CN106861603A - Targeting anchoring agent of sulfide and its preparation method and application in a kind of oil product - Google Patents
Targeting anchoring agent of sulfide and its preparation method and application in a kind of oil product Download PDFInfo
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- CN106861603A CN106861603A CN201710098117.1A CN201710098117A CN106861603A CN 106861603 A CN106861603 A CN 106861603A CN 201710098117 A CN201710098117 A CN 201710098117A CN 106861603 A CN106861603 A CN 106861603A
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- sulfide
- anchoring agent
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0259—Compounds of N, P, As, Sb, Bi
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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
-
- 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
Abstract
Targeting anchoring agent the present invention relates to sulfide in a kind of oil product and its preparation method and application.The preparation method of the targeting anchoring agent of sulfide is comprised the following steps：The anchoring agent presoma metal ion of sulfide is supported on the magnetic nanoparticle surface of coated silica shell by infusion process, and by calcining the composite construction of the magnetic nanoparticle metal nanometre cluster for obtaining stabilization, prepare the targeting anchoring agent of sulfide.Anchoring agent with magnetic nanoparticle as targeting agent, metal nanometer cluster as sulfide, builds the composite construction of magnetic nanoparticle metal nanometre cluster.The targeting anchoring agent can not only avoid the reduction of oil product octane number, at the same can reducing energy consumption, so as to obtain the sweet oil of cleaning, reduce vehicular emission level, improve ambient air quality, with good application prospect.
Description
Technical field
Targeting anchoring agent the present invention relates to sulfide in a kind of oil product and its preparation method and application, belongs to fine oil
Chemical field.
Background technology
China's haze weather is more gradually aggravated in recent years, and the tail gas of the motor vehicle emission of the fuel for being with gasoline is to aggravate environment dirt
One of key factor of dye.As the raising and vehicle fuel index of people's environmental consciousness are to the increasingly strict of sulfur content, production
New challenge and study hotspot that the low-sulfur HC fuel of cleaning faces as petroleum refining industry.To reduce vehicular emission level,
Improve ambient air quality, national environmental protection portion represents at present, the standard of state six will be formulated in the end of the year 2016 and complete and issue, and this is to vapour
Oily desulfurization proposes new challenge.
The method that sulphur in tradition removing oil product is used is mainly hydrodesulfurization (HDS) and absorption desulfurization, such as gasoline, diesel
Various hydrodesulfurizations and catalyst, gasoline absorbing desulfurization S-Zorb techniques etc..Though HDS can effectively deviate from the sulphur in gasoline
The small molecule sulphur such as alcohol, thioether, but the thiophene (TS), benzothiophene (BT) and its derivative high for heat endurance removal effect
It is unsatisfactory, especially there is 4, the 6- dialkyl group dibenzothiophenes of larger space steric hindrance, it is difficult to be removed by HDS.If carry out
Deep desulfuration, then hydrogen consumption, reactor volume can all be sharply increased.And above-mentioned technique can produce octane in gasoline desulfurization application
Value loss, such as 2 or so octane numbers of gasoline hydrogenation General Loss, 0.5 octane number of S-Zorb process loss, cause tremendous economic
Loss.
What magnetic nanoparticle was primarily referred to as the compositions such as iron, nickel, cobalt and its alloy can directly or indirectly produce magnetic
Material, they are also presented in addition to the distinctive skin effect of general nano material, quantum size effect, bulk effect
Go out some unique excellent physical characteristics, such as superparamagnetism, high saturation and magnetic intensity, biocompatibility, hypotoxicity etc..Magnetic
Nano particle is generally divided into five classes according to the magnetic classification of material：Diamagnetism, paramagnetism, anti-ferromagnetism, ferromagnetism and ferrous iron
Magnetic.Superparamagnetism is an extremely unique property in magnetic Nano material paramagnetism, refers at room temperature, working as nanometer
Particle diameter hour between 10nm to 20nm or more, the particle disturbing influence that is heated is presented confusing array, now magnetic with it is former
The paramagnetism of son is similar to be referred to as superparamagnetism.Although the design of magnetic nanoparticle just increasingly attracts attention with preparation,
The numerous areas such as Magnetic Isolation, magnetic probe, biomedicine are applied, but do not find magnetic Nano also in the prior art
Grain is applied in deep desulfuration.
The Fe in numerous superparamagnetic nanoparticles3O4Nano-particle because prepares it is relatively easy, biocompatibility it is preferable and
Turn into the study hotspot for receiving much concern with low toxicity.Current Fe3O4Nano-particle targeted drug delivery, DNA in vivo
Separate transfection, immune detection, genophore is prepared and medical diagnosis aspect all has wide practical use.Nanometer Fe3O4Have
Skin effect, can be enriched with more biomass, it is also possible to carry out the research in the directions such as the sustained release and target administration of medicine.Research
Show, by Fe3O4The various medicines of mediated by nanoparticles targeted delivery have very big possibility, by magnetic Nano Fe3O4As medicine
Thing carrier, surrounding carrying medicament, by externally-applied magnetic field, makes this compound directly reach affected part, can improve insoluble medicine and reach
The efficiency of focus, makes medicine assemble in affected part, treats disease.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide sulfide in a kind of oil product targeting anchoring agent and its
Preparation method and application.Grappling of the preparation method with magnetic nanoparticle as targeting agent, metal nanometer cluster as sulfide
Agent, builds the composite construction of magnetic nanoparticle-metal nanometre cluster, and the targeting anchoring agent for preparing can not only avoid oil product
The reduction of octane number, at the same can reducing energy consumption, so as to obtain the sweet oil of cleaning, reduce vehicular emission level, improve
Ambient air quality, with good application prospect.
In order to achieve the above object, the invention provides a kind of preparation method of the targeting anchoring agent of sulfide in oil product,
The preparation method is comprised the following steps：
Anchoring agent presoma-the metal ion of sulfide is supported on the magnetic of coated silica shell by infusion process
Nano grain surface, and by calcining the composite construction of the magnetic nanoparticle-metal nanometre cluster for obtaining stabilization, prepare oil
The targeting anchoring agent of sulfide in product.
Specific embodiment of the invention, it is preferable that the preparation method is comprised the following steps：By the cladding dioxy
The magnetic nanoparticle of SiClx shell is carried out instead in being scattered in solvent with the anchoring agent presoma-metal ion of the sulfide
Should, product is dried after the completion of reaction, the targeting anchoring agent of sulfide in oil product is obtained after calcining；It is highly preferred that above-mentioned reaction
Time is 5h-10h.
In above-mentioned preparation method, it is preferable that the magnetic nanoparticle of coated silica shell is to use negatively charged height
Molecular material carries out what surface silanization was prepared again after part replacement is carried out to the original surface of magnetic nanoparticle.
In above-mentioned preparation method, it is preferable that the preparation method of the magnetic nanoparticle of coated silica shell includes
Following steps：
Magnetic nanoparticle and PLA are scattered in chloroform, are heated to reflux, received under additional magnetic fields after cooling
Collection magnetic nanoparticle, obtains the magnetic nanoparticle of PLA cladding, and it is scattered in toluene again, adds silicon precursor examination
Agent, and above-mentioned solution is placed on shaking table, after mixing, isometric ultra-pure water is added, and add isometric with silicon precursor reagent
Alkaline silicon crosslinking agent, acutely shake up overnight, collect product after cooling under additional magnetic fields, obtain the cladding after drying
The magnetic nanoparticle of silica shell；It is highly preferred that the temperature of above-mentioned backflow is 50 DEG C -80 DEG C, the time is 3h-5h.
In above-mentioned preparation method, it is preferable that magnetic nanoparticle is 1 with the mass ratio of PLA:4-1:10, PLA
Molecular weight be 200-50000, more preferably 5000；The magnetic nanoparticle of PLA cladding and the mass ratio of silicon precursor reagent
It is 1:(0.3-0.5).
In above-mentioned preparation method, it is preferable that negatively charged macromolecular material is in PLA, polyacrylic acid and polyphenyl sulfonic acid
The combination of one or more；Silicon precursor reagent is one or more in quanmethyl silicate, silicic acid and the allyl ester of silicic acid four
Combination, more preferably quanmethyl silicate；Alkaline silicon crosslinking agent be aminopropyl trimethoxysilane, four (dimethylamino) silane,
(3- aminopropyls) triethoxysilane, Butyldimethyl (dimethylamino) silane, three (dimethylamino) chlorosilanes, trimethoxy
[3- (methylamino) propyl group] silane, two (3- (methylamino) propyl group) trimethoxy silanes, double (dimethylamino) dimethylsilanes,
One kind or several in pi-allyl (lignocaine) dimethylsilane and 3- [double (2- ethoxys) amino] propane-triethoxysilane
The combination planted, more preferably aminopropyl trimethoxysilane.
In above-mentioned preparation method, it is preferable that magnetic nanoparticle is Fe3O4Nano particle, Fe2O3Nano particle, FePt
Alloy nanoparticle, CoPt alloy nano particle, MFe2O4One or more in nano particle and core-shell type composite nano particles
Combination, wherein, MFe2O4M in nano particle is Co, Ni, Mn, Zn, Cu, Ag or Au, and core-shell type composite nano particles are
FePt/CoPt、FePt/Fe3O4Or FePt/Fe2O3.It is highly preferred that Fe of the magnetic nanoparticle for superparamagnetism3O4。
In above-mentioned preparation method, it is preferable that metal in the anchoring agent presoma-metal ion of sulfide is Cu, Ag,
Au, Zn, Ni, Hg, Co, Mn, W, Pt, Pa, Ru or Rh；More preferably Ni.
In above-mentioned preparation method, it is preferable that magnetic nanoparticle and the anchoring agent presoma-metal ion of sulfide
The corresponding relation of addition is 1g:(2-8)mmol；The anchoring agent presoma of sulfide-metal ion concentration in aqueous
It is 1-10M.
In above-mentioned preparation method, it is preferable that solvent is that concentration of volume percent is the ethanol solution of 10%-50%.
In above-mentioned preparation method, it is preferable that calcining is carried out in the protective gas of hydrogen and argon gas, in hydrogen and
In the protective gas of argon gas, the percent by volume of hydrogen is 1%-10%, preferably 2%；
The temperature of calcining is 200 DEG C -600 DEG C, and preferably 400 DEG C, the time of calcining is 1h-5h, preferably 5h.
In above-mentioned preparation method, the Fe of superparamagnetism3O4Can be prepared by method conventional in the prior art, preferably
Ground, the Fe of superparamagnetism3O4Through the following steps that prepare：Ferric acetyl acetonade is mixed with oleic acid, oleyl amine and octadecylene；
The lower heating of argon gas protection, reaction backflow obtains dark solution, ethanol precipitation is added after cooling, collected under additional magnetic fields,
Superparamagnetism Fe is obtained after drying3O4Nano particle.
The present invention also provides a kind of targeting anchoring agent prepared by above-mentioned preparation method.
The present invention also provides application of the above-mentioned targeting anchoring agent in desulfurizing oil.
In above-mentioned application, it is preferable that oil product is gasoline or diesel oil；More preferably catalytically cracked gasoline, the catalysis is split
The sulfur content for changing gasoline is 200-205ppm.
In above-mentioned application, it is preferable that as follows the step of desulfurization：Persistently stirred during above-mentioned targeting anchoring agent is added into oil product
Mix, heating response, complete the desulfurization of oil product.
In above-mentioned application, it is preferable that oil product is (60-100) with the mass ratio of targeting anchoring agent:1, the rotating speed of stirring is
100rpm, the temperature of heating is 50 DEG C -100 DEG C, and the time of heating response is 15min-60min.
In concrete scheme of the invention, it is preferable that in oil product sulfide targeting anchoring agent preparation method include with
Lower step：
(1) superparamagnetic nanoparticle is prepared
(I) 3-5mmol ferric acetyl acetonades (FeAcAc), 10mL oleic acid, 10mL oleyl amines and 10mL octadecylenes are mixed；
(II) 300 DEG C are heated under argon gas protection, reaction backflow obtains dark solution in 3 hours；
(III) a large amount of ethanol precipitations are added after cooling down, product is collected under additional magnetic fields, superparamagnetic is obtained after drying
Property Fe3O4Nano particle.
(2) superparamagnetic nanoparticle of Surface coating silica shell is prepared
(I) by superparamagnetic Fe3O4PLA (the PLA of nano particle and molecular weight 50005000) press 1:6 mass ratio dispersion
In chloroform, flow back 3h-5h at being heated to 50 DEG C -80 DEG C；
(II) magnetic nano particle is collected under additional magnetic fields after cooling down, PLA is obtained5000The superparamagnetic Fe of cladding3O4Receive
Rice grain；
(III) PLA that will be obtained5000The superparamagnetic Fe of cladding3O4Nano particle is scattered in toluene again, in mass ratio
1:(0.3-0.5) adds silicon precursor reagent quanmethyl silicate, and above-mentioned solution is placed on shaking table；
(IV) after mixing, isometric ultra-pure water is added, and add and the isometric aminopropyl trimethoxy of quanmethyl silicate
Base silane, acutely shakes up 24 hours；
(V) collected under additional magnetic fields after cooling down, the superparamagnetic of Surface coating silica shell is obtained after drying
Fe3O4Nano particle.
(3) the targeting anchoring agent of sulfide is prepared
(I) by the superparamagnetic Fe of Surface coating silica shell3O4Nano particle is scattered in the mixed solvent of water and ethanol
In, the concentration of volume percent of ethanol solution is 10%-50%, obtains solution A；
(II) configuration concentration is the NiCl of 1-10M2·6H2The aqueous solution of O, obtains solution B；
(III) by solution B add solution A in, room temperature reaction 5-10 hours, 1g superparamagnetics Fe3O4Nano particle or surface
The superparamagnetic Fe of coated silica shell3O4Nano particle correspondence 2-8mmol NiCl2·6H2O；
(IV) after the completion of reacting, product is suctioned out with magnet, infrared drying, under hydrogen and argon gas mixing gas shielded (
In the protective gas of hydrogen and argon gas, the percent by volume of hydrogen is 1%-10%, is 200-600 in temperature preferably 2%)
High-temperature calcination under conditions of DEG C (preferably 400 DEG C), reaction 1h-5h (preferably 5h), is suctioned out product with magnet, is washed, and is obtained
The targeting anchoring agent of sulfide in oil product, as shown in Figure 2.
The targeting anchoring agent can carry out specific identification to the sulfide of oil product, and under additional magnetic fields, to sulphur
Compound is separated.The reaction is gentle, and energy consumption is low, and the octane number of oil product is not reduced.
In concrete scheme of the invention, the desulfurization for targetting anchoring agent can be followed the steps below：To 50mL high pressures
20mL FCC gasolines (sulfur content is 200ppm) is added in kettle reaction, and to the targeting anchoring agent of addition sulfide in gasoline, two
Person's mass ratio is 70:1, stirred with 100rpm rotating speeds, 50 DEG C of reactions are heated to, stir 15min；After the completion of stirring, in gasoline
Sulfur-containing compound include that hydrogen sulfide, mercaptan, thioether, thiophenic sulfur, benzothiophene sulphur class are all adsorbed to the targeting anchor of sulfide
Determine in agent.After end, in reactor bottom additional magnetite about 15min, magnetic adsorbent is isolated, collect gasoline after desulfurization, adopted
The change of organic sulfur content in front and rear gasoline is adsorbed with fluorescence spectrometry.
The present invention uses outfield intensifying method anchor using the sulphur in novel desulphurization theoretical method targeting grappling oil product
The targeting agent for determining sulfur-bearing hydrocarbon molecule is separated with without sulphur hydrocarbon molecule.It is assumed that in gasoline 10% hydrocarbon molecule sulfur-bearing, 90% not sulfur-bearing enters
Through above-mentioned technical process the hydrocarbon molecule of 90% not sulfur-bearing is directly carried out adjusting oil after material, and the hydrocarbon molecule of 10% sulfur-bearing is carried out subsequently
PROCESS FOR TREATMENT, such as hydrodesulfurization or polarity desulfurization, so as to the subversiveness for realizing desulfurizing oil is changed, are not dropped as far as possible with reaching desulfurization
The target of low octane rating.
Brief description of the drawings
Fig. 1 is the superparamagnetic Fe of Surface coating silica shell in embodiment 13O4The stereoscan photograph of nano particle.
Fig. 2 is the transmission electron microscope photo of preparation-obtained targeting anchoring agent in embodiment 1.
Fig. 3 is the preparation process of the targeting anchoring agent of sulfide.
Specific embodiment
In order to be more clearly understood to technical characteristic of the invention, purpose and beneficial effect, now to skill of the invention
Art scheme carry out it is described further below, but it is not intended that to it is of the invention can practical range restriction.
Embodiment 1
The present embodiment provides a kind of targeting anchoring agent of sulfide, and it is through the following steps that prepare：
1st, the preparation of superparamagnetic nanoparticle
5mmol ferric acetyl acetonades (FeAcAc), 10mL oleic acid, 10mL oleyl amines and 10mL octadecylenes are mixed；Protected in argon gas
300 DEG C are heated under shield, reaction backflow obtains dark solution in 3 hours；A large amount of ethanol precipitations are added after cooling, is made in externally-applied magnetic field
With lower collection product, superparamagnetism Fe is obtained after drying3O4Nano particle.
2nd, the superparamagnetic nanoparticle of Surface coating silica shell is prepared
By superparamagnetic Fe3O4PLA (the PLA of nano particle and molecular weight 50005000) press 1:5 mass ratio is scattered in chlorine
In imitative, flowed back 5 hours at being heated to 80 DEG C；Magnetic nano particle is collected under additional magnetic fields after cooling, PLA is obtained5000Bag
The superparamagnetic Fe for covering3O4Nano particle；
By PLA5000The superparamagnetic Fe of cladding3O4Nano particle is scattered in toluene again, and in mass ratio 1:0.5 adds silicon
Precursor agents quanmethyl silicate, and above-mentioned solution is placed on shaking table；After mixing, add isometric ultra-pure water, and add with
The isometric aminopropyl trimethoxysilane of quanmethyl silicate, acutely shakes up 24 hours；Received under additional magnetic fields after cooling
Collection product, obtains the superparamagnetic Fe of Surface coating silica shell after drying3O4Nano particle, as shown in figure 1, prepared
The Fe of Surface coating silica shell3O4Nano particle yardstick is homogeneous, and average diameter is 12.5 ± 1.3nm.
3rd, the targeting anchoring agent of sulfide is prepared
By the superparamagnetic Fe of Surface coating silica shell3O4Nano particle is scattered in the mixed solvent (second of water and ethanol
The concentration of volume percent of alcohol is in 30%), to obtain solution A；
Configuration concentration is the NiCl of 10M2·6H2The aqueous solution of O, obtains solution B；
By solution B add solution A in, room temperature reaction 10 hours, the superparamagnetic Fe of 1g Surface coating silica shells3O4
Nano particle correspondence 8mmol NiCl2·6H2O；After the completion of reaction, product is suctioned out with magnet, infrared drying, containing 2% hydrogen
Argon gas it is mixed gas protected under, in 400 DEG C of high-temperature calcinations, react 5h, product is suctioned out with magnet, wash, obtain sulfide
Targeting anchoring agent, preparation process is as shown in Figure 3.The targeting anchoring agent for preparing is as shown in Fig. 2 wherein, yardstick is larger
Spheric granules is Fe3O4Nano particle, the little particle adhered on its side is Ni nano-clusters.
Embodiment 2
The present embodiment provides a kind of targeting anchoring agent of sulfide, and it is through the following steps that prepare：
1st, the preparation of FePt nano particles
By 2.5mmol carbonyl irons Fe (Co)5, 2.5mmol acetylacetone,2,4-pentanedione platinum Pt (AcAc), 10mL oleic acid, 5mL oleyl amines and
7.5mL octadecylenes mix；310 DEG C are heated under argon gas protection, reaction backflow obtains dark solution in 2 hours；Added after cooling
A large amount of ethanol precipitations, collect product under additional magnetic fields, and FePt Nanoparticles Nanoparticles are obtained after drying.
2nd, the FePt nano particles of Surface coating silica shell are prepared
By FePt nano particles and the PLA (PLA of molecular weight 50005000) press 1:6 mass ratio is scattered in chloroform,
Flowed back 3 hours at being heated to 80 DEG C；Magnetic nano particle is collected under additional magnetic fields after cooling, PLA is obtained5000Cladding
FePt nano particles；
By PLA5000The FePt nano particles of cladding are scattered in toluene again, and in mass ratio 1:0.3 adds silicon precursor examination
Agent quanmethyl silicate, and above-mentioned solution is placed on shaking table；After mixing, isometric ultra-pure water is added, and add and silicic acid four
The isometric aminopropyl trimethoxysilane of methyl esters, acutely shakes up 24 hours；Product is collected under additional magnetic fields after cooling,
The FePt nano particles of Surface coating silica shell are obtained after drying.
3rd, the targeting anchoring agent of sulfide is prepared
The FePt nano particles of Surface coating silica shell are scattered in the mixed solvent (body of ethanol of water and ethanol
Product percent concentration is in 50%), to obtain solution A；
Configuration concentration is the NiCl of 5M2·6H2The aqueous solution of O, obtains solution B；
By solution B add solution A in, room temperature reaction 8 hours, the FePt nano particles of 1g Surface coating silica shells
Correspondence 5mmol CuCl2；After the completion of reaction, product is suctioned out with magnet, infrared drying, in the argon gas gaseous mixture containing 10% hydrogen
Under body protection, in 600 DEG C of high-temperature calcinations, 5h is reacted, suctioned out product with magnet, washed, obtain the targeting anchoring agent of sulfide.
Embodiment 3
The present embodiment provides a kind of targeting anchoring agent of sulfide, and it is through the following steps that prepare：
1、NiFe2O4The preparation of nano particle
By 5mmol ferric acetyl acetonades Fe (AcAc), 2.5mmol 2.5mmol acetylacetone,2,4-pentanedione platinum Pt (AcAc), 7.5mL oil
The mixing of acid, 2.5mL oleyl amines and 10mL octadecylenes；300 DEG C are heated under argon gas protection, it is molten that reaction backflow obtains black in 2 hours
Liquid；A large amount of ethanol precipitations are added after cooling, product is collected under additional magnetic fields, NiFe is obtained after drying2O4Nano particle.
2nd, the NiFe of Surface coating silica shell is prepared2O4Nano particle
By NiFe2O4PLA (the PLA of nano particle and molecular weight 50005000) press 1:4 mass ratio is scattered in chloroform
In, flowed back 4 hours at being heated to 80 DEG C；Magnetic nano particle is collected under additional magnetic fields after cooling, PLA is obtained5000Cladding
NiFe2O4Nano particle；
By PLA5000The NiFe of cladding2O4Nano particle is scattered in toluene again, and in mass ratio 1:0.5 adds silicon precursor
Reagent quanmethyl silicate, and above-mentioned solution is placed on shaking table；After mixing, isometric ultra-pure water is added, and add and silicic acid
The isometric aminopropyl trimethoxysilane of four methyl esters, acutely shakes up 24 hours；Collected under additional magnetic fields after cooling and produced
Thing, obtains the FePt nano particles of Surface coating silica shell after drying.
3rd, the targeting anchoring agent of sulfide is prepared
By the NiFe of Surface coating silica shell2O4Nano particle be scattered in water and ethanol mixed solvent (ethanol
Concentration of volume percent be 10%) in, obtain solution A；
Configuration concentration is the NiCl of 2M2·6H2The aqueous solution of O, obtains solution B；
By solution B add solution A in, room temperature reaction 5 hours, 1g NiFe2O4Nano particle or Surface coating titanium dioxide
The NiFe of silicon shell2O4Nano particle correspondence 5mmol NiCl2·6H2O；After the completion of reaction, product is suctioned out with magnet, it is infrared
Drying, in the case where the argon gas containing 1% hydrogen is mixed gas protected, in 600 DEG C of high-temperature calcinations, reacts 1h, is suctioned out product with magnet,
Washing, obtains the targeting anchoring agent of sulfide.
Embodiment 4
The present embodiment provides the application in catalytically cracked gasoline desulfurization of targeting anchoring agent, in actual applications, desulfurization
Comprise the following steps：
20mL FCC gasolines (sulfur content is 200ppm) is added in being reacted to 50mL autoclaves, and to adding Fe in gasoline3O4
The targeting anchoring agent of magnetic nanoparticle-Ni nano-clusters, the mass ratio of the two is 70:1, stirred with 100rpm rotating speeds, heating
Reacted under the conditions of to 50 DEG C, stir about 15min or so；
After the completion of stirring, the sulfur-containing compound in gasoline includes hydrogen sulfide, mercaptan, thioether, thiophenic sulfur, benzothiophene sulphur class
Compound is all adsorbed on the targeting anchoring agent of sulfide.
After experiment terminates, in reactor bottom additional magnetite about 15min, magnetic adsorbent is isolated, collect vapour after desulfurization
Oil, using the change of organic sulfur content in gasoline before and after fluorescence spectrometry absorption, is as a result listed in table 1.
Embodiment 5
The present embodiment provides the application in catalytically cracked gasoline desulfurization of targeting anchoring agent, in actual applications, desulfurization
Comprise the following steps：
20mL FCC gasolines (sulfur content is 200ppm) is added in being reacted to 50mL autoclaves, and to adding Fe in gasoline3O4
The targeting anchoring agent of magnetic nanoparticle-Ni nano-clusters, the two mass ratio is 100:1, stirred with 100rpm rotating speeds, it is heated to
Reacted under the conditions of 100 DEG C, stir about 60min or so；
After the completion of stirring, the sulfur-containing compound in gasoline includes hydrogen sulfide, mercaptan, thioether, thiophenic sulfur, benzothiophene sulphur class
Compound is all adsorbed on the targeting anchoring agent of sulfide.
After experiment terminates, in reactor bottom additional magnetite about 15min, magnetic adsorbent is isolated, collect vapour after desulfurization
Oil, using the change of organic sulfur content in gasoline before and after fluorescence spectrometry absorption, is as a result listed in table 1.
Embodiment 6
The present embodiment provides the application in catalytically cracked gasoline desulfurization of targeting anchoring agent, in actual applications, desulfurization
Comprise the following steps：
20mL FCC gasolines (sulfur content is 205ppm) is added in being reacted to 50mL autoclaves, and is added in gasoline
NiFe2O4The targeting anchoring agent of nano particle-Ni nano-clusters, the two mass ratio is 60:1, stirred with 100rpm rotating speeds, heating
Reacted under the conditions of to 65 DEG C, stir about 25min or so；
After the completion of stirring, the sulfur-containing compound in gasoline includes hydrogen sulfide, mercaptan, thioether, thiophenic sulfur, benzothiophene sulphur class
Compound is all adsorbed on the targeting anchoring agent of sulfide.
After experiment terminates, in reactor bottom additional magnetite about 15min, magnetic adsorbent is isolated, collect vapour after desulfurization
Oil, using the change of organic sulfur content in gasoline before and after fluorescence spectrometry absorption, is as a result listed in table 1.
Desulfurization results of the targeting anchoring agent of the sulfide of table 1 in catalytically cracked gasoline
The targeting anchoring agent that result according to given by table 1 can be seen that sulfide of the invention has for desulfurizing oil
There is good effect.
Claims (10)
1. in a kind of oil product the targeting anchoring agent of sulfide preparation method, the preparation method comprises the following steps：
Anchoring agent presoma-the metal ion of sulfide is supported on the magnetic Nano of coated silica shell by infusion process
Particle surface, and by calcining the composite construction of the magnetic nanoparticle-metal nanometre cluster for obtaining stabilization, in preparing oil product
The targeting anchoring agent of sulfide.
2. preparation method as claimed in claim 1, wherein, the preparation method is comprised the following steps：By the cladding titanium dioxide
The magnetic nanoparticle of silicon shell enters in being scattered in solvent with the aqueous solution of the anchoring agent presoma-metal ion of the sulfide
Row reaction, dries product after the completion of reaction, the targeting anchoring agent of sulfide in oil product is obtained after calcining, it is preferable that the reaction
Time be 5h-10h.
3. preparation method as claimed in claim 2, wherein, the magnetic nanoparticle of the coated silica shell is to use
Negatively charged macromolecular material is carried out prepared by surface silanization again after part replacement is carried out to the original surface of magnetic nanoparticle
Obtain；
Preferably, the preparation method of the magnetic nanoparticle of the coated silica shell is comprised the following steps：Magnetic is received
Rice grain is scattered in chloroform with PLA, is heated to reflux, and magnetic nanoparticle is collected under additional magnetic fields after cooling, is obtained
To the magnetic nanoparticle of PLA cladding, it is scattered in toluene again, adds silicon precursor reagent, after mixing, add etc.
The ultra-pure water of volume, and add the alkaline silicon crosslinking agent isometric with the silicon precursor reagent, acutely shakes up overnight, after cooling
Externally-applied magnetic field effect is lower to collect product, and the magnetic nanoparticle of the coated silica shell is obtained after drying；It is highly preferred that
The temperature of the backflow is 50 DEG C -80 DEG C, and the time is 3h-5h；
Preferably, the magnetic nanoparticle and the mass ratio of the PLA are 1:4-1:10, the molecular weight of the PLA
It is 200-50000, more preferably 5000；
The magnetic nanoparticle of the PLA cladding and the mass ratio of the silicon precursor reagent are 1:(0.3-0.5)；
The negatively charged macromolecular material is the combination of one or more in PLA, polyacrylic acid and polyphenyl sulfonic acid；
The silicon precursor reagent is the combination of one or more in quanmethyl silicate, silicic acid and the allyl ester of silicic acid four, preferably
Quanmethyl silicate；
The alkaline silicon crosslinking agent is aminopropyl trimethoxysilane, four (dimethylamino) silane, (3- aminopropyls) three second
TMOS, Butyldimethyl (dimethylamino) silane, three (dimethylamino) chlorosilanes, trimethoxy [3- (methylamino) propyl group]
Silane, two (3- (methylamino) propyl group) trimethoxy silanes, double (dimethylamino) dimethylsilanes, pi-allyl (lignocaine)
The combination of one or more in dimethylsilane and 3- [double (2- ethoxys) amino] propane-triethoxysilane, more preferably
It is aminopropyl trimethoxysilane.
4. preparation method as claimed in claim 3, wherein, the magnetic nanoparticle is Fe3O4Nano particle, Fe2O3Nanometer
Particle, FePt alloy nano particle, CoPt alloy nano particle, MFe2O4In nano particle and core-shell type composite nano particles
The combination of one or more, the MFe2O4M in nano particle is Co, Ni, Mn, Zn, Cu, Ag or Au, described hud typed compound
Nano particle is FePt/CoPt, FePt/Fe3O4Or FePt/Fe2O3；
Preferably, the magnetic nanoparticle is the Fe of superparamagnetism3O4；
Preferably, the metal in the anchoring agent presoma-metal ion of the sulfide be Cu, Ag, Au, Zn, Ni, Hg, Co,
The combination of one or more in Mn, W, Pt, Pa, Ru and Rh；More preferably Ni.
5. preparation method as claimed in claim 4, wherein, the anchoring agent forerunner of the magnetic nanoparticle and the sulfide
The corresponding relation of the addition of body-metal ion is 1g:(2-8)mmol；
The anchoring agent presoma of the sulfide-concentration of the metal ion in the aqueous solution is 1-10M.
6. preparation method as claimed in claim 5, wherein, the solvent is that concentration of volume percent is the second of 10%-50%
Alcoholic solution；
The calcining is what is carried out in the protective gas of hydrogen and argon gas, in the protective gas of the hydrogen and argon gas, hydrogen
The percent by volume of gas is 1%-10%, preferably 2%；
The temperature of the calcining is 200 DEG C -600 DEG C, and preferably 400 DEG C, the time of the calcining is 1h-5h, preferably 5h.
7. preparation method as claimed in claim 6, wherein, the Fe of the superparamagnetism3O4Through the following steps that prepare：
Ferric acetyl acetonade is mixed with oleic acid, oleyl amine, octadecylene, is heated under argon gas protection, reaction backflow obtains dark solution,
Ethanol precipitation is added after cooling, product is collected under additional magnetic fields, superparamagnetism Fe is obtained after drying3O4Nano particle.
8. the targeting anchoring agent of sulfide in the oil product that the preparation method any one of claim 1-7 is prepared.
9. application of the targeting anchoring agent of sulfide in desulfurizing oil in the oil product described in claim 8；
Preferably, the oil product is gasoline or diesel oil；More preferably catalytically cracked gasoline, the sulfur content of the catalytically cracked gasoline
It is 50-500ppm.
10. application as claimed in claim 9, wherein, it is as follows the step of the desulfurization：
Persistently stirred during the targeting anchoring agent of sulfide in the oil product described in claim 8 is added into oil product, heating response, completed
The desulfurization of oil product；
Preferably, the oil product and the mass ratio of the targeting anchoring agent of sulfide in the oil product are (60-100):1, it is described to stir
The rotating speed mixed is 100-1000rpm, and the temperature of the heating is 50 DEG C -100 DEG C, and the time of the heating response is 15min-
60min。
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