CN105879912A - Amphiphilic cobalt-containing sandwich type heteropolyacid and application thereof - Google Patents
Amphiphilic cobalt-containing sandwich type heteropolyacid and application thereof Download PDFInfo
- Publication number
- CN105879912A CN105879912A CN201610234174.3A CN201610234174A CN105879912A CN 105879912 A CN105879912 A CN 105879912A CN 201610234174 A CN201610234174 A CN 201610234174A CN 105879912 A CN105879912 A CN 105879912A
- Authority
- CN
- China
- Prior art keywords
- sandwich type
- cobalt
- amphiphilic
- heteropoly acid
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
-
- 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
- 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
-
- 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
- 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
- C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
-
- 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
-
- 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
- C10G2300/70—Catalyst aspects
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the fields of preparation of functional catalytic materials and fuel purification and relates to amphiphilic cobalt-containing sandwich type heteropolyacid and an application of heteropolyacid in catalytic desulfurization. The molecular formula of the catalyst is [C18H37N(CH3)3]10[Co4(H2O)2(PW9O34)2], and amphiphilic cobalt-containing sandwich type heteropolyacid is obtained through self-assembly of cobalt-containing sandwich type heteropolyacid K10[Co4(H2O)2(PW9O34)2] and a cationic surfactant, namely, octadecyl trimethyl ammonium chloride through ion exchange under electrostatic force. The catalyst is mixed with hydrogen peroxide and an ionic liquid [Bmim]PF6 to form an extraction, catalytic oxidation and desulfurizing system, and the purpose of super-deep desulfurization can be achieved at normal temperature. The preparation method of the catalyst is simple, the desulfurization reaction condition is mild, the catalytic system can be at least used 6 times without remarkable reduction of catalytic efficiency, and the preparation method is an efficient, economical and environment-friendly production process.
Description
Technical field
The invention belongs to preparation and the catalytic desulfurization technical field of function catalysis material, be specifically related to a kind of amphiphilic containing cobalt sandwich type heteropoly acid and the purposes in catalytic desulfurization thereof.
Background technology
Fuel oil mainly includes gasoline, diesel oil etc., and sulfur is one of major impurity element being prevalent in fuel oil.Oxysulfide (SO is generated after sulfur-containing compound burning in fuel oilx), not only can cause the formation of acid rain, and can be to reducing auto-exhaust catalyst to oxynitride NOx, imperfect combustion hydro carbons and particulate matter etc. produce impact, aggravate environmental pollution.Establishing the strictest environmental regulation in world wide, limit the sulfur content of vehicle fuel, the production of low-sulfur " green fuel " becomes inevitable trend.
At present, conventional desulfurization technology is hydrodesulfurization technology.But in hydrodesulfurization technology, in order to obtain ultra low sulfur fuels oil, it is necessary to use high temperature, high pressure and new catalyst, be greatly increased oil refining cost and equipment cost.Non-hydrodesulfurization includes oxidation sweetening, absorption desulfurization, abstraction desulfurization and biological desulphurization etc..Wherein oxidation sweetening has operating condition is under room temperature, normal pressure, equipment and the relatively low advantage of running cost, is that development in recent years is the fastest, the non-hydrodesulfurization of the most potential replacement hydrodesulfurization.Oxidative desulfurization techniques is combined with the desulfurization technology such as extraction, absorption, promotes the desulfurized effect of sulfur-containing compound in fuel oil by further functioning as.
Polyacid because of its composition, size, shape, charge density, heat stability and oxidation-reduction quality all in a wider adjustable extent by people's extensive concern.Such as Keggin-type polyacid has been widely used in homogeneous and inhomogeneous reaction as catalyst.But, sandwich type polyacid K10Co4(H2O)2(PW9O34)2Research in terms of desulfurization is less.In recent years, in the latest developments of polyacid surface chemistry, finding that positively charged surfactant can replace polyoxometallate counter ion counterionsl gegenions, make that surfactant is coated with bunch fits together with core housing.Parents' catalyst, at the interfacial assembly of emulsion droplet, considerably increases total interfacial area, and catalyst can be made preferably to contact with sulfur-containing compound, reaches ultra-deep oxidation sweetening purpose.
Summary of the invention
It is an object of the invention to provide a kind of amphiphilic containing cobalt sandwich type heteropolyacid catalyst, hydrogen peroxide is as oxidant, and ionic liquid, as extractant, forms three-phase microemulsion catalyst system and catalyzing, can be with high-efficiency desulfurization.After reaction, by static breakdown of emulsion, catalyst can be separated by centrifugation.
One of the present invention is amphiphilic containing cobalt sandwich type heteropoly acid, and molecular formula is: [C18H37N(CH3)3]10[Co4(H2O)2(PW9O34)2], molecular weight is: 6054.
The amphiphilic concrete synthesis step of sandwich type heteropoly acid containing cobalt of one of the present invention is as follows:
(1) synthesis containing cobalt sandwich type heteropoly acid:
0.001-0.014mol cobalt nitrate is dissolved in 9-24ml ionized water, in purple solution, under stirring, adds 0.001-0.012mol phosphotungstic acid (A-PW9), heated solution is in homogeneous claret, the potassium chloride (0.05-0.08mmol) of excess is added in above-mentioned solution, generation bluish violet precipitates, after being cooled to room temperature, sucking filtration is dried, and is re-dissolved in by pressed powder in 5-20ml hot water, at 3-8 DEG C of recrystallization, collection obtains bluish violet crystal, is dried 1-3 hour in vacuum drying oven；
(2) the amphiphilic synthesis containing cobalt sandwich type heteropoly acid:
The ethanol solution of the surfactant that concentration is 0.5-2mol/L is slowly dropped to same volume concentration be 0.05-0.2mol/L containing in cobalt sandwich type heteropoly acid aqueous solution, wherein the mol ratio containing cobalt sandwich type heteropoly acid with surfactant is 1:5-1:12, stir 2 hours, centrifugal, several times, under vacuum condition, 60-100 C is dried 6-10 hour and obtains catalyst for ethanol and washing.
The described sandwich type heteropoly acid containing cobalt is K10[Co4(H2O)2(PW9O34)2], described cationic surfactant is octadecyl trimethyl ammonium chloride, and finally obtaining parents' catalyst is [C18H37N(CH3)3]10[Co4(H2O)2(PW9O34)2]
The method of extraction catalytic oxidation desulfurization of the present invention, key step includes:
A) under 25-70 ° of C normal pressure, 500ppm simulated oil, ionic liquid, catalyst and hydrogen peroxide are sequentially added in flask and are sufficiently mixed, catalyst is 1:100-l:20 with the mol ratio of simulated oil, simulated oil sulfur content is 1:2-1:8 with the mol ratio of hydrogen peroxide, react 5-90 minute, will be present in the sulfur compound in simulated oil and be converted into corresponding sulfone；
B), after having reacted, utilize the method toppled over upper strata simulated oil to be poured out, be the oil product after deep desulfuration；
C) after washing several times with dichloromethane, by catalyst and ionic liquid centrifugation, putting into vacuum drying oven 6-12 hour, again obtain catalyst, after using 6 times, catalytic efficiency is without substantially reducing.
Described 500ppm simulated oil is respectively as follows: 0.73g benzothiophene (BT) and 0.5g biphenyl is dissolved in 500ml normal octane and is mixed to prepare；1.0g dibenzothiophenes (DBT) and 0.5g biphenyl are dissolved in 500ml normal octane and are mixed to prepare；1.16g 4,6-dimethyl Dibenzothiophene (4,6-DMDBT) and 0.5g biphenyl are dissolved in 500ml normal octane and are mixed to prepare, corresponding oxidation product be dibenzothiophene sulphone, benzothiophene sulfone, 4,6-dimethyl Dibenzothiophene sulfone.
Described ionic liquid is 1-butyl-3-Methylimidazole. hexafluorophosphate ([Bmim] PF6)。
The positive effect of the present invention is: the present invention be prepared for a kind of surfactant parcel containing cobalt sandwich type heteropoly acid new catalyst, this catalyst forms three-phase microemulsion catalyst system and catalyzing with hydrogen peroxide, ionic liquid and simulated oil, carry out desulfurization at normal temperatures, can be with high-efficiency desulfurization.And catalyst and ionic liquid can be through being recycled for multiple times, desulfuration efficiency, without significantly reducing, is one more successfully sulfur method.
Accompanying drawing explanation
If figure is a kind of amphiphilic infrared spectrogram containing cobalt sandwich type heteropoly acid: a) infrared spectrogram of surfactant；B) infrared spectrogram containing cobalt sandwich type heteropoly acid；C) the amphiphilic infrared spectrogram containing cobalt sandwich type heteropoly acid.
Detailed description of the invention
Embodiment 1:
The amphiphilic concrete synthesis step of sandwich type heteropoly acid containing cobalt of described one is as follows:
(1) synthesis containing cobalt sandwich type heteropoly acid:
0.41g cobalt nitrate is dissolved in 15ml ionized water, in purple solution, under stirring, adds 2.0g phosphotungstic acid (A-PW9), the potassium chloride (4-6g) of excess, in homogeneous claret, is added in above-mentioned solution by heated solution, generation bluish violet precipitates, and after being cooled to room temperature, sucking filtration is dried, and is re-dissolved in by pressed powder in 5-10ml hot water, at 5 DEG C of recrystallization, collect and obtain bluish violet crystal.Vacuum drying oven is dried 2 hours；
(2) the amphiphilic synthesis containing cobalt sandwich type heteropoly acid:
The ethanol solution of the surfactant that concentration is 1mol/L is slowly dropped to same volume concentration be 0.1mol/L containing in cobalt sandwich type heteropoly acid aqueous solution, wherein the mol ratio containing cobalt sandwich type heteropoly acid with surfactant is 1:10, stir 2 hours, centrifugal, several times, under vacuum condition, 80 C are dried 8 hours and obtain catalyst for ethanol and washing.
Embodiment 2: containing the extraction catalytic oxidation desulfurization experiment of benzothiophene simulated oil:
Take 0.73g benzothiophene and 0.5g biphenyl is dissolved in normal octane, be configured to the 500mL simulation oil product containing benzothiophene 500ppm, then by the 23mg catalyst of above-mentioned preparation, 21 μ L hydrogen peroxide, 1mL ionic liquid [Bmim] PF6, 5mL simulated oil is sequentially added in 25mL round-bottomed flask, and at 60 DEG C, magnetic agitation is reacted 60 minutes, wherein takes out the supernatant every 10 minutes, and gas chromatographic analysis, experimental result is shown in Table 1.After reaction terminates, tipping is used residue simulated oil to be poured out.After washing several times with dichloromethane, then by catalyst and ionic liquid centrifugation, put into vacuum drying oven 6 hours, again obtain catalyst and enter in next round reaction.After using 6 times, catalytic efficiency is without substantially reducing.
Embodiment 3: containing the extraction catalytic oxidation desulfurization experiment of dibenzothiophenes simulated oil:
Take 1.0g dibenzothiophenes and 0.5g biphenyl is dissolved in normal octane, be configured to the 500mL simulation oil product containing dibenzothiophenes 500ppm, then by the 23mg catalyst of above-mentioned preparation, 21 μ L hydrogen peroxide, 1mL ionic liquid [Bmim] PF6, 5mL simulated oil is sequentially added in 25mL round-bottomed flask, and at 60 DEG C, magnetic agitation is reacted 80 minutes, wherein takes out the supernatant every 10 minutes, and gas chromatographic analysis, experimental result is shown in Table 1.After reaction terminates, tipping is used residue simulated oil to be poured out.After washing several times with dichloromethane, then by catalyst and ionic liquid centrifugation, put into vacuum drying oven 8 hours, again obtain catalyst and enter in next round reaction.After using 6 times, catalytic efficiency is without substantially reducing.
Embodiment 4: containing the extraction catalytic oxidation desulfurization experiment of 4,6-dimethyl Dibenzothiophene simulated oil:
Taking 1.16g 4,6-DMDBT and 0.5g biphenyl is dissolved in normal octane, is configured to 500mL and contains 4, and the simulation oil product of 6-dimethyl Dibenzothiophene 500ppm, then by the 23mg catalyst of above-mentioned preparation, 21 μ L hydrogen peroxide, 1mL ionic liquid [Bmim] PF6, 5mL simulated oil is sequentially added in 25mL round-bottomed flask, and at 60 DEG C, magnetic agitation is reacted 90 minutes, wherein takes out the supernatant every 10 minutes, and gas chromatographic analysis, experimental result is shown in Table 1.After reaction terminates, tipping is used residue simulated oil to be poured out.After washing several times with dichloromethane, then by catalyst and ionic liquid centrifugation, put into vacuum drying oven 10 hours, again obtain catalyst and enter in next round reaction.After using 6 times, catalytic efficiency is without substantially reducing.
Test example: the one selecting embodiment 1 preparation is amphiphilic containing cobalt sandwich type heteropolyacid catalyst, according to embodiment 2, different reaction substrates is carried out extracting catalytic oxidation desulfurization reaction by 3,4, and result is as shown in table 1:
Table 1:
Conclusion: from table 1 it follows that under identical reaction conditions, catalyst is best to the removal effect of dibenzothiophenes, substantially can remove completely.Removal effect order is: dibenzothiophenes > 4,6-dimethyl Dibenzothiophene > benzothiophene.
Claims (3)
1. one kind amphiphilic containing cobalt sandwich type heteropoly acid, it is characterised in that: molecular formula is: [C18H37N(CH3)3]10[Co4(H2O)2(PW9O34)2], molecular weight is: 6054.
A kind of amphiphilic preparation method containing cobalt sandwich type heteropoly acid the most according to claim 1, it is characterised in that: it is by containing cobalt sandwich type heteropoly acid K10[Co4(H2O)2(PW9O34)2] and cationic surfactant C18H37N(CH3)3Cl is obtained by ion exchange and electrostatic force self assembly, specifically comprises the following steps that
(1) synthesis containing cobalt sandwich type heteropoly acid:
0.001-0.014mol cobalt nitrate is dissolved in 9-24ml ionized water, in purple solution, under stirring, adds 0.001-0.012mol phosphotungstic acid A-PW9Heated solution is in homogeneous claret, the potassium chloride 0.05-0.08mmol of excess is added in above-mentioned solution, generation bluish violet precipitates, after being cooled to room temperature, sucking filtration is dried, and is re-dissolved in by pressed powder in 5-20ml hot water, at 3-8 DEG C of recrystallization, collection obtains bluish violet crystal, is dried 1-3 hour in vacuum drying oven；
(2) the amphiphilic synthesis containing cobalt sandwich type heteropoly acid:
The ethanol solution of the surfactant that concentration is 0.5-2mol/L is slowly dropped to same volume concentration be 0.05-0.2mol/L containing in cobalt sandwich type heteropoly acid aqueous solution, wherein the mol ratio containing cobalt sandwich type heteropoly acid with surfactant is 1:5-1:12, stir 2 hours, centrifugal, ethanol and washing are several times, under vacuum condition, 60-100 C is dried 6-10 hour, obtains catalyst.
A kind of amphiphilic application containing cobalt sandwich type heteropolyacid catalyst in extraction catalytic oxidation desulfurization system the most according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610234174.3A CN105879912B (en) | 2016-04-17 | 2016-04-17 | A kind of amphiphilic heteropoly acid of interlayer type containing cobalt and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610234174.3A CN105879912B (en) | 2016-04-17 | 2016-04-17 | A kind of amphiphilic heteropoly acid of interlayer type containing cobalt and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105879912A true CN105879912A (en) | 2016-08-24 |
| CN105879912B CN105879912B (en) | 2018-02-06 |
Family
ID=56703987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610234174.3A Active CN105879912B (en) | 2016-04-17 | 2016-04-17 | A kind of amphiphilic heteropoly acid of interlayer type containing cobalt and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105879912B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106986778A (en) * | 2017-03-03 | 2017-07-28 | 赵建社 | Surfactant type heteropoly acid and its preparation method and application |
| CN107029804A (en) * | 2017-04-27 | 2017-08-11 | 辽宁大学 | Catalyst carrier PIL rGO with erasable write performance and its preparation method and application |
| CN108855232A (en) * | 2018-07-02 | 2018-11-23 | 东北师范大学 | A kind of composite nano fiber and its preparation method and application |
| CN112898355A (en) * | 2021-01-22 | 2021-06-04 | 北华大学 | Method for preventing lignin degradation intermediate product from polycondensation |
| CN115160144A (en) * | 2022-06-14 | 2022-10-11 | 北京理工大学 | Transition metal substituted heteropoly acid based ionic liquid flame retardant, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2016
- 2016-04-17 CN CN201610234174.3A patent/CN105879912B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| FU CHUN-HUA 等: "Hydrothermal Synthesis and Crystal Structure of a New Hexa-cobalt-containing POM", 《结 构 化 学》 * |
| HONGYING LU 等: "Oxidative desulfurization of dibenzothiophene with molecular oxygen using emulsion catalysis", 《CHEM. COM.》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106986778A (en) * | 2017-03-03 | 2017-07-28 | 赵建社 | Surfactant type heteropoly acid and its preparation method and application |
| CN107029804A (en) * | 2017-04-27 | 2017-08-11 | 辽宁大学 | Catalyst carrier PIL rGO with erasable write performance 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 |
| CN108855232A (en) * | 2018-07-02 | 2018-11-23 | 东北师范大学 | A kind of composite nano fiber and its preparation method and application |
| CN108855232B (en) * | 2018-07-02 | 2021-03-19 | 东北师范大学 | Composite nanofiber and preparation method and application thereof |
| CN112898355A (en) * | 2021-01-22 | 2021-06-04 | 北华大学 | Method for preventing lignin degradation intermediate product from polycondensation |
| CN112898355B (en) * | 2021-01-22 | 2023-01-06 | 北华大学 | Method for preventing lignin degradation intermediate product from polycondensation |
| CN115160144A (en) * | 2022-06-14 | 2022-10-11 | 北京理工大学 | Transition metal substituted heteropoly acid based ionic liquid flame retardant, preparation method and application thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105879912B (en) | 2018-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105879912A (en) | Amphiphilic cobalt-containing sandwich type heteropolyacid and application thereof | |
| CN101220293B (en) | Method for ion liquid abstraction-catalytic oxidation desulfurization | |
| Rezvani et al. | Synthesis and characterization of new substituted Sandwich-type Polyoxometalate-based inorganic–organic hybrid nanocomposites for catalytic oxidative desulfurization of real gasoline | |
| CN105689003A (en) | Amphiphilic vanadium-substituted Keggin type heteropoly acid desulfurization catalyst | |
| CN111135865B (en) | Preparation method of phosphotungstic acid modified MOFs-derived porous carbon oxidative desulfurization catalyst | |
| CN104087336A (en) | Method for removing sulfide from oil product by using choline chloride/oxalic acid type eutectic solvent by virtue of oxidation-extraction integrated process | |
| CN103285923A (en) | Oxidative desulfurization amphiphilic catalyst, and preparation method and applications thereof | |
| CN101260314A (en) | Oil oxidation-extraction desulfurization technique based on ionic liquid composite solvent | |
| CN103831137A (en) | Metal phthalocyanine-sensitized titanium dioxide photocatalyst and preparation method thereof | |
| CN104592119B (en) | Heteropoly acid type ionic liquid and its application in oxidation sweetening | |
| CN103589450B (en) | A kind of Ultra-deep oxidative desulfurization of diesel oil | |
| CN106753514A (en) | A kind of method of choline eutectic solvent abstraction desulfurization | |
| Mirante et al. | Polyoxomolybdate based ionic-liquids as active catalysts for oxidative desulfurization of simulated diesel | |
| CN102146296B (en) | Oxidative desulfurization method based on magnetically separable supported cesium phosphotungstate catalyst | |
| Qader et al. | Novel phenolic deep eutectic solvents for desulfurisation of petrodiesel | |
| CN103464141A (en) | Mesoporous material containing high-dispersive tungsten as well as preparation method and application of mesoporous material containing high-dispersive tungsten | |
| CN108187643A (en) | A kind of petrol and diesel oil efficient desulfurizing agent based on graphene | |
| Xu et al. | A fully-organic polymerization carrier calix [4] resorcinarene supported cobalt ionic liquid catalyst with oxone for desulfurization | |
| CN104593056A (en) | Oxidation desulphurization method for diesel oil by using deep eutectic ionic liquid for extraction coupling | |
| CN105038841A (en) | Method for catalyzing fuel oil oxidation desulphurization by polyether type oxovanadium heteropolyacid ionic liquid | |
| CN104689850A (en) | Amphipathy vanadium-containing polyacid catalyst and application of catalyst in oxidation catalytic desulfuration | |
| CN110157467A (en) | A kind of method of catalyzing hydrogen peroxide oxygenated fuel oil deep desulfuration | |
| CN109266378A (en) | A kind of application of peroxydisulfate class ion liquid compound in desulfurizing oil | |
| CN101302441A (en) | Method for removing sulfide in catalytically cracked gasoline by oxidation-extraction | |
| CN104962311A (en) | Method for desulfurizing diesel oil through oxidizing by using oxygen |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |