CN110317631A - The removal methods of thiophene sulphur in a kind of fuel oil - Google Patents

The removal methods of thiophene sulphur in a kind of fuel oil Download PDF

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CN110317631A
CN110317631A CN201910590126.1A CN201910590126A CN110317631A CN 110317631 A CN110317631 A CN 110317631A CN 201910590126 A CN201910590126 A CN 201910590126A CN 110317631 A CN110317631 A CN 110317631A
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thiophene
aptes
sulphur
sio
fuel oil
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卢永康
张波
陈飞帆
殷路霞
宫婉慧
高建广
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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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
    • B01J20/02—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
    • 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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
    • 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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
    • 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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
    • 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
    • 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
    • C10G25/12—Recovery of used adsorbent
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Dispersion Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The removal methods of thiophene sulphur, belong to fuel oil processing technique field in a kind of fuel oil.This method using ethyl orthosilicate as silicon source, using 3- aminopropyl triethoxysilane as ammonia source, using palladium chloride or palladium sulfate as palladium source, using collosol and gel-atmosphere pressure desiccation be made SiO2It is quantitatively filled in preventing fixed bed adsorber by-APTES-Pd composite aerogel, under certain temperature and air speed, injects the analog gasoline containing thiophene-type sulfide, and the analog gasoline after absorption is collected in the lower end exit of reaction unit carries out chromatography.The result shows that SiO2- APTES-Pd composite aerogel has good absorption property, and SiO of the invention to thiophene-type sulfide2- APTES-Pd composite aerogel has selectivity well, SiO in the present invention to thiophene-type sulfide2The preparation method of-APTES-Pd composite aerogel adsorbent is simple, low in cost, which can repeatedly use, high financial profit, environmental-friendly, its adsorption conditions is mild, the requirement to adsorption plant is low.

Description

The removal methods of thiophene sulphur in a kind of fuel oil
Technical field
The invention belongs to fuel oil processing technique field, it is related to a kind of removal methods of thiophene sulphur in fuel oil, specifically It is related to SiO2- APTES-Pd composite aerogel is the method that adsorbent removes thiophene sulphur in 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 It is traditional hydrodesulfurization, but its operating cost reduces octane number etc. in gasoline and lack compared with high, hydrogen-consuming volume is big, operating condition is harsh Point, and hydrodesulfurization has better effects only for mercaptan, thioether, inorganic sulfur etc., the thiophene-based vulcanization high for thermal stability The desulfurization effect of object is very poor；Desulfurization is adsorbed since its is low in cost, operating condition is mild, and desulfurization effect is good, free from environmental pollution etc. Advantage 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+、Ag+、Ni2+、Co2+、Pd2+Deng.And prepare π complexing desulfuration adsorbent, must by these metals from Son 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, activity Charcoal class, metal oxide-type.
Desulfuration adsorbent is complexed by the π of carrier of molecular sieve.108949220 A of Chinese patent CN is solidifying by using colloidal sol- Gluing method is prepared for a kind of containing Pd2+Mesoporous Si base composite aerogel.Keeping high hole, high-specific surface area, intraskeletal work Property component sufficiently expose while, by that will have the transition metal Pd of π complexing2+It is added thereto, not only overcomes micropore Hole wall effect and steric hindrance problem existing for adsorbent, and improved by π complexing and thiophene-type sulfide is adsorbed Capacity, to significantly improve desulfuration efficiency.But Si skeleton structure present in the π adsorbent prepared by this method is easy It collapses, the problems such as transition metal ions incorporation is not high, suction-operated mechanism is relatively simple, it is made to be difficult to reach deep desulfuration Purpose meets industrialized production.
Desulfuration adsorbent is complexed by the π of carrier of active carbon.Shenyang University of Chemical Technology (103143322 A of publication number CN) system A kind of standby acticarbon for having loaded Fe ion, to the thiophene and derivatives in gasoline have biggish adsorption capacity with Selectivity, and preparation method is simple, regeneration is easy, adsorbent long service life.Sinopec Group is (open Number 104549143 A of CN) by using salt and H containing metals such as Al, Zn, Ni3PO4Active carbon is modified as auxiliary agent It is modified, preferably solve in gas raw material adsorption cleaning desulfurization technology there are single adsorbent cannot and meanwhile effectively remove it is a variety of Sulfide, the problems such as removal efficiency is low and the working sulfur capacity of desulfurizing agent is low of sulphur.But the pore structure of active carbon is changed based on micropore The active carbon of property is still very small to the adsorption capacity of thiophene-based macromolecular sulfide, it is difficult to meet industrial requirement.
Desulfuration adsorbent is complexed by the π of carrier of metal oxide.Nantong University (10300787 A of publication number CN) with Mesoporous γ-the Al of copper doping2O3It is contacted with the fuel oil of sulfur-bearing, realizes desulfurization using absorption method, operating cost is low, absorption Capacity is big, and regenerates conveniently.Sinopec Group (10161923 A of publication number CN) is prepared for a kind of de- Sulfur absorbent, the adsorbent include using aluminium oxide as binder, and zinc oxide is carrier, then contacts with enveloping agent solution, is then born Carry metallic promoter agent.For the desulfurization of fuel oil, activity is high, and absorption sulfur capacity is big.But during the preparation process, metal ion is easy stifled Metal oxide duct is filled in, the active component of load is caused to be accumulated on surface, offer active sites in duct are provided, reduces and inhales Attached desulfurization performance, and this method is more difficult applied to industrialized production.
Zhejiang Polytechnical University (publication number CN 201811557282) is prepared for highly selective, the SiO of high reproducibility2- APTES hybrid aerogel desulfuration adsorbent, by by SiO2It is hybrid cross-linked with APTES, in SiO2Surface introducing-NH2With thiophene-based Sulfide forms hydrogen bond and improves desulfurization absorption property.But in SiO2- APTES aeroge there are obvious adsorption capacity it is not high lack Point, for this purpose, by that will have the metal ion Pd of π Absorptive complex wave ability2+With SiO2The amido on surface forms coordination, is utilizing hydrogen While key, π complexing synergistic effect improve thiophene-type sulfide adsorption capacity, also solve above-mentioned adsorbent it is existing by There is no anchoring group in carrier, lead to problems such as the metallic particles of load reunite, dispersion degree decline, is inhaled to reach and improve desulfurization The purpose of attached ability and metal ion dispersion degree.
Summary of the invention
The removal methods of thiophene sulphur in a kind of fuel oil, it is characterised in that SiO2The compound airsetting of-APTES-Pd Glue adsorbent is prepared using collosol and gel-atmosphere pressure desiccation.
The removal methods of thiophene sulphur in a kind of fuel oil, it is characterised in that with SiO2The compound gas of-APTES-Pd Gel is adsorbent, and the absorbent filling is entered in preventing fixed bed adsorber, at a temperature of 0 ~ 100 DEG C, with 1 ~ 10 h-1Sky Speed is passed through the analog gasoline containing thiophene sulphur, and the analog gasoline of 1ppm or less sulphur concentration is obtained after adsorbing.
The removal methods of thiophene sulphur in a kind of fuel oil, it is characterised in that adsorbed thiophene sulphur is thiophene Pheno, benzothiophene and dibenzothiophenes.
The removal methods of thiophene sulphur in a kind of fuel oil, it is characterised in that SiO2The compound airsetting of-APTES-Pd Glue adsorbent is prepared using silicon source, ammonia source and palladium source as raw material using collosol and gel-atmosphere pressure desiccation.
The removal methods of thiophene sulphur in a kind of fuel oil, it is characterised in that preparation SiO2- APTES-Pd is compound The silicon source of aeroge adsorbent is ethyl orthosilicate, preferably ethyl orthosilicate；Ammonia source is 3- aminopropyl triethoxysilane；Palladium Source is palladium chloride or palladium sulfate, preferably palladium chloride.
The removal methods of thiophene sulphur in a kind of fuel oil, it is characterised in that SiO2The compound airsetting of-APTES-Pd Silicon palladium molar ratio in glue adsorbent is 508-2544:1, preferably 508:1,636:1,848:1,1272:1 or 2544:1, most Excellent is 848:1.
The removal methods of thiophene sulphur in a kind of fuel oil, it is characterised in that be passed through the simulation containing thiophene sulphur The air speed of gasoline is 1 ~ 5 h-1。
The removal methods of thiophene sulphur in a kind of fuel oil, it is characterised in that SiO2The compound airsetting of-APTES-Pd The adsorption temp that glue adsorbs thiophene sulphur is 0 ~ 40 DEG C.
The removal methods of thiophene sulphur in a kind of fuel oil, it is characterised in that thiophene sulphur is dense in analog gasoline Degree is 0.1 ~ 10mgS/g, preferably 0.1 ~ 5 mgS/g.
The removal methods of thiophene sulphur in a kind of fuel oil, it is characterised in that the analog gasoline containing thiophene sulphur It is middle to mix 20wt% cyclohexene, 20wt% toluene respectively.
The removal methods of thiophene sulphur in a kind of fuel oil, it is characterised in that SiO2The compound airsetting of-APTES-Pd Regenerating solvent used after glue absorption thiophene sulphur is cyclohexene, ether, benzene, toluene.
By using above-mentioned technology, compared with prior art, beneficial effects of the present invention are as follows:
1) SiO of the invention2- APTES-Pd composite aerogel has typical meso pore characteristics aperture (5 ~ 20 nm), high porosity (85 ~ 99%), high-specific surface area (600 ~ 1500 m2/ g) etc. unique physico-chemicals property, therefore thiophene-type sulfide can be without hindrance Ground enters in aeroge duct, comes into full contact with and is adsorbed；
2) SiO of the invention2- APTES-Pd composite aerogel, by that will have the metal ion Pd of π Absorptive complex wave ability2+With SiO2The amido on surface forms coordination, with SiO2Aeroge is compared, its introducing-NH in aeroge silicon skeleton structure2,-NH2It can Hydrogen bond is formed with the S in thiophene, benzothiophene or dibenzothiophenes, while by coordination by-NH2The Pd of anchoring2+It can be with π complexing occurs for thiophene-type sulfide, is improving thiophene-type sulfide adsorption capacity using hydrogen bond, π complexing synergistic effect, is mentioning High metal ion Pd2+Incorporation and dispersion degree, meanwhile, also solve existing adsorbent it is existing since carrier does not have anchor Gu group leads to problems such as the metallic particles of load reunite, dispersion degree decline, improves desulfurization adsorption capacity and metal to reach The purpose of ion dispersion degree；
3) SiO of the invention2- APTES-Pd composite aerogel forms unique physics knot compared with other existing adsorbents Structure, the three-dimensional network shape meso-hole structure of Gao Kongrong, influences its adsorption process by diffusion smaller, and thiophene and derivatives And Pd2+The π complexing of formation is better than benzene or cyclohexene and Pd2+The π complexing of formation, it is also contemplated that due to coupling-NH2 Distinctive interaction of hydrogen bond, therefore in the presence of aromatic hydrocarbons, alkene, still to the thiophene-type sulfide in analog gasoline Adsorptive selectivity with higher and adsorption capacity；
4) SiO of the invention2- APTES-Pd composite aerogel adsorbent has good absorption property to thiophene-type sulfide, leads to Crossing solvent washing can regenerate, and still have 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, easy to operate, And there is good adsorption effect to thiophenes.
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in This.
Embodiment 1: being the SiO of 848:1 with silicon palladium molar ratio2For-APTES-Pd composite aerogel adsorbent, preparation Method is as follows:
By 20mL EtOH, 8 mL TEOS, 2 mL H2The mixed solution of O is vigorously stirred uniformly mixed, addition in acid condition Ammonium hydroxide adjusts pH value to 6.5, adds and is slowly added to 1mL APTES, stands about 15 min at room temperature and obtain SiO2- APTES hydridization Alcogel, then the aging 16h in the dehydrated alcohol that volume ratio is 25:15/positive silicoacetic acid ester, to enhance the skeleton structure of gel, Solvent displacement carried out to gel with n-hexane again, replacement solvent twice in 24 h, remove ethyl alcohol in gel, water, acid and other Organic molecule pulverizes to obtain aeroge.Subsequent 0.03g PdCl2It is dissolved in 1 mL deionized water, by above-mentioned PdCl2Solution drips dropwise It adds in the aeroge pulverized, is placed in heating water bath pot and keeps 45 DEG C of constant temperature stirring 4h(solution colours by pale brown color change At faint yellow).Gained yellow solution is finally placed at 120 DEG C dry 4h, obtains the SiO that silicon palladium molar ratio is 848:12- APTES-Pd composite aerogel.
Embodiment 1 ~ 2: the SiO in different palladium sources2- APTES-Pd composite aerogel is to thiophene-type sulfide in analog gasoline Absorption property.
In the SiO using sol-gel method preparation2In-APTES-Pd composite aerogel, silicon source used is positive silicic acid second Ester, the SiO that preparation is completed2- APTES-Pd composite aerogel carries out penetrating absorption desulfurization, and concrete operations are as follows: solid In fixed bed reactor, the bottom loads suitable absorbent cotton, then loads the SiO of 1 g2- APTES-Pd composite aerogel and suitable The quartz sand of amount.Before adsorption experiment starts, loaded adsorbent is sufficiently soaked with normal heptane.It is passed through analog gasoline, is being reacted The analog gasoline after absorption is collected in the lower end exit of device, carries out chromatography, when sulphur concentration is 0.005mgS/g in efflux Shi Dingwei breakthrough point.Obtained thiophene, benzothiophene and dibenzothiophenes penetrate adsorption capacity, the results are shown in Table 1.
The SiO in the different palladiums of table 1 source2Adsorptivity of-APTES-Pd the composite aerogel to thiophene-type sulfide in analog gasoline Energy
As it can be seen from table 1 palladium source should select palladium chloride, synthesized SiO2- APTES-Pd composite aerogel is penetrating absorption In experiment, there is biggish adsorption capacity to thiophene, benzothiophene and dibenzothiophenes.
Embodiment 3 ~ 7: the SiO of different silicon palladium molar ratios2- APTES-Pd composite aerogel is to thiophene sulphur in analog gasoline The absorption property of compound.
Silicon palladium molar ratio is selected to distinguish 2544,1272,848,636,508 SiO2- APTES-Pd composite aerogel, to mould Thiophene-type sulfide carries out penetrating adsorption experiment in quasi- gasoline.It penetrates adsorption experiment operation with embodiment 1 ~ 2, and absorption result is shown in Table 2.
The SiO of the different silicon palladium molar ratios of table 22- APTES-Pd composite aerogel is to thiophene-type sulfide in analog gasoline Absorption property
From table 2 it can be seen that the SiO of different silicon palladium molar ratios2- APTES-Pd composite aerogel is passed with silicon palladium molar ratio Subtract, the adsorption capacity that penetrates of thiophene and benzothiophene is first increased and drops afterwards.When silicon palladium molar ratio is 848:1, thiophene, benzothiophene Reach maximum with the adsorption capacity that penetrates of dibenzothiophenes, therefore the SiO that preferred silicon palladium molar ratio is 848:12- APTES-Pd is multiple Close aeroge.
Case study on implementation 8 ~ 12: different air speeds are to SiO2- APTES-Pd composite aerogel vulcanizes thiophene-based in analog gasoline The absorption property of object
Selecting silicon palladium molar ratio is the SiO of 848:12- APTES-Pd composite aerogel.It is 1 h in air speed-1、3 h-1、5 h-1、8 h-1、10 h-1Under, thiophene-type sulfide in analog gasoline is carried out to penetrate adsorption experiment.It penetrates adsorption experiment operation with implementation Example 1 ~ 2, absorption result is shown in Table 3.
SiO under the different air speeds of table 32Adsorptivity of-APTES-Pd the composite aerogel to thiophene-type sulfide in analog gasoline Energy
From table 3 it can be seen that the reduction of air speed, thiophene, benzothiophene and dibenzothiophenes penetrate adsorption capacity and can gradually increase Greatly, when air speed is reduced to 3 h-1Later, to thiophene-type sulfide penetrate adsorption capacity variation less, therefore preferably air speed be 1 ~ 3 h-1。
Case study on implementation 13 ~ 17: different adsorption temps are to SiO2- APTES-Pd composite aerogel is to thiophene-based in analog gasoline The absorption property of sulfide
Select silicon palladium molar ratio 848:1, SiO2- APTES-Pd composite aerogel.Adsorption temp is selected as 0 DEG C, 25 DEG C, 40 respectively DEG C, 80 DEG C, 100 DEG C, thiophene-type sulfide in analog gasoline is carried out to penetrate adsorption experiment.Adsorption experiment operation is penetrated with implementation Example 1 ~ 2, absorption result is shown in Table 4.
SiO under the different adsorption temps of table 42Suction of-APTES-Pd the composite aerogel to thiophene-type sulfide in analog gasoline Attached performance
From table 4, it can be seen that with the raising of adsorption temp, thiophene, benzothiophene and dibenzothiophenes penetrate adsorption capacity It is gradually reduced, after 80 DEG C, the adsorption penetration capacity of thiophene, benzothiophene and dibenzothiophenes is very small, shows warm herein Under degree, by SiO2Thiophene, benzothiophene and the dibenzothiophenes of-APTES-Pd composite aerogel absorption have been desorbed.Therefore preferential Adsorption temp is 0 ~ 40 DEG C.
Case study on implementation 18 ~ 23: SiO under different sulphur concentrations in analog gasoline2- APTES-Pd composite aerogel is to thiophene sulphur The absorption property of compound
Select the SiO of silicon palladium molar ratio 848:12- APTES-Pd composite aerogel.Thiophene, benzothiophene in analog gasoline or The sulphur concentration of dibenzothiophenes be respectively 0.1mgS/g, 0.5 mgS/g, 1 mgS/g, 2 mgS/g, 5 mgS/g, 10 mgS/g into Row penetrates adsorption experiment.Adsorption operations are penetrated with embodiment 1 ~ 2, absorption result is shown in Table 5.
SiO under different sulphur concentrations in 5 analog gasoline of table2Absorption of-APTES-Pd the composite aerogel to thiophene-type sulfide Performance
As can be seen from Table 5, in analog gasoline thiophene, benzothiophene or dibenzothiophenes sulphur concentration increase, SiO2-APTES- Pd composite aerogel penetrates adsorption capacity in downward trend to thiophene, benzothiophene and dibenzothiophenes, therefore preferably simulation Thiophene or benzothiophene sulphur concentration are 0.1 ~ 2 mgS/g in gasoline.
Case study on implementation 24 ~ 25: different alkene is to SiO2- APTES-Pd composite aerogel vulcanizes thiophene-based in analog gasoline The absorption property of object influences.
SiO2- APTES-Pd composite aerogel to the thiophene-based analog gasoline of cyclohexene containing 20wt%, 20wt% cyclopentene into Row penetrates adsorption experiment.It penetrates adsorption experiment operation with embodiment 1 ~ 2, and absorption result is shown in Table 6.
6 alkene competitive Adsorption of table is to SiO2The influence of-APTES-Pd composite aerogel desulfurization absorption property
As can be seen from Table 6, cyclohexene, cyclopentene are mixed in analog gasoline to SiO2The desulfurization of-APTES-Pd composite aerogel Property influence it is smaller.
Case study on implementation 26 ~ 27: different aromatic hydrocarbons are to SiO2- APTES-Pd composite aerogel vulcanizes thiophene-based in analog gasoline The absorption property of object influences.
SiO2- APTES-Pd composite aerogel penetrates the thiophene-based analog gasoline of benzene containing 20wt%, 20wt% toluene Adsorption experiment.It penetrates adsorption experiment operation with embodiment 1 ~ 2, and absorption result is shown in Table 7.
7 aromatic hydrocarbons competitive Adsorption of table is to SiO2The influence of-APTES-Pd composite aerogel desulfurization absorption property
As can be seen from Table 7, benzene, toluene are mixed in analog gasoline to SiO2The desulphurizing ability of-APTES-Pd composite aerogel influences It is smaller.
Case study on implementation 28 ~ 31: different regenerated solvents are to SiO2- APTES-Pd composite aerogel is to thiophene-based in analog gasoline The regenerative adsorption performance of sulfide
Cyclohexene is first used, ether, benzene, toluene is to the SiO after using2In-APTES-Pd composite aerogel thiophene-type sulfide into Row elution, then again with normal heptane to SiO2Regenerated solvent is eluted in-APTES-Pd composite aerogel, then to analog gasoline Middle thiophene-type sulfide carries out penetrating adsorption experiment.Adsorption experiment operation is penetrated with embodiment 1 ~ 2, absorption result is shown in Table 8.
The different regenerated solvents of table 8 are to SiO2Suction of-APTES-Pd the composite aerogel to thiophene-type sulfide in analog gasoline Attached performance
As can be seen from Table 8, SiO is regenerated2Solvent used in-APTES-Pd composite aerogel has cyclohexene, ether, benzene, toluene, There is good regeneration effect.When selecting benzene, SiO2- APTES-Pd composite aerogel is to thiophene, benzothiophene and dibenzo thiophene Pheno regeneration effect is best.Therefore preferably regenerated solvent is benzene.
Case study on implementation 32-33:APTES-SiO2 composite aerogel and APTES-SiO2-Pd composite aerogel are to analog gasoline The comparison of the absorption property of middle thiophene-type sulfide
APTES-SiO2 composite aerogel and APTES-SiO2-Pd composite aerogel carry out thiophene-type sulfide in analog gasoline Penetrate adsorption experiment.It penetrates adsorption experiment operation with embodiment 1 ~ 2, and absorption result is shown in Table 9.
9 APTES-SiO2 composite aerogel of table and APTES-SiO2-Pd composite aerogel are to thiophene sulphur in analog gasoline The absorption property of compound
As can be seen from Table 9, compared to simple coupling APTES, to graft the interaction of hydrogen bond that-NH2 has.Pass through SiO2 aeroge is first coupled APTES, then is coordinated Pd2+, combines π possessed by Pd2+ that phase interaction is complexed while forming hydrogen bond With more can significantly improving Si base aeroge to the adsorption capacity of thiophene-type sulfide.

Claims (10)

1. the removal methods of thiophene sulphur in a kind of fuel oil, it is characterised in that with SiO2- APTES-Pd composite aerogel is absorption Agent enters the absorbent filling in preventing fixed bed adsorber, at a temperature of 0 ~ 100 DEG C, with 1 ~ 10 h-1Air speed be passed through containing The analog gasoline of thiophene sulphur obtains the analog gasoline of 1ppm or less sulphur concentration after adsorbing.
2. the removal methods of thiophene sulphur in a kind of fuel oil according to claim 1, it is characterised in that adsorbed thiophene Pheno class sulphur is thiophene, benzothiophene and dibenzothiophenes.
3. the removal methods of thiophene sulphur in a kind of fuel oil according to claim 1 or 2, it is characterised in that SiO2- APTES-Pd composite aerogel adsorbent is using silicon source, ammonia source and palladium source as raw material, using collosol and gel-atmosphere pressure desiccation preparation ?.
4. the removal methods of thiophene sulphur in a kind of fuel oil according to claim 3, it is characterised in that preparation SiO2- The silicon source of APTES-Pd composite aerogel adsorbent is ethyl orthosilicate, preferably ethyl orthosilicate；Ammonia source is 3- aminopropyl three Ethoxysilane；Palladium source is palladium chloride or palladium sulfate, preferably palladium chloride.
5. the removal methods of thiophene sulphur in a kind of fuel oil according to claim 3, it is characterised in that SiO2-APTES- Silicon palladium molar ratio in Pd composite aerogel adsorbent is 508-2544:1, preferably 508:1,636:1,848:1,1272:1 or 2544:1, optimal is 848:1.
6. the removal methods of thiophene sulphur in a kind of fuel oil according to claim 1, it is characterised in that be passed through containing thiophene The air speed of the analog gasoline of pheno class sulphur is 1 ~ 5 h-1。
7. the removal methods of thiophene sulphur in a kind of fuel oil according to claim 1, it is characterised in that SiO2-APTES- The adsorption temp that Pd composite aerogel adsorbs thiophene sulphur is 0 ~ 40 DEG C.
8. the removal methods of thiophene sulphur in a kind of fuel oil according to claim 1, it is characterised in that in analog gasoline The concentration of thiophene sulphur is 0.1 ~ 10mgS/g, preferably 0.1 ~ 5 mgS/g.
9. the removal methods of thiophene sulphur in a kind of fuel oil according to claim 1, it is characterised in that contain thiophene-based 20wt% cyclohexene, 20wt% toluene are mixed in the analog gasoline of sulphur respectively.
10. the removal methods of thiophene sulphur in a kind of fuel oil according to claim 1, it is characterised in that SiO2-APTES- Regenerating solvent used after Pd composite aerogel absorption thiophene sulphur is cyclohexene, ether, benzene, toluene.
CN201910590126.1A 2019-07-02 2019-07-02 The removal methods of thiophene sulphur in a kind of fuel oil Pending CN110317631A (en)

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Application publication date: 20191011