CN107216909B - A kind of fuel oil magnetism desulfurizing agent based on supermolecular mechanism - Google Patents
A kind of fuel oil magnetism desulfurizing agent based on supermolecular mechanism Download PDFInfo
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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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
- B01J20/28002—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 physical properties
- B01J20/28009—Magnetic properties
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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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Abstract
The invention discloses a kind of fuel oil magnetism desulfurizing agent based on supermolecular mechanism, the fuel oil magnetism desulfurizing agent are made of the ferriferrous oxide nano sphere that beta-cyclodextrin, coupling agent 3- aminopropyl trimethoxy siloxane or 3- aminopropyl-triethoxy siloxanes, the carrier silicas of the coordination modification of active component bivalent cupric ion wrap up.The coordination modification for the bivalent cupric ion for having desulphurizing activated is carried out on beta-cyclodextrin, desulphurizing activated component is formed, mainly by the coordination realization desulfurization that beta-cyclodextrin inner chamber body size and lightweight thiophene-type sulfide matching are preferable and bivalent cupric ion is to thiophene-type sulfide.The fuel oil magnetism desulfurizing agent has and can be recycled for multiple times, and regeneration is convenient, advantages of environment protection.
Description
Technical field
The present invention relates to a kind of fuel oil magnetism desulfurizing agent based on supermolecule clathration belongs to PETROLEUM PROCESSING neck
Domain.
Background technique
Sulphur is mainly present in combustion with molecular forms such as mercaptan, thioether, disulphide, thiophene, benzothiophene and its derivatives
Expect in oil product.What content was most in gasoline is lightweight thiophene sulphur, accounts for about the 60%~70% of total sulfur content.From this, wanting
The sulfur content in gasoline is reduced, mainly different types of lightweight thiophene-type sulfide in removing gasoline.
For many years, people have carried out a large amount of scientific research in desulfurizing oil field, for example desulfurization is theoretical, technique skill
Art and catalyst etc., but really economical and efficient and environmental-friendly sulfur method and few are mainly with hydrodesulfurization
It is main.Require sulfur content must not in the state VI motor petrol standard in the state V motor petrol standard that the whole nation is implemented and from now at present
More than 10 μ gg-1, hydrodesulfurization is difficult to meet the requirement of other properties of deep desulfuration and gasoline.Oil product deep desulfuration at present
Research be still important topic, and the research of sulfur method develops towards the less expensive and more environment-friendly direction of cost,
So seeking a kind of novel great necessity of deep desulfuration technology, urgency and challenge.
Research both at home and abroad in terms of supramolecular chemistry is in the ascendant, but the simple property using supermolecule main block carries out
Using, it is commonly encountered some difficult or technical bottleneck, researchers and usually passes through the nanometer new material constructed based on supermolecule main block,
It is comprehensive to play efficiency, realize the expansion of its application range.Patent CN105126768A discloses a kind of based on supermolecule inclusion work
Light Oil Desulfurization agent, the desulfurizing agent are made of active component beta-cyclodextrin or derivatives thereof and NaOH solution, but its
Desulfurization degree is low, it is difficult to meet the requirement of light-end products deep desulfuration.The present invention is super by the sufficiently exposure of carrier high specific area characteristic
The cavity of molecular bulk gives full play to the clathration of supermolecule main block, while by the coordination and carrier of metal ion
The physisorption on surface, three kinds of effects have synergistic effect, carry out the design of novel supermolecule main block composite material, close
At raising desulfuration efficiency realizes deep desulfuration.
On the basis of abundant investigation, carrier selects magnetic Fe3O4Nanoparticle, itself has magnetism, is easily recycled regeneration
And specific surface area is larger.But Fe3O4Magnetism is relatively strong and surface hydroxyl activity is not strong, and the ferroso-ferric oxide of Silica-coated can
Disadvantage mentioned above is overcome to a certain extent.The grafting for the bivalent cupric ion for having desulphurizing activated is carried out on beta-cyclodextrin simultaneously, altogether
With desulphurizing activated component is formed, mainly preferably and two by beta-cyclodextrin inner chamber body size and lightweight thiophene-type sulfide matching
Valence copper ion realizes desulfurization to the coordination of thiophene-type sulfide.The fuel oil magnetism desulfurizing agent has and can repeatedly follow
Ring uses, and regeneration is convenient, advantages of environment protection.
Summary of the invention
Although problem to be solved by this invention is that there are many current non-hydrodesulfurization type, various methods all have
There is apparent limitation, lack the non-hydrodesulfurization that can really realize industrialization, greenization, needs to seek to develop one kind
Novel deep desulfuration technology.Using cyclodextrin supermolecule main block to the clathration of sulfide, in combination with living with desulfurization
Property metal ion (bivalent cupric ion), construct cyclodextrin nano desulfurization new material, develop the oil based on supermolecular mechanism principle
Light green color New Machining Technology.The Novel oil product desulfurizing agent developed can be recycled for multiple times, and be easy to regenerate, environmental-friendly, simultaneously
Meet the requirement of green chemistry chemical technology.
The technical solution of the heretofore described fuel oil magnetism desulfurizing agent based on supermolecular mechanism are as follows:
Beta-cyclodextrin, the coupling agent 3- aminopropyl three that the fuel oil magnetism desulfurizing agent is modified by bivalent cupric ion coordination
The ferriferrous oxide nano sphere composition of methoxy radical siloxane or 3- aminopropyl-triethoxy siloxanes and carrier silicas package.
The coupling agent of the fuel oil magnetism desulfurizing agent is 3- aminopropyl trimethoxy siloxane, three ethoxy of 3- aminopropyl
The one or two of radical siloxane are compound.
The beta-cyclodextrin of bivalent cupric ion coordination modification accounts for the mass fraction of carrier in the fuel oil magnetism desulfurizing agent
For 0.1-10%, the mass fraction that coupling agent accounts for carrier is 1-10%.
The fuel oil magnetism desulfurizing agent is for lightweight thiophene-type sulfide (thiophene, benzothiophene, two in fuel oil
Benzothiophene) removing.
The preparation step of the fuel oil magnetism desulfurizing agent is as follows: surface is passed through to the silica of coupling agent modified
The ferriferrous oxide nano sphere of package (is denoted as APTS-SiO2@Fe3O4) and bivalent cupric ion coordination modification beta-cyclodextrin (be denoted as
Cu (II)-β-CD) it is placed in N-Methyl pyrrolidone, wherein APTS-SiO2@Fe3O4With the gross mass and N- of Cu (II)-β-CD
The mass ratio of methyl pyrrolidone is 0.01-0.05:1, is reacted 6-12 hours at 80-100 DEG C, Magnetic Isolation, ethanol washing,
Constant weight is dried under vacuum to get fuel oil magnetism desulfurizing agent, is denoted as Cu (II)-β-CD@SiO2@Fe3O4。
Fuel oil magnetism desulfurizing agent removing lightweight thiophene-type sulfide of the present invention based on supermolecular mechanism
Method are as follows: the oil product of desulfurizing agent and the thiophene-type sulfide containing lightweight is in certain agent oil quality ratio, temperature, desulfurization under the time；Wherein,
Lightweight thiophene-type sulfide has thiophene, benzothiophene, dibenzothiophenes, and normal heptane is as simulation oil product, normal pressure, agent oil quality ratio
For 1:10-100, desulfurization temperature is 25-50 DEG C, and desulfurization time is 15-90 minutes.
The advantages of fuel oil magnetism desulfurizing agent of the present invention based on supermolecular mechanism, is:
(1) beta-cyclodextrin, coupling agent that fuel oil magnetism desulfurizing agent of the present invention is modified by bivalent cupric ion coordination
The ferroso-ferric oxide of 3- aminopropyl trimethoxy siloxane or 3- aminopropyl-triethoxy siloxanes and carrier silicas package
Nanosphere composition, the fuel oil magnetism desulfurizing agent have and can be recycled for multiple times, and regeneration is convenient, environmental-friendly etc. excellent
Point.
The ruler of lightweight thiophene-type sulfide (thiophene, benzothiophene, dibenzothiophenes) molecular dimension and cyclodextrin inner chamber body
Very little close, intermolecular matching is good, and supermolecule clathration is strong, is extremely easy into the inner chamber body of cyclodextrin.Desulfurization simultaneously
Contain bivalent cupric ion in agent, can be coordinated with the sulphur atom in thiophene-type sulfide, improves sulfide and magnetic desulfurization
Interaction between agent.In addition, carrier large specific surface area, is easy to generate physisorption to sulfide.Three kinds of separation fluid effects
Comprehensive function efficiently removes sulfide from oil product.
(2) coupling agent 3- aminopropyl trimethoxy siloxane or 3- aminopropyl-triethoxy siloxanes and bivalent cupric ion are matched
It is to be pasted by β-ring of amino part in coupling agent and bivalent cupric ion coordination modification that the key of the beta-cyclodextrin of position modification, which connects mode,
The copper ion part of essence is connected by coordinate bond.Design is unique, between reasonably optimizing fuel oil magnetism desulfurizing agent respectively forms
Interaction, plays desulfurization performance to the maximum extent.
(3) preparation method of fuel oil magnetism desulfurizing agent of the present invention, it is easily operated, batch production can be amplified.
Detailed description of the invention
Fig. 1 is Cu (II)-β-CD@SiO2@Fe3O4、Cu(II)-β-CD、SiO2@Fe3O4And APTS-SiO2@Fe3O4) to benzene
The removal effect of bithiophene compares (1, inventive desulfurization agent Cu (II)-β-CD@SiO2@Fe3O4；2,Cu(II)-β-CD；3,
SiO2@Fe3O4；4,APTS-SiO2@Fe3O4).Fig. 2 is that inventive desulfurization agent compares (1, thiophene to the removal effect of different sulfide
Pheno；2, benzothiophene；3, dibenzothiophenes).Fig. 3 is that situation is reused in inventive desulfurization agent.
Specific embodiment
In order to make the content of the present invention more clearly understood, make below according to specific embodiments of the present invention into one
Step detailed description.But the present invention is not limited to given examples.
Embodiment 1
Beta-cyclodextrin, the coupling agent 3- aminopropyl front three that fuel oil magnetism desulfurizing agent A is modified by bivalent cupric ion coordination
The ferriferrous oxide nano sphere composition of oxygroup siloxanes and carrier silicas package, the β-that wherein bivalent cupric ion coordination is modified
The mass fraction that cyclodextrin accounts for carrier is 0.1%, and the mass fraction that coupling agent 3- aminopropyl trimethoxy siloxane accounts for carrier is
1%.Synthesis step: surface (is denoted as APTS- by the ferriferrous oxide nano sphere of the Silica-coated of coupling agent modified
SiO2@Fe3O4) and bivalent cupric ion coordination modification beta-cyclodextrin (being denoted as Cu (II)-β-CD) be placed in N-Methyl pyrrolidone
In, wherein APTS-SiO2@Fe3O4It is 0.01:1 with the gross mass of Cu (II)-β-CD and the mass ratio of N-Methyl pyrrolidone,
It is reacted 6 hours at 80 DEG C, Magnetic Isolation, ethanol washing, is dried under vacuum to constant weight to get fuel oil magnetism desulfurizing agent A.
By desulfurizing agent A and and the thiophene-type sulfide containing lightweight oil product certain agent oil quality ratio, temperature, under the time take off
Sulphur；Wherein thiophenic sulfur initial concentration is 100 μ gg-1, normal heptane is 1:20 as oil product, atmospheric operation, agent oil quality ratio, is taken off
Sulphur temperature is 30 DEG C, and desulfurization time is 60 minutes.Desulfurization degree at this time is 48.0%.
Embodiment 2
Beta-cyclodextrin, the coupling agent 3- aminopropyl front three that fuel oil magnetism desulfurizing agent B is modified by bivalent cupric ion coordination
The ferriferrous oxide nano sphere composition of oxygroup siloxanes and carrier silicas package, the β-that wherein bivalent cupric ion coordination is modified
The mass fraction that cyclodextrin accounts for carrier is 1%, and the mass fraction that coupling agent 3- aminopropyl trimethoxy siloxane accounts for carrier is
2%.Synthesis step: surface (is denoted as APTS- by the ferriferrous oxide nano sphere of the Silica-coated of coupling agent modified
SiO2@Fe3O4) and bivalent cupric ion coordination modification beta-cyclodextrin (being denoted as Cu (II)-β-CD) be placed in N-Methyl pyrrolidone
In, wherein APTS-SiO2@Fe3O4It is 0.02:1 with the gross mass of Cu (II)-β-CD and the mass ratio of N-Methyl pyrrolidone,
It is reacted 12 hours at 100 DEG C, Magnetic Isolation, ethanol washing, is dried under vacuum to constant weight to get fuel oil magnetism desulfurizing agent B.
By the oil product of desulfurizing agent B and the thiophene-type sulfide containing lightweight in certain agent oil quality ratio, temperature, desulfurization under the time,
Wherein thiophenic sulfur initial concentration is 20 μ gg-1, normal heptane is 1:10, desulfurization temperature as oil product, atmospheric operation, agent oil quality ratio
Degree is 25 DEG C, and desulfurization time is 15 minutes.Desulfurization degree at this time is 33.5%.
Embodiment 3
Fuel oil magnetism desulfurizing agent C is coordinated the beta-cyclodextrin of modification, three second of coupling agent 3- aminopropyl by bivalent cupric ion
The ferriferrous oxide nano sphere composition of oxygroup siloxanes and carrier silicas package, the β-that wherein bivalent cupric ion coordination is modified
The mass fraction that cyclodextrin accounts for carrier is 3%, and the mass fraction that coupling agent 3- aminopropyl-triethoxy siloxanes accounts for carrier is
3%.Synthesis step: surface (is denoted as APTS- by the ferriferrous oxide nano sphere of the Silica-coated of coupling agent modified
SiO2@Fe3O4) and bivalent cupric ion coordination modification beta-cyclodextrin (being denoted as Cu (II)-β-CD) be placed in N-Methyl pyrrolidone
In, wherein APTS-SiO2@Fe3O4It is 0.05:1 with the gross mass of Cu (II)-β-CD and the mass ratio of N-Methyl pyrrolidone,
It is reacted 8 hours at 90 DEG C, Magnetic Isolation, ethanol washing, is dried under vacuum to constant weight to get fuel oil magnetism desulfurizing agent C.
By the oil product of desulfurizing agent C and the thiophene-type sulfide containing lightweight in certain agent oil quality ratio, temperature, desulfurization under the time,
Wherein benzothiophene sulphur initial concentration is 100 μ gg-1, normal heptane is 1:40 as oil product, atmospheric operation, agent oil quality ratio, is taken off
Sulphur temperature is 30 DEG C, and desulfurization time is 75 minutes.Desulfurization degree at this time is 35.3%.
Embodiment 4
Fuel oil magnetism desulfurizing agent D is coordinated the beta-cyclodextrin of modification, three second of coupling agent 3- aminopropyl by bivalent cupric ion
The ferriferrous oxide nano sphere composition of oxygroup siloxanes and carrier silicas package, the β-that wherein bivalent cupric ion coordination is modified
The mass fraction that cyclodextrin accounts for carrier is 5%, and the mass fraction that coupling agent 3- aminopropyl-triethoxy siloxanes accounts for carrier is
5%.Synthesis step: surface (is denoted as APTS- by the ferriferrous oxide nano sphere of the Silica-coated of coupling agent modified
SiO2@Fe3O4) and bivalent cupric ion coordination modification beta-cyclodextrin (being denoted as Cu (II)-β-CD) be placed in N-Methyl pyrrolidone
In, wherein APTS-SiO2@Fe3O4It is 0.03:1 with the gross mass of Cu (II)-β-CD and the mass ratio of N-Methyl pyrrolidone,
It is reacted 10 hours at 90 DEG C, Magnetic Isolation, ethanol washing, is dried under vacuum to constant weight to get fuel oil magnetism desulfurizing agent D.
By the oil product of desulfurizing agent D and the thiophene-type sulfide containing lightweight in certain agent oil quality ratio, temperature, desulfurization under the time,
Wherein dibenzothiophenes sulphur initial concentration is 50 μ gg-1, normal heptane is 1:80 as oil product, atmospheric operation, agent oil quality ratio,
Desulfurization temperature is 50 DEG C, and desulfurization time is 90 minutes.Desulfurization degree at this time is 23.1%.
Embodiment 5
Fuel oil magnetism desulfurizing agent E is coordinated the beta-cyclodextrin of modification, three second of coupling agent 3- aminopropyl by bivalent cupric ion
The ferriferrous oxide nano sphere composition of oxygroup siloxanes, 3- aminopropyl trimethoxy siloxane and carrier silicas package,
The mass fraction that the beta-cyclodextrin of middle bivalent cupric ion coordination modification accounts for carrier is 10%, coupling agent 3- aminopropyl-triethoxy silicon
The mass fraction that oxygen alkane, 3- aminopropyl trimethoxy siloxane account for carrier is 5%.Synthesis step: coupling agent is passed through on surface
The ferriferrous oxide nano sphere of the Silica-coated of modified (is denoted as APTS-SiO2@Fe3O4) and bivalent cupric ion coordination repair
The beta-cyclodextrin (being denoted as Cu (II)-β-CD) of decorations is placed in N-Methyl pyrrolidone, wherein APTS-SiO2@Fe3O4With Cu (II)-
The gross mass of β-CD and the mass ratio of N-Methyl pyrrolidone are 0.05:1, are reacted 9 hours at 90 DEG C, Magnetic Isolation, ethyl alcohol
Washing, is dried under vacuum to constant weight to get fuel oil magnetism desulfurizing agent E.
By the oil product of desulfurizing agent E and the thiophene-type sulfide containing lightweight in certain agent oil quality ratio, temperature, desulfurization under the time,
Wherein benzothiophene sulphur initial concentration is 300 μ gg-1, normal heptane is 1:20 as oil product, atmospheric operation, agent oil quality ratio, is taken off
Sulphur temperature is 30 DEG C, and desulfurization time is 60 minutes.Desulfurization degree at this time is 69.5%.
Embodiment 6
Fuel oil magnetism desulfurizing agent F is coordinated the beta-cyclodextrin of modification, three second of coupling agent 3- aminopropyl by bivalent cupric ion
The ferriferrous oxide nano sphere composition of oxygroup siloxanes, 3- aminopropyl trimethoxy siloxane and carrier silicas package,
The mass fraction that the beta-cyclodextrin of middle bivalent cupric ion coordination modification accounts for carrier is 3%, coupling agent 3- aminopropyl-triethoxy silicon
The mass fraction that oxygen alkane, 3- aminopropyl trimethoxy siloxane account for carrier is 3%.Synthesis step: coupling agent is passed through on surface
The ferriferrous oxide nano sphere of the Silica-coated of modified (is denoted as APTS-SiO2@Fe3O4) and bivalent cupric ion coordination repair
The beta-cyclodextrin (being denoted as Cu (II)-β-CD) of decorations is placed in N-Methyl pyrrolidone, wherein APTS-SiO2@Fe3O4With Cu (II)-
The gross mass of β-CD and the mass ratio of N-Methyl pyrrolidone are 0.04:1, are reacted 12 hours at 85 DEG C, Magnetic Isolation, ethyl alcohol
Washing, is dried under vacuum to constant weight to get fuel oil magnetism desulfurizing agent F.
By the oil product of desulfurizing agent F and the thiophene-type sulfide containing lightweight in certain agent oil quality ratio, temperature, desulfurization under the time,
Wherein dibenzothiophenes sulphur initial concentration is 500 μ gg-1, normal heptane is 1 as oil product, atmospheric operation, agent oil quality ratio:
100, desulfurization temperature is 25 DEG C, and desulfurization time is 90 minutes.Desulfurization degree at this time is 25.4%.
Embodiment 7
Fuel oil magnetism desulfurizing agent G is coordinated the beta-cyclodextrin of modification, three second of coupling agent 3- aminopropyl by bivalent cupric ion
The ferriferrous oxide nano sphere composition of oxygroup siloxanes, 3- aminopropyl trimethoxy siloxane and carrier silicas package,
The mass fraction that the beta-cyclodextrin of middle bivalent cupric ion coordination modification accounts for carrier is 5%, coupling agent 3- aminopropyl-triethoxy silicon
The mass fraction that oxygen alkane, 3- aminopropyl trimethoxy siloxane account for carrier is 4%.Synthesis step: coupling agent is passed through on surface
The ferriferrous oxide nano sphere of the Silica-coated of modified (is denoted as APTS-SiO2@Fe3O4) and bivalent cupric ion coordination repair
The beta-cyclodextrin (being denoted as Cu (II)-β-CD) of decorations is placed in N-Methyl pyrrolidone, wherein APTS-SiO2@Fe3O4With Cu (II)-
The gross mass of β-CD and the mass ratio of N-Methyl pyrrolidone are 0.02:1, are reacted 11 hours at 95 DEG C, Magnetic Isolation, ethyl alcohol
Washing, is dried under vacuum to constant weight to get fuel oil magnetism desulfurizing agent G.
By the oil product of desulfurizing agent G and the thiophene-type sulfide containing lightweight in certain agent oil quality ratio, temperature, desulfurization under the time,
Wherein benzothiophene sulphur initial concentration is 100 μ gg-1, normal heptane is 1:60 as oil product, atmospheric operation, agent oil quality ratio, is taken off
Sulphur temperature is 40 DEG C, and desulfurization time is 30 minutes.Desulfurization degree at this time is 30.2%.
Embodiment 8
Fuel oil magnetism desulfurizing agent H is coordinated the beta-cyclodextrin of modification, three second of coupling agent 3- aminopropyl by bivalent cupric ion
The ferriferrous oxide nano sphere composition of oxygroup siloxanes and carrier silicas package, the β-that wherein bivalent cupric ion coordination is modified
The mass fraction that cyclodextrin accounts for carrier is 7%, and the mass fraction that coupling agent 3- aminopropyl-triethoxy siloxanes accounts for carrier is
8%.Synthesis step: surface (is denoted as APTS- by the ferriferrous oxide nano sphere of the Silica-coated of coupling agent modified
SiO2@Fe3O4) and bivalent cupric ion coordination modification beta-cyclodextrin (being denoted as Cu (II)-β-CD) be placed in N-Methyl pyrrolidone
In, wherein APTS-SiO2@Fe3O4It is 0.01:1 with the gross mass of Cu (II)-β-CD and the mass ratio of N-Methyl pyrrolidone,
It is reacted 12 hours at 90 DEG C, Magnetic Isolation, ethanol washing, is dried under vacuum to constant weight to get fuel oil magnetism desulfurizing agent H.
By the oil product of desulfurizing agent H and the thiophene-type sulfide containing lightweight in certain agent oil quality ratio, temperature, desulfurization under the time,
Wherein dibenzothiophenes sulphur initial concentration is 400 μ gg-1, normal heptane is 1:20 as oil product, atmospheric operation, agent oil quality ratio,
Desulfurization temperature is 50 DEG C, and desulfurization time is 45 minutes.Desulfurization degree at this time is 47.5%.
Implement comparative example
First by fuel oil magnetism desulfurizing agent H or active component Cu (II)-β-CD or carrier S iO2@Fe3O4Or
APTS-SiO2@Fe3O4(wherein APTS is 3- aminopropyl-triethoxy siloxanes, accounts for SiO2@Fe3O4Mass fraction be 8%) and
To carry out desulfurization at agent oil quality ratio 1:20,30 DEG C, (sulphur initial concentration is 100 μ gg to normal heptane containing benzothiophene-1), desulfurization
Time is 75 minutes, and desulfurization degree is as shown in Figure 1.
It can be seen that fuel oil magnetism desulfurizing agent H compared with Cu (II)-β-CD or SiO from Fig. 1 data2@Fe3O4Or
APTS-SiO2@Fe3O4There is obvious raising to the removing of benzothiophene sulphur, illustrates that desulfurizing agent design of the invention, synthesis are skilful
It is wonderful, and the simple combination of inactive ingredients and carrier, there is the significant desulfurization performance of comparison.
In addition removal effect of the comparison fuel oil magnetism desulfurizing agent H to different sulfide, controlling agent oil quality ratio are investigated
1:20,30 DEG C, sulphur initial concentration is 100 μ gg-1, desulfurization time is 90 minutes, and sulfide selects thiophene, benzothiophene, hexichol
Bithiophene, removal effect are as shown in Figure 2.
As seen from Figure 2, inventive desulfurization agent all has preferable removal effect, three kinds of sulfide to thiophene-type sulfide
Removal effect size be benzothiophene > dibenzothiophenes > thiophene.
Desulfurizing agent reusing
The inventive desulfurization agent H of de- benzothiophene sulphur is separated, is stirred 1 hour under 60 DEG C of petroleum ether, makes benzene
Bithiophene sulphur is released from desulfurizing agent, filtering, the desulfurizing agent after being drying to obtain regeneration.It is carried out under identical desulfurization condition
De- benzothiophene sulphur, is reused 5 times.Desulfurizing agent recycling HDS evaluation effect is shown in Fig. 3.
From figure 3, it can be seen that this desulfurizing agent reusing is good, desulphurization cost can be effectively reduced, application prospect is preferable.
Obviously, the above embodiments are merely examples for clarifying the description, and not to fuel oil of the invention
The restriction of magnetic desulfurizing agent embodiment.For those of ordinary skill in the art, on the basis of the above description also
It can make other variations or changes in different ways.Here it is not necessarily to, all embodiments can not also be enumerated.And by
The obvious changes or variations that this extends out are still within the protection scope of the invention.
Claims (4)
1. a kind of fuel oil magnetism desulfurizing agent based on supermolecular mechanism, which is characterized in that the fuel oil magnetism desulfurization
Three ethoxy of beta-cyclodextrin, coupling agent 3- aminopropyl trimethoxy siloxane or 3- aminopropyl that agent is modified by bivalent cupric ion coordination
The ferriferrous oxide nano sphere composition of radical siloxane and carrier silicas package；The preparation of the fuel oil magnetism desulfurizing agent
Steps are as follows: surface is matched by the ferriferrous oxide nano sphere and bivalent cupric ion of the Silica-coated of coupling agent modified
The beta-cyclodextrin of position modification is placed in N-Methyl pyrrolidone, and wherein the Silica-coated of coupling agent modified is passed through on surface
The quality of the gross mass and N-Methyl pyrrolidone of ferriferrous oxide nano sphere and the beta-cyclodextrin of bivalent cupric ion coordination modification
Than being reacted 6-12 hours at 80-100 DEG C, Magnetic Isolation, ethanol washing is dried under vacuum to constant weight, i.e., for 0.01-0.05:1
Obtain fuel oil magnetism desulfurizing agent.
2. fuel oil magnetism desulfurizing agent according to claim 1, which is characterized in that the fuel oil magnetism desulfurizing agent
Coupling agent be one or both of 3- aminopropyl trimethoxy siloxane, 3- aminopropyl-triethoxy siloxanes it is compound.
3. fuel oil magnetism desulfurizing agent according to claim 1, which is characterized in that the fuel oil magnetism desulfurizing agent
The mass fraction that the beta-cyclodextrin of middle bivalent cupric ion coordination modification accounts for carrier is 0.1-10%, and coupling agent accounts for the quality point of carrier
Number is 1-10%.
4. fuel oil magnetism desulfurizing agent according to claim 1, which is characterized in that the fuel oil magnetism desulfurizing agent
Removing for lightweight thiophene-type sulfide thiophene, benzothiophene, dibenzothiophenes in fuel oil.
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| CN109351338B (en) * | 2018-12-19 | 2022-02-15 | 浙江工业大学 | By SiO2Method for removing thiophene sulfides in fuel oil by using APTES hybrid aerogel as adsorbent |
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| CN105126768A (en) * | 2015-09-11 | 2015-12-09 | 中国石油大学(华东) | Light-weight oil desulfurizing agent based on supra-molecular inclusion effect and application method thereof |
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| CN105126768A (en) * | 2015-09-11 | 2015-12-09 | 中国石油大学(华东) | Light-weight oil desulfurizing agent based on supra-molecular inclusion effect and application method thereof |
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