CN105879912B - A kind of amphiphilic heteropoly acid of interlayer type containing cobalt and its application - Google Patents
A kind of amphiphilic heteropoly acid of interlayer type containing cobalt and its application Download PDFInfo
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
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- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
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- 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
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- 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
- C10G2300/70—Catalyst aspects
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Abstract
The invention belongs to the preparation of function catalysis material and fuel detergenting field, is related to a kind of application of parental type interlayer type containing cobalt heteropoly acid and its catalytic desulfurization.The molecular formula of the catalyst is：[C18H37N(CH3)3]10[Co4(H2O)2(PW9O34)2], by the heteropoly acid of interlayer type containing cobalt K10[Co4(H2O)2(PW9O34)2] obtained with cationic surfactant OTAC by ion exchange and electrostatic force self assembly.The catalyst and hydrogen peroxide and ionic liquid [Bmim] PF6Extraction catalytic oxidation desulfurization system is mixed to form, the purpose of ultra-deep desulfuration can be reached at normal temperatures.The preparation method of catalyst of the present invention is simple, desulphurization reaction mild condition, and catalyst system and catalyzing can at least recycle 6 times and catalytic efficiency is without significantly reducing, and is a kind of production technology efficiently, economic, environmentally friendly.
Description
Technical field
The invention belongs to the preparation of function catalysis material and catalytic desulfurization technical field, and in particular to one kind is amphiphilic to contain cobalt
Interlayer type heteropoly acid and its purposes in catalytic desulfurization.
Background technology
Fuel oil mainly includes gasoline, diesel oil etc., and sulphur is to be prevalent in one of major impurity element of fuel oil.In fuel oil
Oxysulfide (SO is generated after sulfur-containing compound burningx), it can not only trigger the formation of acid rain, and can urge reducing vehicle exhaust
Agent is to oxynitrides NOx, imperfect combustion hydro carbons and particulate matter etc. have an impact, aggravate environmental pollution.World wide
Increasingly strict environmental regulation is inside established, limits the sulfur content of vehicle fuel, the production of low-sulfur " green fuel " turns into inevitable
Trend.
At present, conventional desulfurization technology is hydrodesulfurization technology.But in hydrodesulfurization technology, in order to obtain super-low sulfur
Fuel oil, it is necessary to using high temperature, high pressure and new catalyst, greatly increase oil refining cost and equipment cost.Non- hydrodesulfurization
Technology includes oxidation sweetening, absorption desulfurization, abstraction desulfurization and biological desulphurization etc..It is normal that wherein oxidation sweetening, which has operating condition,
Temperature, under normal pressure, the advantages of equipment and relatively low running cost, be it is with fastest developing speed in recent years, it is most potential to substitute the non-of hydrodesulfurization
Hydrodesulfurization technology.Oxidative desulfurization techniques and the desulfurization technologies such as extraction, absorption are combined, promotion fuel oil will be further functioned as
The desulfurized effect of middle sulfur-containing compound.
Polyacid because its composition, size, shape, charge density, heat endurance and oxidation-reduction quality it is one wider can
In the range of tune and by people's extensive concern.Such as Keggin-type polyacid as catalyst be widely used in it is homogeneous and it is non-
In phase reaction.However, interlayer type polyacid K10Co4(H2O)2(PW9O34)2Research in terms of desulfurization is less.In recent years, in polyacid
The latest developments of surface chemistry, it is found that positively charged surfactant can substitute polyoxometallate counter ion counterionsl gegenions, make table
The cluster of face activating agent cladding fits together with core-housing.Parents' catalyst is greatly increased in the interfacial assembly of emulsion droplet
Total interfacial area, can be such that catalyst is preferably contacted with sulfur-containing compound, reach ultra-deep oxidation sweetening purpose.
The content of the invention
It is an object of the invention to provide a kind of amphiphilic heteropolyacid catalyst of interlayer type containing cobalt, and hydrogen peroxide is as oxidation
Agent, for ionic liquid as extractant, formation three-phase micro emulsion catalyst system and catalyzing can be with high-efficiency desulfurization.After reaction, by static demulsification,
Centrifugation can separate catalyst.
The amphiphilic heteropoly acid of interlayer type containing cobalt of one kind of the present invention, molecular formula are：[C18H37N(CH3)3]10[Co4
(H2O)2(PW9O34)2], molecular weight is：6054.
The specific synthesis step of the amphiphilic heteropoly acid of interlayer type containing cobalt of one kind of the present invention is as follows：
(1) synthesis of the heteropoly acid of interlayer type containing cobalt：
0.001-0.014mol cobalt nitrates are dissolved in 9-24ml ionized waters, added under stirring into purple solution
0.001-0.012mol phosphotungstic acids (A-PW9), heated solution is to being in homogeneous claret, by the potassium chloride (0.05- of excess
0.08mmol) add in above-mentioned solution, generation bluish violet precipitation, drying is filtered after being cooled to room temperature, solid powder is again molten
Solution in 5-20ml hot water, 3-8 DEG C recrystallization, collection obtain bluish violet crystal, in vacuum drying chamber dry 1-3 hours be
Can；
(2) synthesis of the amphiphilic heteropoly acid of interlayer type containing cobalt：
It is 0.05- that the ethanol solution for the surfactant that concentration is 0.5-2mol/L is slowly dropped into same volume concentration
In the 0.2mol/L heteropoly acid aqueous solution of interlayer type containing cobalt, wherein the mol ratio of the heteropoly acid of interlayer type containing cobalt and surfactant is
1:5-1:12, stir 2 hours, centrifugation, several times, 60-100oC dries 6-10 hours and urged under vacuum condition for ethanol and washing
Agent.
The described heteropoly acid of interlayer type containing cobalt is K10[Co4(H2O)2(PW9O34)2], described cationic surfactant is
OTAC, it is [C to finally obtain parents' catalyst18H37N(CH3)3]10[Co4(H2O)2(PW9O34)2]
The method of extraction catalytic oxidation desulfurization of the present invention, key step include：
A) under 25-70 °C of normal pressure, 500ppm simulation oils, ionic liquid, catalyst and hydrogen peroxide are sequentially added into burning
It is sufficiently mixed in bottle, the mol ratio of catalyst and simulation oil is 1:100-l:20, mole of simulation oil sulfur content and hydrogen peroxide
Than for 1:2-1:8,5-90 minutes are reacted, the sulfur compound that will be present in simulation oil is converted into corresponding sulfone；
B) after the completion of reacting, upper strata simulation oil is poured out using the method toppled over, as the oil product after deep desulfuration；
C) after being washed several times with dichloromethane, catalyst and ionic liquid is centrifuged, it is small to be put into vacuum drying chamber 6-12
When, catalyst is obtained again, is reduced using catalytic efficiency after 6 times without obvious.
Described 500ppm simulation oils are respectively：It is just pungent that 0.73g benzothiophenes (BT) and 0.5g biphenyl are dissolved in 500ml
Alkane is mixed to prepare；1.0g dibenzothiophenes (DBT) and 0.5g biphenyl are dissolved in 500ml normal octanes and are mixed to prepare；1.16g 4,6-
Dimethyl Dibenzothiophene (4,6-DMDBT) and 0.5g biphenyl are dissolved in 500ml normal octanes and are mixed to prepare, corresponding oxidation product
For dibenzothiophene sulphone, benzothiophene sulfone, 4,6- dimethyl Dibenzothiophene sulfones.
Described ionic liquid is 1- butyl -3- methylimidazoles hexafluorophosphates ([Bmim] PF6)。
The positive effect of the present invention is：The present invention is prepared for a kind of heteropoly acid of interlayer type containing cobalt of surfactant parcel
New catalyst, the catalyst form three-phase micro emulsion catalyst system and catalyzing with hydrogen peroxide, ionic liquid and simulation oil, entered at normal temperatures
Row desulfurization, can be with high-efficiency desulfurization.And catalyst and ionic liquid can pass through and be recycled for multiple times, desulfuration efficiency is without substantially subtracting
It is few, it is a kind of more successful sulfur method.
Brief description of the drawings
If figure is a kind of infrared spectrogram of the amphiphilic heteropoly acid of interlayer type containing cobalt：a）The infrared spectrum of surfactant
Figure；b）The infrared spectrogram of the heteropoly acid of interlayer type containing cobalt；c）The infrared spectrogram of the amphiphilic heteropoly acid of interlayer type containing cobalt.
Embodiment
Embodiment 1:
A kind of described specific synthesis step of amphiphilic heteropoly acid of interlayer type containing cobalt is as follows：
(1) synthesis of the heteropoly acid of interlayer type containing cobalt：
0.41g cobalt nitrates are dissolved in 15ml ionized waters, add 2.0g phosphotungstic acids (A- under stirring into purple solution
PW9), heated solution adds the potassium chloride (4-6g) of excess in above-mentioned solution to being in homogeneous claret, and generation bluish violet is sunk
Form sediment, filter drying after being cooled to room temperature, solid powder is re-dissolved in 5-10ml hot water, in 5 DEG C of recrystallizations, collection obtains
Bluish violet crystal.Dried 2 hours in vacuum drying chamber；
(2) synthesis of the amphiphilic heteropoly acid of interlayer type containing cobalt：
It is 0.1mol/L's that the ethanol solution for the surfactant that concentration is 1mol/L is slowly dropped into same volume concentration
In the heteropoly acid aqueous solution of interlayer type containing cobalt, wherein the mol ratio of the heteropoly acid of interlayer type containing cobalt and surfactant is 1:10, stirring 2
Hour, centrifugation, several times, 80oC is dried 8 hours and is obtained catalyst under vacuum condition for ethanol and washing.
Embodiment 2：The extraction catalytic oxidation desulfurization experiment of simulation oil containing benzothiophene：
Take 0.73g benzothiophenes and 0.5g biphenyl to be dissolved in normal octane, be configured to 500mL 500ppm containing benzothiophene mould
Intend oil product, then by the 23mg catalyst of above-mentioned preparation, 21 μ L hydrogen peroxide, 1mL ionic liquids [Bmim] PF6, 5mL simulations
Oil is sequentially added in 25mL round-bottomed flasks, and magnetic agitation is reacted 60 minutes at 60 DEG C, wherein supernatant liquor was taken out every 10 minutes,
Gas chromatographic analysis, experimental result are shown in Table 1.After reaction terminates, remaining simulation oil is poured out using tipping.Use dichloromethane
After washing several times, then catalyst and ionic liquid centrifuged, be put into vacuum drying chamber 6 hours, obtain catalyst again and enter
Enter in next round reaction.Reduced using catalytic efficiency after 6 times without obvious.
Embodiment 3：The extraction catalytic oxidation desulfurization experiment of simulation oil containing dibenzothiophenes：
Take 1.0g dibenzothiophenes and 0.5g biphenyl to be dissolved in normal octane, be configured to 500mL 500ppm's containing dibenzothiophenes
Oil product is simulated, then by the 23mg catalyst of above-mentioned preparation, 21 μ L hydrogen peroxide, 1mL ionic liquids [Bmim] PF6, 5mL moulds
Intend oil to sequentially add in 25mL round-bottomed flasks, magnetic agitation is reacted 80 minutes at 60 DEG C, wherein it is clear to take out upper strata every 10 minutes
Liquid, gas chromatographic analysis, experimental result are shown in Table 1.After reaction terminates, remaining simulation oil is poured out using tipping.Use dichloro
After methane is washed several times, then catalyst and ionic liquid centrifuged, be put into vacuum drying chamber 8 hours, be catalyzed again
Agent enters in next round reaction.Reduced using catalytic efficiency after 6 times without obvious.
Embodiment 4：The extraction catalytic oxidation desulfurization experiment of the simulation oil of dimethyl Dibenzothiophene containing 4,6-：
1.16g 4 is taken, 6-DMDBT and 0.5g biphenyl is dissolved in normal octane, is configured to 500mL dimethyl dibenzo containing 4,6-
Thiophene 500ppm simulation oil product, then by the 23mg catalyst of above-mentioned preparation, 21 μ L hydrogen peroxide, 1mL ionic liquids
[Bmim]PF6, 5mL simulation oils are sequentially added in 25mL round-bottomed flasks, and magnetic agitation is reacted 90 minutes at 60 DEG C, wherein every 10
Minute takes out supernatant liquor, gas chromatographic analysis, and experimental result is shown in Table 1.After reaction terminates, residue is simulated using tipping
Oil is poured out.After being washed several times with dichloromethane, then catalyst and ionic liquid centrifuged, it is small to be put into vacuum drying chamber 10
When, catalyst is obtained again to be entered in next round reaction.Reduced using catalytic efficiency after 6 times without obvious.
Test example：A kind of amphiphilic heteropolyacid catalyst of interlayer type containing cobalt prepared by selection example 1, according to embodiment 2,
3,4 pairs of different reaction substrates carry out extracting catalytic oxidation desulfurization reaction, as a result as shown in table 1：
Table 1：
Conclusion：From table 1 it follows that under identical reaction conditions, removal effect of the catalyst to dibenzothiophenes
Preferably, can remove completely substantially.Removal effect order be：Dibenzothiophenes>4,6- dimethyl Dibenzothiophenes>Benzo thiophene
Fen.
Claims (2)
- A kind of 1. amphiphilic heteropoly acid of interlayer type containing cobalt, it is characterised in that：Molecular formula is：[C18H37N(CH3)3]10[Co4(H2O)2 (PW9O34)2], molecular weight is：6054；It is by the heteropoly acid of interlayer type containing cobalt K10[Co4(H2O)2(PW9O34)2] and cationic surfactant C18H37N(CH3)3•Cl Obtained, comprised the following steps that by ion exchange and electrostatic force self assembly：(1) synthesis of the heteropoly acid of interlayer type containing cobalt：0.001-0.014mol cobalt nitrates are dissolved in 9-24ml deionized waters, added under stirring into purple solution 0.001-0.012mol phosphotungstic acids, heated solution add the potassium chloride 0.05-0.08mmol of excess to being in homogeneous claret Enter in above-mentioned solution, generation bluish violet precipitation filters drying after being cooled to room temperature, and solid powder is re-dissolved in into 5-20ml heat In water, in 3-8 DEG C of recrystallization, collection obtains bluish violet crystal, and 1-3 hours are dried in vacuum drying chamber；(2) synthesis of the amphiphilic heteropoly acid of interlayer type containing cobalt：It is 0.05- that the ethanol solution for the surfactant that concentration is 0.5-2mol/L is slowly dropped into same volume concentration In the 0.2mol/L heteropoly acid aqueous solution of interlayer type containing cobalt, wherein the mol ratio of the heteropoly acid of interlayer type containing cobalt and surfactant is 1:5-1:12, stir 2 hours, centrifugation, several times, 60-100oC dries 6-10 hours under vacuum condition, obtains for ethanol and washing Catalyst.
- 2. the amphiphilic heteropolyacid catalyst of interlayer type containing cobalt of one kind according to claim 1 is in extraction catalytic oxidation desulfurization body Application in system.
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| CN106986778A (en) * | 2017-03-03 | 2017-07-28 | 赵建社 | Surfactant type heteropoly acid and its preparation method and application |
| CN107029804B (en) * | 2017-04-27 | 2020-02-07 | 辽宁大学 | Catalyst with erasable performance and preparation method and application thereof |
| CN108855232B (en) * | 2018-07-02 | 2021-03-19 | 东北师范大学 | Composite nanofiber and preparation method and application thereof |
| CN112898355B (en) * | 2021-01-22 | 2023-01-06 | 北华大学 | Method for preventing lignin degradation intermediate product from polycondensation |
| CN115160144B (en) * | 2022-06-14 | 2024-02-27 | 北京理工大学 | Transition metal substituted heteropolyacid-based ionic liquid flame retardant, preparation method and application thereof |
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| CN104910214A (en) * | 2015-04-22 | 2015-09-16 | 河南师范大学 | Weakley polyacid compound containing mixed cations, and preparation method and application thereof |
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| CN101433854A (en) * | 2007-11-14 | 2009-05-20 | 中国科学院大连化学物理研究所 | Hydrotalcite-like in situ assembled nano multiple-metal oxygen-containing cluster catalyst and application |
| CN104910214A (en) * | 2015-04-22 | 2015-09-16 | 河南师范大学 | Weakley polyacid compound containing mixed cations, and preparation method and application thereof |
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