CN109111943A - Cu2O/SiO2-TiO2The method of thiophene-type sulfide in-GO composite aerogel adsorbing and removing fuel oil - Google Patents
Cu2O/SiO2-TiO2The method of thiophene-type sulfide in-GO composite aerogel adsorbing and removing fuel oil Download PDFInfo
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- CN109111943A CN109111943A CN201810602653.5A CN201810602653A CN109111943A CN 109111943 A CN109111943 A CN 109111943A CN 201810602653 A CN201810602653 A CN 201810602653A CN 109111943 A CN109111943 A CN 109111943A
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- 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
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
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- 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
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- 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
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses Cu2O/SiO2‑TiO2The method of thiophene-type sulfide in-GO composite aerogel adsorbing and removing fuel oil, it is with Cu2O/SiO2‑TiO2Graphene oxide composite aerogel is adsorbent, preventing fixed bed adsorber is filled into, at a temperature of 0 ~ 100 DEG C, with 1 ~ 10 h‑1Air speed be passed through the analog gasoline containing thiophene-type sulfide, the analog gasoline of 1ppm or less sulphur concentration is obtained after adsorbing.The Cu that the present invention uses2O/SiO2‑TiO2Graphene oxide composite aerogel, graphene oxide is introduced in aeroge silicon skeleton structure, it is not only due to the excellent physical characteristic of graphene oxide and enhances the intensity and its heat-resisting quantity of aeroge skeleton, and there is the surface of graphene oxide introduced abundant oxygen-containing functional group to be also beneficial to the absorption property for further increasing it to thiophene-type sulfide；By using the adsorbent, carry out adsorption reaction under normal pressure, adsorption conditions are mild, the requirement to adsorption plant is low, easy to operate, the sulphur concentration of thiophene-type sulfide can reach 1ppm or less in analog gasoline after adsorbing.
Description
Technical field
The invention belongs to fuel oil processing technique fields, and in particular to a kind of Cu2O/SiO2-TiO2- GO composite aerogel is inhaled
The method of thiophene-type sulfide in attached removing fuel oil.
Background technique
With greatly developing for automobile-used industry, a large amount of discharges of vehicle exhaust sulfide not only make problem of environmental pollution increasingly
Seriously, equally also threaten the health of the mankind.Fuel cell also has quite high requirement to the sulfur content in fuel oil, has
The presence of machine sulfide can make the catalyst poisoning in fuel cell electrode, prevent fuel cell from effectively will be in bavin gasoline
Chemical energy be converted to electric energy.Therefore, have become the focus of global concern to the deep desulfuration of fuel oil.
Currently, the sulfur removal technology of fuel oil mainly has hydrodesulfurization technology, alkylating desulfurization technology, biological desulphurization skill
Art, abstraction desulfurization technology, oxidative desulfurization techniques, absorption desulfurization technology etc..In present industrial production, the main technique of desulfurization is still
Traditional hydrodesulfurization, but its there are operating costs compared with high, hydrogen-consuming volume is big, operating condition is harsh, and reduce pungent in gasoline
The disadvantages of alkane value.And hydrodesulfurization has preferable removal effect only for mercaptan, thioether, inorganic sulfur etc., for thermal stability pole
The desulfurization effect of high thiophene-type sulfide is very poor.Absorption desulfurization technical costs is cheap, and operating condition is mild, and desulfurization effect is good,
Free from environmental pollution, wherein the desulfurization of π Absorptive complex wave is selective relative to physical absorption desulfurization, relative to chemisorption desulfurization
It is easier to desorption and regeneration, is current most promising sulfur method.
The key of π Absorptive complex wave desulfurization is to prepare a kind of efficient π complexing adsorbent.It is usually used in preparing π complexing desulfurization
The metal ion of adsorbent has Cu2+、Cu+、Ni2+、Co2+Deng.And π complexing desulfuration adsorbent is prepared, it must be by these metal ions point
It is dispersed on the carrier of high-specific surface area.According to the difference of carrier, π complexing desulfuration adsorbent can be divided into molecular sieve, active carbon class,
Metal oxide-type.
103170305 A of Chinese patent CN is de- for depth using the 13X molecular sieve of loaded Cu ion as desulfuration adsorbent
Except the thiophene and derivatives and benzothiophene in gasoline.Wherein the constituent content of copper accounts for the 3%~5% of total sorbent weight,
Copper is ionic state.1511629 A of Chinese patent CN is prepared for a kind of adsorbent of molecular sieve of deep sulfide removing, by Y
The molecular sieve carried metallic salt composition of type.It is above-mentioned using molecular sieve as the π complexing adsorbent of carrier, carrier is cheap, preparation side
Method is simple, recyclable regenerative, but the transition metal ions Limited Number that molecular sieve sweetneing adsorbent is exchanged, the suction to sulfide
Attached capacity is little, and the microcellular structure of micro porous molecular sieve itself, the thiophene-type sulfide of macromolecular due to molecular dimension effect without
Method, which enters in duct, forms π complexing with metal ion, that is, is unable to reach deep desulfuration.
103143322 A of Chinese patent CN is prepared for a kind of acticarbon for having loaded Fe ion, in gasoline
Thiophene and derivatives have biggish adsorption capacity and selectivity, and preparation method is simple, and regeneration is easy, adsorbent service life
It is long.104549143 A of Chinese patent CN is by using salt and H containing metals such as Al, Zn, Ni3PO4As auxiliary agent to active carbon into
Row modification, preferably solve in gas raw material adsorption cleaning desulfurization technology there are single adsorbent cannot and meanwhile it is effectively de-
Except the problems such as removal efficiency of a variety of sulfide, sulphur is low and the working sulfur capacity of desulfurizing agent is low.But the pore structure of active carbon is with micropore
Based on, modified active carbon is still very small to the adsorption capacity of thiophene-based macromolecular sulfide, it is difficult to meet industrial
It is required that.
Mesoporous γ-the Al that 103007873 A of Chinese patent CN is adulterated with copper2O3It is contacted with the fuel oil of sulfur-bearing, benefit
Desulfurization is realized with absorption method, and operating cost is low, and adsorption capacity is big, and regenerates conveniently.101619231 A of Chinese patent CN preparation
A kind of desulfuration adsorbent, the adsorbent include using aluminium oxide as binder, and zinc oxide is carrier, then is connect with enveloping agent solution
Touching, then carried metal promotor, is used for the desulfurization of fuel oil, and activity is high, and absorption sulfur capacity is big.But it is above-mentioned to be with metal oxide
During the preparation process, metal ion is easy blocking metal oxide duct to the adsorbent of carrier, and the active component of load is caused to exist
Surface accumulation cannot be introduced into offer active sites in duct, reduce absorption desulfurization performance, and this method is more difficult applied to industrial metaplasia
It produces.
Summary of the invention
Desulfuration adsorbent above problem present in thiophene-type sulfide in removing fuel oil is complexed for existing π, this
The purpose of invention is Cu2O/SiO2-TiO2The method of thiophene-type sulfide in-GO composite aerogel adsorbing and removing fuel oil, this
The Cu of invention2O/SiO2-TiO2Graphene oxide composite aerogel adsorbent is acted in removing fuel oil by π Absorptive complex wave
Thiophene-type sulfide has the advantages that large amount of adsorption, easily regeneration and adsorption conditions are mild.
The Cu2O/SiO2-TiO2The method of thiophene-type sulfide in-GO composite aerogel adsorbing and removing fuel oil,
It is characterized in that with Cu2O/SiO2-TiO2Graphene oxide composite aerogel is adsorbent, preventing fixed bed adsorber is filled into, 0
At a temperature of~100 DEG C, with 1~10h-1Air speed be passed through the analog gasoline containing thiophene-type sulfide, 1ppm is obtained after adsorbing
The analog gasoline of following sulphur concentration, GO are the abbreviation of graphene oxide, similarly hereinafter.
The Cu2O/SiO2-TiO2The method of thiophene-type sulfide in-GO composite aerogel adsorbing and removing fuel oil,
It is characterized in that adsorbed thiophene-type sulfide is thiophene or benzothiophene.
The Cu2O/SiO2-TiO2The method of thiophene-type sulfide in-GO composite aerogel adsorbing and removing fuel oil,
It is characterized in that in analog gasoline that thiophene or benzothiophene sulphur concentration are 0.1mgS/g~10mgS/g, preferably 0.1~5mgS/g.
The Cu2O/SiO2-TiO2The method of thiophene-type sulfide in-GO composite aerogel adsorbing and removing fuel oil,
It is characterized in that Cu2O/SiO2-TiO2Graphene oxide composite aerogel using graphene oxide, silicon source, copper source and titanium source as raw material,
CuO/SiO is prepared using collosol and gel-atmosphere pressure desiccation2-TiO2Composite aerogel, CuO/SiO2-TiO2Compound gas
Gel obtains Cu through hydrogen reducing2O/SiO2-TiO2Graphene oxide composite aerogel.
The Cu2O/SiO2-TiO2The method of thiophene-type sulfide in-GO composite aerogel adsorbing and removing fuel oil,
It is characterized in that silicon source is methyl orthosilicate, ethyl orthosilicate, silica solution or waterglass；Titanium source is butyl titanate, and copper source is chlorine
Change copper or copper acetate, preferably silicon source is ethyl orthosilicate, and copper source is copper acetate.
The Cu2O/SiO2-TiO2The method of thiophene-type sulfide in-GO composite aerogel adsorbing and removing fuel oil,
It is characterized in that reduction temperature is 100~220 DEG C, preferably 140~180 DEG C；Recovery time is 3~7h, preferably 4~6h.
The Cu2O/SiO2-TiO2The method of thiophene-type sulfide in-GO composite aerogel adsorbing and removing fuel oil,
It is characterized in that Cu2O/SiO2-TiO2Silicon titanium molar ratio in graphene oxide composite aerogel adsorbent is 2~150:1, preferably
For 20~50:1；Copper silicon molar ratio is 2~150:1, preferably 40~70:1.
The Cu2O/SiO2-TiO2The method of thiophene-type sulfide in-GO composite aerogel adsorbing and removing fuel oil,
It is characterized in that Cu2O/SiO2-TiO2In graphene oxide composite aerogel adsorbent, the mass percentage of graphene oxide is
0.67 ‰ -3.33 ‰, preferably 1.33 ‰ -2.67 ‰.
The Cu2O/SiO2-TiO2The method of thiophene-type sulfide in-GO composite aerogel adsorbing and removing fuel oil,
It is characterized in that adsorption temp is 0~40 DEG C；Air speed is 1~4h when being passed through the analog gasoline containing thiophene or benzothiophene-1。
The Cu2O/SiO2-TiO2The method of thiophene-type sulfide in-GO composite aerogel adsorbing and removing fuel oil,
Cu after being characterized in that absorption2O/SiO2-TiO2Graphene oxide composite aerogel adsorbent is described molten through solvent zeolite regeneration
Agent is cyclohexene, ether, benzene or toluene, preferably benzene.
By using above-mentioned technology, compared with prior art, beneficial effects of the present invention are as follows:
1) Cu of the invention2O/SiO2-TiO2Graphene oxide composite aerogel have typical meso pore characteristics aperture (5~
20nm), high porosity (85~99%), high-specific surface area (600~1500m2/ g) etc. unique physico-chemicals property, therefore thiophene
Class sulfide can unhinderedly enter in aeroge duct, and its structure is made of nanoscale skeleton particle, intraskeletal
Active component can sufficiently expose, this come into full contact with the active component of aeroge can with thiophene-type sulfide, i.e. Cu2O/SiO2-
TiO2Graphene oxide composite aerogel has good absorption property to thiophene-type sulfide；
2) Cu of the invention2O/SiO2-TiO2Desulfuration adsorbent and other is complexed as π in graphene oxide composite aerogel
π complexing adsorbent is compared, it introduces Ti in silicon skeleton structure2+, Ti has very strong oxygen storage capacity, can be in Cu2+It is reduced into Cu+'s
In the process, make Cu2O structure is more stable, increases aeroge inner surface active component Cu+Quantity.And its structure is by nanoscale
Skeleton particle is constituted, and expose intraskeletal active component can sufficiently.In the synthesis process of aeroge, can there will be π complexing
The transition metal salt of effect is added thereto, therefore the amount of its active component is adjustable；
3) Cu of the invention2O/SiO2-TiO2Graphene oxide composite aerogel, with Cu2O/SiO2Aeroge is compared, it
Graphene oxide is introduced in aeroge silicon skeleton structure, the excellent physical characteristic of graphene oxide is not only due to and enhances airsetting
The intensity of glue skeleton and its heat-resisting quantity, and there is the surface of graphene oxide introduced oxygen-containing functional group abundant to be also beneficial to
Further increase its absorption property to thiophene-type sulfide；
4) Cu of the invention2O/SiO2-TiO2Graphene oxide composite aerogel π complexing adsorbent is to thiophene-type sulfide
There is good absorption property, can be regenerated by solvent washing, still there is good absorption property after regeneration；
5) adsorption reaction of the invention carries out under normal pressure, adsorption conditions are mild, the requirement to adsorption plant is low, operation side
Just, the sulphur concentration of thiophene-type sulfide can reach 1ppm or less in analog gasoline after adsorbing.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
Embodiment:
Cu2O/SiO2-TiO2The preparation of graphene oxide composite aerogel adsorbent:
To fix copper silicon molar ratio as 50, silicon titanium molar ratio is 20, the Cu that graphene oxide incorporation is 2 ‰2O/SiO2-
TiO2For graphene oxide composite aerogel adsorbent, prepared using collosol and gel-atmosphere pressure desiccation, preparation step is such as
Under:
Prepare 2 beakers A and B first.It weighs 0.006g graphene oxide and is added to the A beaker containing 20mL dehydrated alcohol
Dissolution, and ultrasound 30min or so；0.611g butyl titanate is slowly added to A beaker, mixing is equal under the conditions of magnetic agitation
It is even；8mL ethyl orthosilicate is added to the mixing of A beaker again and adjusts pH to 1.5 or so with hydrochloric acid solution, weighs 0.14g copper acetate
It is dissolved in the B beaker containing 3mL water, forms B solution；When mixed solution in A beaker is uniformly mixed, in the case of stirring
B solution is added in A beaker dropwise, obtained A mixed liquor.After hydrolyzing 90min, addition ammonium hydroxide adjusting pH value to 6.5, room temperature
Lower standing about 5min obtains Cu2O/SiO2-TiO2The compound alcogel of graphene oxide, then volume ratio be 25:15 dehydrated alcohol/
Aging 16h in positive silicoacetic acid ester to enhance the skeleton structure of gel, then with n-hexane carries out solvent displacement to gel, it is interior for 24 hours more
Solvent twice is changed, ethyl alcohol, water, acid and other organic molecules in gel are removed.Dry 2h, obtains silicon at last 80 DEG C~150 DEG C
The CuO/SiO of copper molar ratio 50:12-TiO2Graphene oxide composite aerogel, then 5h is restored at 160 DEG C through hydrogen, obtain silicon
The Cu of copper molar ratio 50:12O/SiO2-TiO2Graphene oxide composite aerogel.
Examples 1 to 5: different silica sources, the Cu of copper source2O/SiO2-TiO2Graphene oxide composite aerogel is to simulation vapour
The absorption property of thiophene-type sulfide in oil
In the copper silicon molar ratio for using sol-gel method to prepare for 50, silicon titanium molar ratio 20, graphene oxide incorporation
2 ‰ Cu2O/SiO2-TiO2In graphene oxide composite aerogel, silicon source used have methyl orthosilicate, ethyl orthosilicate,
Silica solution, copper source have copper nitrate, copper acetate.The Cu that preparation is completed2O/SiO2-TiO2Graphene oxide composite aerogel carries out
Penetrate absorption desulfurization, concrete operations are as follows: in preventing fixed bed adsorber, the bottom loads suitable absorbent cotton, then
Load the Cu of 1g2O/SiO2-TiO2Graphite oxide aerogel and suitable quartz sand.Before adsorption experiment starts, normal heptane is used
Sufficiently the loaded adsorbent of wetting.Analog gasoline (1mgS/g), air speed 2h are passed through at 25 DEG C-1, in the lower end of reactor
The analog gasoline after absorption is collected in exit, is analyzed with the gas-chromatography (0.5 μ gS/g of detection limit) equipped with FPD detector,
It is set to breakthrough point when sulphur concentration is 0.001mgS/g in efflux.The absorption that penetrates of obtained thiophene and benzothiophene is held
Amount, the results are shown in Table 1, table 2.
The Cu of 1 different silica sources of table2O/SiO2-TiO2Graphene oxide composite aerogel is to thiophene in analog gasoline
The absorption property of pheno class sulfide
The Cu of the different copper sources of table 22O/SiO2-TiO2Graphene oxide composite aerogel is to thiophene in analog gasoline
The absorption property of pheno class sulfide
From table 1, table 2 as can be seen that in synthesis Cu2O/SiO2-TiO2Silicon source used in graphene oxide composite aerogel,
Copper source, when silicon source selects ethyl orthosilicate, and copper source selects copper acetate, synthesized Cu2O/SiO2-TiO2Graphene oxide is multiple
Aeroge is closed in penetrating adsorption experiment, has to thiophene and benzothiophene and maximum penetrates adsorption capacity.Therefore preferably silicon source is
Ethyl orthosilicate, copper source are copper acetate.
Embodiment 6~10: the Cu of different silicon titanium molar ratios2O/SiO2-TiO2Graphene oxide composite aerogel is to simulation
The absorption property of thiophene-type sulfide in gasoline
Copper silicon molar ratio 50:1, silicon titanium molar ratio difference 5,10,20,50,100 are selected, graphene oxide incorporation is 2 ‰
Cu2O/SiO2-TiO2Graphene oxide composite aerogel adsorbent, the Cu that other conditions are prepared with embodiment 22O/SiO2-
TiO2Graphene oxide composite aerogel carries out thiophene-type sulfide in analog gasoline to penetrate adsorption experiment.It penetrates absorption
The same Examples 1 to 5 of experimental implementation, absorption result are shown in Table 3.
The Cu of the different silicon titanium molar ratios of table 32O/SiO2-TiO2Graphene oxide composite aerogel is to thiophene in analog gasoline
The absorption property of class sulfide
From table 3 it can be seen that the Cu of different silicon titanium molar ratios2O/SiO2-TiO2Graphene oxide composite aerogel with
The reduction of silicon titanium molar ratio is the increase of Ti content, and the adsorption capacity that penetrates of thiophene and benzothiophene is first increased and dropped afterwards.In silicon titanium
When molar ratio is 20:1, the adsorption capacity that penetrates of thiophene and benzothiophene reaches maximum, therefore preferably silicon titanium molar ratio is 20:1
The Cu of~50:12O/SiO2-TiO2Graphene oxide composite aerogel.
Embodiment 11~15: the Cu of different copper silicon molar ratios2O/SiO2-TiO2Graphene oxide composite aerogel is to simulation
The absorption property of thiophene-type sulfide in gasoline
Copper silicon molar ratio difference 40,50,70,100 is selected, silicon titanium molar ratio is 20, and graphene oxide incorporation is 2 ‰
Cu2O/SiO2-TiO2Graphene oxide composite aerogel adsorbent, the Cu that other conditions are prepared with embodiment 22O/SiO2-
TiO2Graphene oxide composite aerogel carries out thiophene-type sulfide in analog gasoline to penetrate adsorption experiment.It penetrates absorption
The same Examples 1 to 5 of experimental implementation, absorption result are shown in Table 4.
The Cu of the different copper silicon molar ratios of table 42O/SiO2-TiO2Graphene oxide composite aerogel is to thiophene in analog gasoline
The absorption property of class sulfide
From table 4, it can be seen that Cu2O/SiO2-TiO2Graphene oxide composite aerogel with copper silicon molar ratio reduction
That is the increase of copper content first increases and subtracts afterwards to the adsorption capacity that penetrates of thiophene and benzothiophene.After copper silicon molar ratio is 50:1, thiophene
Pheno and the adsorption capacity that penetrates of benzothiophene reach maximum, therefore the Cu that preferred copper silicon molar ratio is 50:1~70:12O/SiO2-
TiO2Graphene oxide composite aerogel.
Case study on implementation 16~20: different content graphene oxide is to Cu2O/SiO2-TiO2Graphene oxide composite aerogel
To the absorption property of thiophene-type sulfide in analog gasoline
Select copper silicon molar ratio be 50, silicon titanium molar ratio be 20, mix graphene oxide amount difference 0.67 ‰,
1.33 ‰, 2 ‰, 2.67 ‰, 3.33 ‰ Cu2O/SiO2-TiO2Graphene oxide composite aerogel, the same embodiment of other conditions
The Cu of 2 preparations2O/SiO2-TiO2Graphene oxide composite aerogel carries out thiophene-type sulfide in analog gasoline to penetrate suction
Attached experiment.It penetrates adsorption experiment and operates same Examples 1 to 5, and absorption result is shown in Table 5.
The Cu of the incorporation different content graphene oxide of table 52O/SiO2-TiO2Graphene oxide composite aerogel is to simulation vapour
The absorption property of thiophene-type sulfide in oil
As can be seen from Table 5, Cu2O/SiO2-TiO2Graphene oxide composite aerogel is with graphene oxide incorporation
Increase, the adsorption capacity that penetrates of thiophene and benzothiophene is first increased and subtracts afterwards.When graphene oxide incorporation reaches 2 ‰, thiophene
Pheno and the adsorption capacity that penetrates of benzothiophene reach maximum, therefore preferably graphene oxide incorporation is 1.33 ‰ -2.67 ‰
Cu2O/SiO2-TiO2Graphene oxide composite aerogel.
Embodiment 21-27:CuO/SiO2-TiO2Obtained by graphene oxide composite aerogel restores under different reduction temperatures
Cu2O/SiO2-TiO2Influence of the graphene oxide composite aerogel to thiophene-type sulfide in absorption analog gasoline
Selecting fixed copper silicon molar ratio is 50, and silicon titanium molar ratio is 20, the Cu that graphene oxide incorporation is 2 ‰2O/
SiO2-TiO2Graphene oxide composite aerogel adsorbent, reduction temperature are respectively 100,120,140,160,180,200,220
DEG C, the Cu that other conditions are prepared with embodiment 22O/SiO2-TiO2Graphene oxide composite aerogel, to thiophene in analog gasoline
Class sulfide carries out penetrating adsorption experiment.It penetrates adsorption experiment and operates same Examples 1 to 5, and absorption result is shown in Table 6.
6 difference Cu of table2O/SiO2-TiO2The reduction temperature of graphene oxide composite aerogel is to thiophene in absorption analog gasoline
The influence of pheno class sulfide
As can be seen from Table 6, CuO/SiO2-TiO2Graphene oxide composite aerogel with reduction temperature rising,
SiO2/Cu2O-TiO2The adsorption capacity that penetrates of thiophene and benzothiophene is first increased drop afterwards therewith.When reduction temperature is 160 DEG C,
The adsorption capacity that penetrates of thiophene and benzothiophene reaches maximum, therefore preferably reduction temperature is 140~180 DEG C.
Case study on implementation 28~32: the different recovery times are to Cu2O/SiO2-TiO2Graphene oxide composite aerogel adsorbs mould
The influence of thiophene-type sulfide in quasi- gasoline
Selecting fixed copper silicon molar ratio is 50, and silicon titanium molar ratio is 20, the Cu that graphene oxide incorporation is 2 ‰2O/
SiO2-TiO2Graphene oxide composite aerogel adsorbent, recovery time are respectively 3h, 4h, 5h, 6h, 7h, and other conditions are the same as real
Apply the Cu of the preparation of example 22O/SiO2-TiO2Graphene oxide composite aerogel wears thiophene-type sulfide in analog gasoline
Saturating adsorption experiment.It penetrates adsorption experiment and operates same Examples 1 to 5, and absorption result is shown in Table 7.
Influence of the different recovery times of table 7 to thiophene-type sulfide in absorption analog gasoline
As can be seen from Table 7, with the lengthening of recovery time, thiophene and benzothiophene are penetrated after adsorption capacity can first increase
Subtract, when the recovery time increasing to 6h, the adsorption capacity that penetrates of thiophene-type sulfide is become most significantly, therefore the preferred recovery time
For 4~6h.
Case study on implementation 32~36: different air speeds are to Cu2O/SiO2-TiO2Graphene oxide composite aerogel is to analog gasoline
The absorption property of middle thiophene-type sulfide
Selecting fixed copper silicon molar ratio is 50, and silicon titanium molar ratio is 20, the Cu that graphene oxide incorporation is 2 ‰2O/
SiO2-TiO2Graphene oxide composite aerogel adsorbent is 1h in air speed-1、2h-1、4h-1、6h-1、8h-1Under, to simulation vapour
Thiophene-type sulfide carries out penetrating adsorption experiment in oil.It penetrates adsorption experiment and operates same Examples 1 to 5, and absorption result is shown in Table
8。
Cu under the different air speeds of table 82O/SiO2-TiO2Graphene oxide composite aerogel vulcanizes thiophene-based in analog gasoline
The absorption property of object
As can be seen from Table 8, penetrating adsorption capacity and being gradually increased for the reduction of air speed, thiophene and benzothiophene, works as sky
Speed is reduced to 4h-1Later, adsorption capacity variation is penetrated less to thiophene-type sulfide, therefore preferably air speed is 1~4h-1。
Case study on implementation 37~41: different adsorption temps are to Cu2O/SiO2-TiO2Graphene oxide composite aerogel is to simulation
The absorption property of thiophene-type sulfide in gasoline
Selecting fixed copper silicon molar ratio is 50, and silicon titanium molar ratio is 20, the Cu that graphene oxide incorporation is 2 ‰2O/
SiO2-TiO2Graphene oxide composite aerogel adsorbent.Adsorption temp is selected as 0 DEG C, 25 DEG C, 40 DEG C, 80 DEG C, 100 DEG C respectively,
Thiophene-type sulfide in analog gasoline is carried out to penetrate adsorption experiment.It penetrates adsorption experiment and operates same Examples 1 to 5, absorption knot
Fruit is shown in Table 9.
Cu under the different adsorption temps of table 92O/SiO2-TiO2Graphene oxide composite aerogel is to thiophene-based in analog gasoline
The absorption property of sulfide
As can be seen from Table 9, with the raising of adsorption temp, the adsorption capacity that penetrates of thiophene and benzothiophene gradually subtracts
Small, after 80 DEG C, the adsorption penetration capacity of thiophene and benzothiophene is very small, shows at this temperature, by Cu2O/SiO2-
TiO2The thiophene of graphene oxide composite aerogel absorption has been desorbed with benzothiophene.Therefore Preferential adsorption temperature is 0~40
℃。
Case study on implementation 42~47: different sulphur concentrations are to Cu2O/SiO2-TiO2Graphene oxide composite aerogel is to simulation vapour
The absorption property of thiophene-type sulfide in oil
Selecting fixed copper silicon molar ratio is 50, and silicon titanium molar ratio is 20, the Cu that graphene oxide incorporation is 2 ‰2O/
SiO2-TiO2Graphene oxide composite aerogel adsorbent.The sulphur concentration of thiophene or benzothiophene in analog gasoline is respectively
0.1mgS/g, 0.5mgS/g, 1mgS/g, 2mgS/g, 5mgS/g, 10mgS/g carry out penetrating adsorption experiment.It is same to penetrate adsorption operations
Examples 1 to 5, absorption result are shown in Table 10.
The different sulphur concentrations of table 10 are to Cu2O/SiO2-TiO2Graphene oxide composite aerogel is to thiophene-based in analog gasoline
The absorption property of sulfide
As can be seen from Table 10, in analog gasoline thiophene or benzothiophene sulphur concentration increase, Cu2O/SiO2-TiO2Oxygen
Graphite alkene composite aerogel penetrates adsorption capacity in the trend risen to thiophene and benzothiophene, and absorption is held after reaching 5mgS/g
Amount varies less, therefore preferably thiophene or benzothiophene sulphur concentration are 0.1~5mgS/g in analog gasoline.
Case study on implementation 48~51: different regenerated solvents are to Cu2O/SiO2-TiO2Graphene oxide composite aerogel is to simulation
The regenerative adsorption performance of thiophene-type sulfide in gasoline
Selecting fixed copper silicon molar ratio is 50, and silicon titanium molar ratio is 20, and graphene oxide incorporation is penetrating for 2 ‰ thiophene
Adsorption capacity and benzothiophene penetrate the Cu that adsorption capacity is respectively 19.36mgS/g and 21.76mgS/g2O/SiO2-TiO2-
Graphene oxide composite aerogel adsorbent first uses cyclohexene, and ether, benzene, toluene is to the Cu after using2O/SiO2-TiO2Oxygen
Thiophene-type sulfide is eluted in graphite alkene composite aerogel, then again with normal heptane to Cu2O/SiO2-TiO2Aoxidize stone
Regenerated solvent is eluted in black alkene composite aerogel, then carries out penetrating adsorption experiment to thiophene-type sulfide in analog gasoline.
It penetrates adsorption experiment and operates same Examples 1 to 5, absorption result is shown in Table 11
The different regenerated solvents of table 11 are to Cu2O/SiO2-TiO2Graphene oxide composite aerogel is to thiophene in analog gasoline
The absorption property of class sulfide
As can be seen from Table 11, Cu is regenerated2O/SiO2-TiO2Solvent used in graphene oxide composite aerogel has hexamethylene
Alkene, ether, benzene, toluene.When selecting benzene, the Cu after regeneration2O/SiO2-TiO2Graphene oxide composite aerogel to thiophene with
The adsorption capacity of benzothiophene is maximum.Therefore preferably regenerated solvent is benzene.
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered
When the concrete form for being seen as limited by embodiment and being stated, protection scope of the present invention is also only in those skilled in the art's root
According to present inventive concept it is conceivable that equivalent technologies mean.
Claims (10)
1. Cu2O/SiO2-TiO2The method of thiophene-type sulfide, feature exist in-GO composite aerogel adsorbing and removing fuel oil
In with Cu2O/SiO2-TiO2Graphene oxide composite aerogel is adsorbent, preventing fixed bed adsorber is filled into, at 0 ~ 100 DEG C
At a temperature of, with 1 ~ 10 h-1Air speed be passed through the analog gasoline containing thiophene-type sulfide, it is dense that 1ppm or less sulphur is obtained after adsorbing
The analog gasoline of degree.
2. Cu according to claim 12O/SiO2-TiO2Thiophene-based vulcanizes in-GO composite aerogel adsorbing and removing fuel oil
The method of object, it is characterised in that adsorbed thiophene-type sulfide is thiophene or benzothiophene.
3. Cu according to claim 22O/SiO2-TiO2Thiophene sulphur in-GO composite aerogel adsorbing and removing fuel oil
The method of compound, it is characterised in that thiophene or benzothiophene sulphur concentration are 0.1mgS/g ~ 10mgS/g in analog gasoline, preferably
0.1~5 mgS/g。
4. Cu according to claim 12O/SiO2-TiO2Thiophene sulphur in-GO composite aerogel adsorbing and removing fuel oil
The method of compound, it is characterised in that Cu2O/SiO2 - TiO2Graphene oxide composite aerogel is with graphene oxide, silicon source, copper
Source and titanium source are raw material, and CuO/SiO is prepared using collosol and gel-atmosphere pressure desiccation2-TiO2Composite aerogel, CuO/
SiO2-TiO2Composite aerogel obtains Cu through hydrogen reducing2O/SiO2-TiO2Graphene oxide composite aerogel.
5. Cu according to claim 42O/SiO2-TiO2Thiophene-based vulcanizes in-GO composite aerogel adsorbing and removing fuel oil
The method of object, it is characterised in that silicon source is methyl orthosilicate, ethyl orthosilicate, silica solution or waterglass；Titanium source is four fourth of metatitanic acid
Ester, copper source are copper chloride or copper acetate, and preferably silicon source is ethyl orthosilicate, and copper source is copper acetate.
6. Cu according to claim 42O/SiO2-TiO2Thiophene sulphur in-GO composite aerogel adsorbing and removing fuel oil
The method of compound, it is characterised in that reduction temperature is 100 ~ 220 DEG C, preferably 140 ~ 180 DEG C；Recovery time is 3 ~ 7 h, excellent
It is selected as 4 ~ 6 h.
7. Cu according to claim 12O/SiO2-TiO2Thiophene sulphur in-GO composite aerogel adsorbing and removing fuel oil
The method of compound, it is characterised in that Cu2O/SiO2- TiO2Silicon titanium molar ratio in graphene oxide composite aerogel adsorbent
For 2 ~ 150:1, preferably 20 ~ 50:1；Copper silicon molar ratio is 2 ~ 150: 1, preferably 40 ~ 70: 1.
8. Cu according to claim 12O/SiO2-TiO2Thiophene-based vulcanizes in-GO composite aerogel adsorbing and removing fuel oil
The method of object, it is characterised in that Cu2O/SiO2-TiO2In graphene oxide composite aerogel adsorbent, the matter of graphene oxide
Measuring percentage composition is 0.67 ‰ -3.33 ‰, preferably 1.33 ‰ -2.67 ‰.
9. Cu according to claim 12O/SiO2-TiO2Thiophene sulphur in-GO composite aerogel adsorbing and removing fuel oil
The method of compound, it is characterised in that adsorption temp is 0 ~ 40 DEG C；Air speed when being passed through the analog gasoline containing thiophene or benzothiophene
For 1 ~ 4 h-1。
10. Cu according to claim 12O/SiO2-TiO2Thiophene sulphur in-GO composite aerogel adsorbing and removing fuel oil
The method of compound, it is characterised in that the Cu after absorption2O/SiO2-TiO2Graphene oxide composite aerogel adsorbent is washed through solvent
De- regeneration, the solvent are cyclohexene, ether, benzene or toluene, preferably benzene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110354811A (en) * | 2019-07-18 | 2019-10-22 | 浙江工业大学 | With Pd (II)-SiO2- GO composite aerogel is the method that adsorbent removes thiophene-type sulfide in fuel oil |
| CN110354813A (en) * | 2019-07-18 | 2019-10-22 | 浙江工业大学 | With SiO2- MTES- graphene oxide composite aerogel is the method that adsorbent removes thiophene-type sulfide in fuel oil |
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|---|---|---|---|---|
| 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 |
| CN107033946A (en) * | 2017-03-14 | 2017-08-11 | 浙江工业大学 | One kind is with Cu2O/SiO2‑TiO2Composite aerogel is the method that adsorbent removes thiophene sulphur in fuel oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN107033946A (en) * | 2017-03-14 | 2017-08-11 | 浙江工业大学 | One kind is with Cu2O/SiO2‑TiO2Composite aerogel is the method that adsorbent removes thiophene sulphur in fuel oil |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110354811A (en) * | 2019-07-18 | 2019-10-22 | 浙江工业大学 | With Pd (II)-SiO2- GO composite aerogel is the method that adsorbent removes thiophene-type sulfide in fuel oil |
| CN110354813A (en) * | 2019-07-18 | 2019-10-22 | 浙江工业大学 | With SiO2- MTES- graphene oxide composite aerogel is the method that adsorbent removes thiophene-type sulfide in fuel oil |
| CN110354813B (en) * | 2019-07-18 | 2022-03-11 | 浙江工业大学 | With SiO2Method for removing thiophene sulfides in fuel oil by taking-MTES-graphene oxide composite aerogel as adsorbent |
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