CN108949220A - One kind is with Pd (II)-SiO2Composite aerogel is the method that adsorbent removes thiophene-type sulfide in fuel oil - Google Patents
One kind is with Pd (II)-SiO2Composite aerogel is the method that adsorbent removes thiophene-type sulfide in fuel oil Download PDFInfo
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- CN108949220A CN108949220A CN201810759040.2A CN201810759040A CN108949220A CN 108949220 A CN108949220 A CN 108949220A CN 201810759040 A CN201810759040 A CN 201810759040A CN 108949220 A CN108949220 A CN 108949220A
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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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- 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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- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses one kind with Pd (II)-SiO2Composite aerogel is the method that adsorbent removes thiophene-type sulfide in fuel oil, with Pd (II)-SiO2Composite aerogel is adsorbent, is filled into preventing fixed bed adsorber, under 0 ~ 100 DEG C of adsorption temp, 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.Pd (II)-SiO of the invention2Composite aerogel adsorbent introduces Pd (II) in silicon skeleton structure, and Pd (II) is more stable and because incorporation is relatively low, Pd (II)-SiO2The preparation cost of composite aerogel is low, by using the adsorbent, carries 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 desulfurization of fuel oil technical fields, and in particular to one kind is with Pd (II)-SiO2Composite aerogel is to inhale
The method of thiophene-type sulfide in attached dose of 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 fuel oil
Chemical energy is 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 coin
Element 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 type
Molecular sieve carried metallic salt composition.It is above-mentioned using molecular sieve as the π complexing adsorbent of carrier, carrier is cheap, preparation method
Simply, recyclable regenerative, but the transition metal ions Limited Number that molecular sieve sweetneing adsorbent is exchanged, the absorption to sulfide
Capacity is little, and the microcellular structure of micro porous molecular sieve itself, and the thiophene-type sulfide of macromolecular can not due to molecular dimension effect
π complexing is formed with metal ion in into duct, 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 sulphur break through volume of desulfurizing agent is low.But the pore structure of active carbon is with micro-
Based on hole, modified active carbon is still very small to the adsorption capacity of thiophene-based macromolecular sulfide, it is difficult to meet industrial production
Requirement.
Mesoporous γ-the Al that Chinese patent CN 103007873A is adulterated with copper2O3It contacts, utilizes with the fuel oil of sulfur-bearing
Absorption method carries out desulfurization, and operating cost is low, and adsorption capacity is big, and regenerates conveniently.101619231 A of Chinese patent CN is prepared for
A kind of desulfuration adsorbent, the adsorbent include using aluminium oxide as binder, and zinc oxide is carrier, then contacts with enveloping agent solution,
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 with metal oxide be carry
During the preparation process, metal ion is easy blocking metal oxide duct to the adsorbent of body, causes the active component of load in table
Face accumulation cannot be introduced into offer active sites in duct, reduce absorption desulfurization performance, and this method is more difficult applied to industrialized production.
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 one kind with Pd (II)-SiO2Composite aerogel is the side that adsorbent removes thiophene-type sulfide in fuel oil
Method, Pd of the invention (II)-SiO2Composite aerogel adsorbent passes through thiophene-based vulcanization in π Absorptive complex wave effect removing fuel oil
Object has the advantages that large amount of adsorption, easily regeneration and adsorption conditions are mild.
One kind is with Pd (II)-SiO2Composite aerogel is the method that adsorbent removes thiophene-type sulfide in fuel oil,
It is characterized in that with Pd (II)-SiO2Composite aerogel is adsorbent, is filled into preventing fixed bed adsorber, in 0 ~ 100 DEG C of absorption
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.
Described one kind is with Pd (II)-SiO2Composite aerogel is the side that adsorbent removes thiophene-type sulfide in fuel oil
Method, it is characterised in that adsorbed thiophene-type sulfide is thiophene or benzothiophene.
Described one kind is with Pd (II)-SiO2Composite aerogel is the side that adsorbent removes thiophene-type sulfide in fuel oil
Method, it is characterised in that the sulphur concentration of thiophene or benzothiophene is 0.1 ~ 10mgS/g, preferably 0.1 ~ 5 mgS/g in analog gasoline.
Described one kind is with Pd (II)-SiO2Composite aerogel is the side that adsorbent removes thiophene-type sulfide in fuel oil
Method, it is characterised in that Pd (II)-SiO2Composite aerogel is using silicon source and palladium source as raw material, using collosol and gel-atmosphere pressure desiccation
It is prepared into Pd (II)-SiO2Composite aerogel.
Described one kind is with Pd (II)-SiO2Composite aerogel is the side that adsorbent removes thiophene-type sulfide in fuel oil
Method, it is characterised in that silicon source is methyl orthosilicate, ethyl orthosilicate, silica solution or waterglass；Palladium source is palladium chloride or palladium sulfate；
It is preferred that silicon source is ethyl orthosilicate, palladium source is palladium chloride.
Described one kind is with Pd (II)-SiO2Composite aerogel is the side that adsorbent removes thiophene-type sulfide in fuel oil
Method, it is characterised in that Pd (II)-SiO2Silicon, palladium molar ratio in composite aerogel adsorbent are 80 ~ 1300: 1, preferably
160~650 : 1。
Described one kind is with Pd (II)-SiO2Composite aerogel is the side that adsorbent removes thiophene-type sulfide in fuel oil
Method, it is characterised in that adsorption temp is 0 ~ 40 DEG C；Air speed is 1 ~ 5 h when being passed through the analog gasoline containing thiophene or benzothiophene-1。
Described one kind is with Pd (II)-SiO2Composite aerogel is the side that adsorbent removes thiophene-type sulfide in fuel oil
Method, it is characterised in that Pd (II)-SiO after absorption2For composite aerogel adsorbent through solvent zeolite regeneration, the solvent is hexamethylene
Alkene, 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) Pd of the invention (II)-SiO2Composite aerogel has typical meso pore characteristics, such as aperture (5 ~ 20 nm), high porosity
(85 ~ 99%) and high-specific surface area (600 ~ 1500 m2/ g) etc. unique physico-chemicals property, therefore thiophene-type sulfide can be without hindrance
Enter in aeroge duct with hindering, and its structure is made of nanoscale skeleton particle, intraskeletal active component can be abundant
Exposure, this come into full contact with the active component of aeroge can with thiophene-type sulfide, i.e. Pd (II)-SiO2Composite aerogel pair
Thiophene-type sulfide has good absorption property.It, can be by the transition metal with π complexing in the synthesis process of aeroge
Salt is added thereto, therefore the amount of its active component is adjustable；
(2) Pd of the invention (II)-SiO2Composite aerogel adsorbent is as π complexing desulfuration adsorbent and Cu (I)-SiO2It is compound
Aeroge and Ag (I)-SiO2Composite aerogel is compared, and Cu (I) is easy that disproportionated reaction generation Cu (0) or Cu occur in air
(II), Ag (I) is light-exposed is easy to be reduced to Ag (0), introduces Pd (II) in silicon skeleton structure, and Pd (II) is more stable and because mixes
It is relatively low to enter amount, Pd (II)-SiO2The preparation cost of composite aerogel is not high；
(3) Pd of the invention (II)-SiO2Composite aerogel adsorbent has good absorption property to thiophene-type sulfide, absorption
It can be regenerated by solvent washing afterwards, still there is good absorption property after regeneration；
(4) of the invention with Pd (II)-SiO2Composite aerogel is the method that adsorbent removes thiophene-type sulfide in fuel oil,
Adsorption reaction carries out under normal pressure, adsorption conditions are mild, and has the advantages that requirement to adsorption plant is low and easy to operate,
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: Pd (II)-SiO2The preparation of composite aerogel adsorbent
Pd (the II)-SiO for being 320 with silicon palladium molar ratio2For composite aerogel adsorbent, using collosol and gel-constant pressure and dry
Method preparation, preparation step are as follows:
It weighs 0.04g palladium chloride to be added in the A beaker containing 5mL water, pH to 1.5 or so is adjusted with hydrochloric acid solution, at 40 DEG C
Stirring dissolves it sufficiently；Then the ethyl orthosilicate of the dehydrated alcohol of 25mL and 16mL are added in beaker A, stirring hydrolysis 90
After min, ammonium hydroxide is added and adjusts pH value to 6.5, obtains Pd (II)-SiO being stored at room temperature about 5 min2Compound alcogel, then in volume
Than 16 h of aging in dehydrated alcohol/ethyl orthosilicate for 25:15, to enhance the skeleton structure of gel, then with n-hexane pair
Gel carries out solvent displacement, replaces solvent twice in 24 h, removes ethyl alcohol, water and other organic molecules in gel.Last 80
DEG C ~ 150 DEG C at dry 2 h, obtain Pd (II)-SiO of silicon palladium molar ratio 320:12Composite aerogel.
Embodiment 1 ~ 5: different silica sources, Pd (the II)-SiO in palladium source2Composite aerogel vulcanizes thiophene-based in analog gasoline
The absorption property of object
Using Pd (the II)-SiO of the silicon palladium molar ratio of sol-gel method preparation for 3202In composite aerogel adsorbent, institute
Silicon source has methyl orthosilicate, ethyl orthosilicate, silica solution, and there are palladium sulfate, palladium chloride in palladium source.The Pd that preparation is completed
(Ⅱ)-SiO2Composite aerogel carries out penetrating absorption desulfurization, and concrete operations are as follows: filling out in the preventing fixed bed adsorber bottom
Suitable absorbent cotton is filled, Pd (II)-SiO of 1 g is then loaded2Composite aerogel and suitable quartz sand.Adsorption experiment starts
Before, loaded adsorbent is sufficiently soaked with normal heptane.It is passed through analog gasoline (1mgS/g) at 25 DEG C, is passed through analog gasoline sky
Speed is 2 h-1, the analog gasoline after adsorbing is collected in the lower end exit of reactor, with the gas-chromatography that FPD detector is housed
(0.5 μ gS/g of detection limit) is analyzed, and is set to breakthrough point when sulphur concentration is 1 μ gS/g in efflux.Obtained thiophene
Adsorption capacity is penetrated with benzothiophene, the results are shown in Table 1, table 2.
Pd (II)-SiO of 1 different silica sources of table2Absorption property of the composite aerogel to thiophene-type sulfide in analog gasoline
Pd (the II)-SiO in the different palladiums of table 2 source2Absorption property of the composite aerogel to thiophene-type sulfide in analog gasoline
From table 1, table 2 as can be seen that in synthesis Pd (II)-SiO2Silicon source used in composite aerogel, palladium source, when silicon source is selected just
Silester, when palladium chloride is selected in palladium source, synthesized Pd (II)-SiO2Composite aerogel is in penetrating adsorption experiment, to thiophene
Pheno and benzothiophene, which have, maximum penetrates adsorption capacity.Therefore preferably silicon source is ethyl orthosilicate, and palladium source is palladium chloride.
Embodiment 6 ~ 10: Pd (II)-SiO of different silicon palladium molar ratios2Composite aerogel is to thiophene sulphur in analog gasoline
The absorption property of compound
Selecting silicon palladium molar ratio is respectively 1300,640,320,160,110 Pd (II)-SiO2Aeroge, other conditions are the same as real
Apply Pd (II)-SiO of the preparation of example 22Composite aerogel carries out thiophene-type sulfide in analog gasoline to penetrate adsorption experiment.Its
Adsorption experiment operation is penetrated with embodiment 1 ~ 5, absorption result is shown in Table 3.
Pd (II)-SiO of the different silicon palladium molar ratios of table 32Suction of the composite aerogel to thiophene-type sulfide in analog gasoline
Attached performance
From table 3 it can be seen that Pd (II)-SiO2Aeroge is with the increase that the reduction of silicon palladium molar ratio is palladium content, to thiophene
First increase and subtract afterwards with the adsorption capacity that penetrates of benzothiophene.After silicon palladium molar ratio is 320:1, thiophene and benzothiophene penetrate suction
Attached capacity reaches maximum, therefore Pd (II)-SiO that preferred silicon palladium molar ratio is 160:1 ~ 320:12Aeroge.
Case study on implementation 11 ~ 15: different analog gasoline sample introduction air speeds are to Pd (II)-SiO2Composite aerogel is to analog gasoline
The absorption property of middle thiophene-type sulfide
Select Pd (the II)-SiO for being 320 with silicon palladium molar ratio2Composite aerogel adsorbent.It is 1 h in air speed-1、2 h-1、4 h-1、6 h-1、8 h-1Under, thiophene-type sulfide in analog gasoline is carried out to penetrate adsorption experiment.It is same that it penetrates adsorption experiment operation
Embodiment 1 ~ 5, absorption result is shown in Table 4.
Pd (II)-SiO under the different air speeds of table 42Absorption property of the composite aerogel to thiophene-type sulfide in analog gasoline
From table 4, it can be seen that with the increase of analog gasoline sample introduction air speed, the adsorption capacity that penetrates of thiophene and benzothiophene can be by
It is decrescence small, when air speed increases to 4 h-1Later, to thiophene-type sulfide to penetrate adsorption capacity smaller, therefore preferably air speed be 1 ~
4h-1。
Case study on implementation 16 ~ 20: different adsorption temps are to Pd (II)-SiO2Composite aerogel is to thiophene sulphur in analog gasoline
The absorption property of compound
Select Pd (the II)-SiO for being 320 with silicon palladium molar ratio2Composite aerogel adsorbent.Adsorption temp be selected as respectively 0 DEG C,
25 DEG C, 40 DEG C, 80 DEG C, 100 DEG C, carry out thiophene-type sulfide in analog gasoline to penetrate adsorption experiment.It is real to penetrate absorption
Operation is tested with embodiment 1 ~ 5, absorption result is shown in Table 8.
Pd (II)-SiO under the different adsorption temps of table 52Absorption of the composite aerogel to thiophene-type sulfide in analog gasoline
Performance
As can be seen from Table 5, with the raising of adsorption temp, the adsorption capacity that penetrates of thiophene and benzothiophene is gradually reduced,
After 80 DEG C, the adsorption penetration capacity of thiophene and benzothiophene is very small, shows at this temperature, by Pd (II)-SiO2It is compound
The thiophene of aeroge absorption has been desorbed with benzothiophene.Therefore Preferential adsorption temperature is 0 ~ 40 DEG C.
Case study on implementation 21 ~ 26: different sulphur concentrations are to Pd (II)-SiO2Composite aerogel vulcanizes thiophene-based in analog gasoline
The absorption property of object
Select Pd (the II)-SiO for being 320 with silicon palladium molar ratio2Composite aerogel adsorbent.Thiophene or benzo in analog gasoline
The sulphur concentration of thiophene is respectively that 0.1mgS/g, 0.5 mgS/g, 1 mgS/g, 2 mgS/g, 5 mgS/g, 10 mgS/g are penetrated
Adsorption experiment.Adsorption operations are penetrated with embodiment 1 ~ 5, absorption result is shown in Table 6.
The different sulphur concentrations of table 6 are to Pd (II)-SiO2Adsorptivity of the composite aerogel to thiophene-type sulfide in analog gasoline
Energy
It can be seen that the increase with thiophene or benzothiophene sulphur concentration in analog gasoline, Pd (II)-SiO from table 62Compound gas
Gel penetrates adsorption capacity in downward trend after first rising to thiophene and benzothiophene, thus preferably in analog gasoline thiophene or
Benzothiophene sulphur concentration is 0.5 ~ 5 mgS/g.
Case study on implementation 27 ~ 30: different regenerated solvents are to Pd (II)-SiO2Composite aerogel is to thiophene sulphur in analog gasoline
The regenerative adsorption performance of compound
Select with silicon palladium molar ratio be 320, thiophene penetrate adsorption capacity and the adsorption capacity that penetrates of benzothiophene is respectively
Pd (II)-SiO of 12.75mgS/g and 13.66 mgS/g2Composite aerogel adsorbent first uses cyclohexene, ether, benzene, toluene
To Pd (II)-SiO after using2Thiophene-type sulfide is eluted in composite aerogel, then again with normal heptane to Pd (II)-
SiO2Regenerated solvent is eluted in composite aerogel, then carries out penetrating adsorption experiment to thiophene-type sulfide in analog gasoline.
Adsorption experiment operation is penetrated with embodiment 1 ~ 5, absorption result is shown in Table 7.
The different regenerated solvents of table 7 are to Pd (II)-SiO2Absorption of the composite aerogel to thiophene-type sulfide in analog gasoline
Performance
As can be seen from Table 7, Pd (II)-SiO is regenerated2Solvent used in composite aerogel has cyclohexene, ether, benzene, toluene.Choosing
Pd (II)-SiO when with benzene, after regeneration2Composite aerogel is maximum to thiophene and benzothiophene adsorption capacity.Therefore it preferably regenerates
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 (8)
1. one kind is with Pd (II)-SiO2Composite aerogel is the method that adsorbent removes thiophene-type sulfide in fuel oil, feature
It is with Pd (II)-SiO2Composite aerogel is adsorbent, is filled into preventing fixed bed adsorber, in 0 ~ 100 DEG C of adsorption temp
Under, with 1 ~ 10 h-1Air speed be passed through the analog gasoline containing thiophene-type sulfide, 1ppm or less sulphur concentration is obtained after adsorbing
Analog gasoline.
2. one kind according to claim 1 is with Pd (II)-SiO2Composite aerogel is that adsorbent removes thiophene-based in fuel oil
The method of sulfide, it is characterised in that adsorbed thiophene-type sulfide is thiophene or benzothiophene.
3. one kind according to claim 2 is with Pd (II)-SiO2Composite aerogel is that adsorbent removes thiophene-based in fuel oil
The method of sulfide, it is characterised in that the sulphur concentration of thiophene or benzothiophene is 0.1 ~ 10mgS/g in analog gasoline, preferably
0.1~5 mgS/g。
4. one kind according to claim 1 is with Pd (II)-SiO2Composite aerogel is that adsorbent removes thiophene-based in fuel oil
The method of sulfide, it is characterised in that Pd (II)-SiO2Composite aerogel is using silicon source and palladium source as raw material, using collosol and gel-
Atmosphere pressure desiccation is prepared into Pd (II)-SiO2Composite aerogel.
5. one kind according to claim 4 is with Pd (II)-SiO2Composite aerogel is that adsorbent removes thiophene-based in fuel oil
The method of sulfide, it is characterised in that silicon source is methyl orthosilicate, ethyl orthosilicate, silica solution or waterglass；Palladium source is chlorination
Palladium or palladium sulfate；It is preferred that silicon source is ethyl orthosilicate, palladium source is palladium chloride.
6. one kind according to claim 1 is with Pd (II)-SiO2Composite aerogel is that adsorbent removes thiophene-based in fuel oil
The method of sulfide, it is characterised in that Pd (II)-SiO2Silicon, palladium molar ratio in composite aerogel adsorbent are 80 ~ 1300:
1, preferably 160 ~ 650: 1.
7. one kind according to claim 1 is with Pd (II)-SiO2Composite aerogel is that adsorbent removes thiophene-based in fuel oil
The method of sulfide, it is characterised in that adsorption temp is 0 ~ 40 DEG C；It is passed through the analog gasoline space-time containing thiophene or benzothiophene
Speed is 1 ~ 5 h-1。
8. one kind according to claim 1 is with Pd (II)-SiO2Composite aerogel is that adsorbent removes thiophene-based in fuel oil
The method of sulfide, it is characterised in that Pd (II)-SiO after absorption2Composite aerogel adsorbent is described through solvent zeolite regeneration
Solvent is cyclohexene, ether, benzene or toluene, preferably benzene.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317631A (en) * | 2019-07-02 | 2019-10-11 | 浙江工业大学 | The removal methods of thiophene sulphur in a kind of fuel oil |
| 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 |
| CN112473575A (en) * | 2020-11-19 | 2021-03-12 | 浙江工业大学 | CeO (CeO)2-Ag2O(PdO)/SiO2Preparation method and application of composite aerogel |
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| CN106118717A (en) * | 2016-07-07 | 2016-11-16 | 浙江工业大学 | A kind of with Ag2o/SiO2composite aerogel is the method for thiophene sulphur in adsorbent removing fuel oil |
| CN106111054A (en) * | 2016-07-07 | 2016-11-16 | 浙江工业大学 | A kind of with SiO2/ Cu2o composite aerogel is the method for thiophene sulphur in adsorbent removing fuel oil |
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| 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 |
| CN112473575A (en) * | 2020-11-19 | 2021-03-12 | 浙江工业大学 | CeO (CeO)2-Ag2O(PdO)/SiO2Preparation method and application of composite aerogel |
| CN112473575B (en) * | 2020-11-19 | 2023-09-19 | 浙江工业大学 | CeO (CeO) 2 -Ag 2 O(PdO)/SiO 2 Preparation method and application of composite aerogel |
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