * | 2015-08-20 | 2016-01-06 | 西南交通大学 | The preparation method of a kind of graphene oxide/SiO 2 hybrid aerogel |
| CN106118717A (en) * | 2016-07-07 | 2016-11-16 | 浙江工业大学 | A Method for Removing Thiophene Sulfur from Fuel Oil Using Ag2O/SiO2 Composite Airgel as Adsorbent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108854953A (en) | 2018-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106118717B (en) | One kind is with Ag2O/SiO2Composite aerogel is the method that adsorbent removes thiophene sulphur in fuel oil | |
| CN109351338B (en) | By SiO2Method for removing thiophene sulfides in fuel oil by using APTES hybrid aerogel as adsorbent | |
| CN103120929B (en) | Solid desulfuration adsorbent and its production and use | |
| CN112452262B (en) | Preparation method and application of dopamine/silicon dioxide composite aerogel | |
| CN105921097A (en) | Preparation method and application of mesoporous graphite phase carbon nitride | |
| CN108342217A (en) | One kind is with Ag2O/SiO2Graphene oxide composite aerogel is the method that adsorbent removes thiophene sulphur in fuel oil | |
| CN104226240A (en) | Preparation method for catalysis/adsorption material by taking kieselguhr as carrier | |
| CN106590728B (en) | One kind is with Cu2O/SiO2-Al2O3The method that composite aerogel removes thiophene sulphur in fuel oil for adsorbent | |
| CN108893138B (en) | Method for removing thiophene sulfides from fuel oil by using Ag2O/SiO2-ZrO2 composite aerogel as adsorbent | |
| CN106111054A (en) | A method for removing thiophene-like sulfur in fuel oil using SiO2/Cu2O composite airgel as an adsorbent | |
| CN108940186B (en) | Method for adsorption and removal of thiophene sulfides in fuel oil by Ag2O/SiO2-TiO2 composite aerogel | |
| CN106423075A (en) | Silica gel immobilization functionalized ionic liquid adsorbing agent, preparation method and application | |
| CN105709685B (en) | One kind is with SiO2CoO composite aerogels are the method that adsorbent removes thiophene sulphur in gasoline | |
| CN108949220A (en) | One kind is with Pd (II)-SiO2Composite aerogel is the method that adsorbent removes thiophene-type sulfide in fuel oil | |
| CN108854953B (en) | Method for adsorption and removal of thiophene sulfur in fuel oil by Ag2O/SiO2-TiO2-graphene oxide composite aerogel | |
| CN110354812B (en) | With SiO2Method for removing thiophene sulfides in fuel oil by using-MTES-APTES composite aerogel as adsorbent | |
| CN107033946B (en) | One kind is with Cu2O/SiO2-TiO2Composite aerogel is the method that adsorbent removes thiophene sulphur in fuel oil | |
| CN110354809B (en) | A method for removing thiophene sulfides in fuel oil by using SiO2-APTES-Ag composite aerogel as adsorbent | |
| CN108311099A (en) | Ag2O/SiO2-Al2O3The method that graphene oxide composite aerogel removes thiophene sulphur in fuel oil | |
| CN108192656A (en) | The removal methods of thiophene sulphur in a kind of fuel oil | |
| CN110317631A (en) | The removal methods of thiophene sulphur in a kind of fuel oil | |
| CN105623711B (en) | One kind is with SiO2NiO composite aerogels are the new method of thiophene sulphur in adsorbent removing gasoline | |
| CN109111943A (en) | Cu2O/SiO2-TiO2The method of thiophene-type sulfide in-GO composite aerogel adsorbing and removing fuel oil | |
| CN110354810B (en) | Method for removing thiophene sulfides from fuel oil by using SiO2-MTES-APTES-Ag composite aerogel | |
| CN109550479A (en) | Cu2O/SiO2The method of thiophene-type sulfide in graphene oxide composite aerogel adsorbing and removing fuel oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |