CN101474574A - Solid catalyst for petroleum liquid component sweetening and preparation method - Google Patents
Solid catalyst for petroleum liquid component sweetening and preparation method Download PDFInfo
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- CN101474574A CN101474574A CN 200810051326 CN200810051326A CN101474574A CN 101474574 A CN101474574 A CN 101474574A CN 200810051326 CN200810051326 CN 200810051326 CN 200810051326 A CN200810051326 A CN 200810051326A CN 101474574 A CN101474574 A CN 101474574A
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Abstract
Disclosed is a solid catalyst used for removal of mercaptans of petroleum liquid ingredients. The catalyst uses gamma-Al2O3 as a carrier, first loads a metal nitrate on the carrier by immersion method and then bakes the metal nitrate to realize loading of alkali metal oxide on the carrier gamma-Al2O3 so as to produce the alkali catalyst carrier, and then uses the mixed solution of sulfonated cobalt phthalocyanine and ethanol water added with quaternary ammonium salt or organic base as impregnating solution to impregnate the carrier to obtain the target catalyst after drying. The catalyst is mainly suitable for removal of mercaptans of liquefied petroleum gas, gasoline, kerosene, naphtha, aviation fuel, liquid propylene and other liquefied petroleum ingredients. Experiments prove that the thiol conversion rate can stand at 100% in 20min and the life of the catalyst exceeds 300h.
Description
Technical field
The present invention relates to a kind of solid catalyst for petroleum liquid component sweetening and preparation method.
Background technology
Contain a considerable amount of sulfide in the oil product, wherein mercaptan (RSH) having the greatest impact to oil quality.It not only makes oil product produce foul smell, and influences the stability of oil product.In addition, under the temperature condition with higher, mercaptan also has corrosivity.Therefore, in petroleum refining process, must carry out deodorizing and refining to oil product and handle to remove mercaptan or mercaptan is converted into the less disulphide of harm.Relevant oil product deodorizing and refining, the technical process that generally adopts is that caustic prescrub adds deodorization both at home and abroad, its developing direction mainly is to reduce even eliminate fully the discharging of spent lye, improves deodorization efficiency.Occurred technologies such as no caustic alkali deodorization and non-alkali liquor deodorization at present, but be noted that and also need constantly to add alkali lye (minimum alkalimetry) and water (non-alkali liquor method) in the use, thereby the inreal problem of environmental pollution that solves liquid base.
Therefore, in order to adapt to the needs of petroleum refining industry's development, satisfy strict day by day environmental requirement, reduce the discharging and the processing of spent lye, the solid base catalyst that exploitation is suitable is expected fundamentally to eliminate the discharging of spent lye, reduces desulphurization cost, simplifies the desulfurization program.
Present employing solid catalyst is as follows:
Polymeric solid alkali.Polymeric solid alkali is a kind of product that replaces traditional aqueous caustic that grows up in the seventies.A.L.German (Influence of base density withpolymeric ligand) etc. use the polyvinyl lactam of amido modified as solid base carrier and catalyst oxidation 1-ethanethio, combination with stronger oxidation and basic center function, compare with the CoPc/NaOH system, an activity that significantly strengthens is arranged.Its shortcoming is: the swellability of macromolecule carrier can cause the gathering of CoPc molecule, thereby has reduced catalyst activity or caused catalysqt deactivation, and the regeneration of catalyst is very difficult.
Inoganic solids alkali.With a kind of particulate minerals-shepardite, its main component is Mg (OH) to F.T.Gardner (Mg (OH) in the petroleum Industr) etc. in gasoline refining
2, found that Mg (OH)
2In gasoline refining, has following effect: (1) dephenolize; (2) depriving hydrogen sulphide; (3) in and acidic materials; (4) gasoline deodorization.But when carrying out deodorization with magnesium hydroxide, must be in gasoline addition element sulphur, easy like this cause deodorization after the oil product copper strip test defective.
Load-type solid.American UOP company has developed a kind of catalyst and has used the deodorizing technology (USP5286372) of this catalyst, and this catalyst is loaded on a kind of solid base by metal complex and forms; Metal complex is metal phthalocyanine preferably, most preferably sulfonated phthalocyanine cobalt; Solid base wherein can be solid solution, stratiform dihydroxide or their mixture of metal oxide.It is both as solid base, again as the carrier of metal complex.Use the deodorizing technology of this catalyst not need to add liquid base, but this activity of such catalysts and stability are not ideal enough.
Jiang Deen etc. prepare the MgO-ZrO of high-specific surface area
2Carrier (Preparation ofZrO2-supported MgO with high surface area and its use in mercaptanoxidation of jetfuel), the XRD diffraction found that 0.25gMgO/gZrO
2Have bigger specific area, more alkali center, decentralization largely.Behind the load C oPcS, be that disulphide has good initial activity, but the life-span is short to the aviation fuel mercaptan oxidation.
Summary of the invention
Purpose of the present invention just is to avoid deficiency of the prior art, and a kind of preparation method who is used for a kind of solid catalyst for petroleum liquid component sweetening of oil refinery is provided.It can replace liquid base, and eradicates the discharging of spent lye, makes technology reach the requirement of refined oil simultaneously.
A kind of preparation method who is used for the solid base catalyst of oil refinery removal of mercaptans who the present invention relates to, its characteristics be mainly by with metal-nitrate solutions, by dip loading at carrier γ-Al
2O
3On, make nitrate on carrier, be decomposed into metal oxide through calcination activation then and form the strong basicity center, again the phthalocyanines metal complex is loaded on the catalyst, suppress the polymerization of phthalocyanines metal complex by adding quantitative quaternary ammonium salt simultaneously, this has not only increased the basicity of catalyst, and has improved activity of such catalysts and life-span.
The prescription of the constituent of a kind of solid catalyst for petroleum liquid component sweetening provided by the invention is as follows: it is the mixture of A, B, C and D; The A:B:C:D mass ratio is 10-20:10-30:5-15:0.1-1:0.1-0.5;
A is through dried γ-Al
2O
3
B is Mg (NO
3)
26H
2O;
C is co-catalyst Ni (NO
3)
26H
2O, Fe (NO
3)
3, Co (NO
3)
3, Cu (NO
3)
2, Na (NO
3) or K (NO
3); D is a sulfonated phthalocyanine cobalt; E is quaternary ammonium salt or organic base, and preferred quaternary ammonium salt is for being dodecyl bromination ammonium, cetyl ammonium bromide, octadecyl diethyl benzylic hydrogens amine-oxides, octadecyl dimethyl benzyl ammonium hydroxide, trihydroxyethyl benzylic hydrogens amine-oxides or octadecyl dihydroxy ethyl benzylic hydrogens amine-oxides.
The preparation method's of a kind of solid catalyst for petroleum liquid component sweetening provided by the invention step and condition are as follows:
γ-Al
2O
3It in vacuum vacuum drying under the condition of 0.08Mpa-0.1MPa; Get dried γ-Al by proportioning
2O, Mg (NO
3)
26H
2O and co-catalyst are with they common maceration extracts of making soluble in water, dry γ-Al
2O
3: water quality is than being 1:1-3;
Described co-catalyst comprises: Ni (NO
3)
26H
2O, Fe (NO
3)
3, Co (NO
3)
3, Cu (NO
3)
2, Na (NO
3) or K (NO
3);
First step dipping: with γ-Al
2O
3Be immersed in the above-mentioned maceration extract, in the dipping process, adopt supersonic oscillations, frequency of ultrasonic is 40KHz, and dipping temperature is 10-50 ℃, preferred temperature 20-30 ℃, and dip time 1-30 hour;
Take out the γ-Al after flooding
2O
3, be to carry out roasting after the vacuum drying under the condition of 0.08Mpa-0.1MPa in vacuum, sintering temperature is 400-800 ℃, preferred temperature 500-600 ℃; Roasting time is 1-10 hour, obtains the base catalysis agent carrier behind the calcination activation;
The second step dipping: sulfonated phthalocyanine cobalt and quaternary ammonium salt are dissolved in ethanol: water volume ratio is that be made into mixed impregnant liquor, sulfonated phthalocyanine cobalt: the mass ratio of quaternary ammonium salt is 1-10:1-5 in the mixed solution of second alcohol and water of 6-2:1; The quaternary ammonium salt that uses is dodecyl bromination ammonium, cetyl ammonium bromide, octadecyl diethyl benzylic hydrogens amine-oxides, octadecyl dimethyl benzyl ammonium hydroxide, trihydroxyethyl benzylic hydrogens amine-oxides or octadecyl dihydroxy ethyl benzylic hydrogens amine-oxides;
The base catalysis agent carrier behind the above-mentioned calcination activation, put into above-mentioned mixed impregnant liquor and carry out dip loading; Dipping temperature is 10-30 ℃, preferred 15-20 ℃; Dip time is 12-48 hour, preferred 20-30 hour; Be vacuum drying 24 hours under the condition of 0.08Mpa-0.1MPa in vacuum after the load, obtain a kind of solid catalyst for petroleum liquid component sweetening.
Catalyst of the present invention is applicable to the removal of mercaptans of liquefied petroleum gas (LPG), gasoline, kerosene, naphtha, aviation fuel, liquid propene and other liquid petroleum component.
Beneficial effect: catalyst provided by the present invention does not need to add liquid base when being used for the removal of mercaptans oxidation, simultaneously owing to the mixed solution with the second alcohol and water is maceration extract and adds quantitative quaternary ammonium salt, phthalocyanine cobalt molecule is evenly disperseed by electrostatic interaction on carrier surface, and quaternary ammonium salt can increase the basicity of catalyst, thereby makes the mercaptan oxidation activity and the stability of this catalyst obviously improve.
The specific embodiment
1 example of embodiment provides Preparation of catalysts of the present invention
First step dipping: get 15.0g γ-Al
2O
3Vacuum drying seals preservation after 24 hours.With 30.0g Mg (NO
3)
26H
2O and co-catalyst 6.0g Ni (NO
3)
26H
2O is dissolved in the maceration extract of making first step dipping in the 30.0g distilled water jointly; Carrier γ-Al that drying is good
2O
3Be immersed in the above-mentioned maceration extract, adopt supersonic oscillations in the dipping process, frequency of ultrasonic is 40KHz, and dipping temperature is 30 ℃, dip time 24 hours; Dipping finishes the back and takes out carrier, and roasting is carried out in vacuum drying then, and sintering temperature is 500 ℃, and roasting time is 5 hours, obtains the base catalysis agent carrier behind the calcination activation;
The second step dipping: get 0.5g sulfonated phthalocyanine cobalt and 0.1g C
12H
28BrN is dissolved in the mixed solution of the second alcohol and water of 5:1 proportioning by volume, makes the maceration extract of the second step dipping; The maceration extract of base catalysis agent carrier behind the above-mentioned calcination activation being put into the second step dipping carries out dip loading, and load time is 24 hours, and dry 24 hours of load final vacuum obtains the target catalyst.
The experimental technique of 2 example explanations of embodiment catalyst desulfurizing activity
1), static test
The gasoline liquid that 25ml is contained mercaptan joins in the closed reactor that the 1.0g catalyst is housed, static placement, the concentration of mensuration mercaptan.
2), simulation dynamic test
The gasoline liquid that 25ml is contained mercaptan joins in the closed reactor that the 1.0g catalyst is housed, and concussion is stirred, and measures the concentration of mercaptan.
Concentrations of mercaptans adopts the gas chromatograph of flame photometric detector to analyze.Chromatographic column is a capillary column, analysis condition: the post case: 50 ℃; 200 ℃ of injectors; 220 ℃ of detectors; Carrier gas (N
2): 25ml/min; H
2: 30ml/min; Air: 300ml/min; Sampling volume: 0.5 μ L.The Determination of Trace Sulfur determining alcohol all has the analysis to measure that the method is carried out in following examples.
3 example explanations of embodiment catalyst formulation parameter is to the influence of catalyst
In the preparation process of this example catalyst, other preparation process conditions and parameter all conform to example 1 except that formulation parameter shown in the form.It is as shown in the table for removal of mercaptans activity analysis data:
4 example explanations of embodiment co-catalyst is to the influence of catalyst activity
In the Preparation of catalysts process, the co-catalyst of first step dipping is chosen respectively: Ni (NO
3)
26H
2O, Fe (NO
3)
3, Co (NO
3)
3, Cu (NO
3)
2, Na (NO
3) or K (NO
3), other preparation process conditions and parameter all conform to example 1.Removal of mercaptans activity analysis data are as follows:
5 example explanations of embodiment sintering temperature is to the influence of catalyst
In the Preparation of catalysts process, the γ-Al behind the first step dipping
2O
3Carry out the calcination activation temperature and choose 500 ℃, 600 ℃, 700 ℃, 800 ℃ respectively, other preparation process conditions and parameter all conform to example 1.Removal of mercaptans activity analysis data are as follows:
Sintering temperature is to the influence (reaction time 20min) of yield
6 actual gains explanations of embodiment maceration extract component is to the influence of catalyst activity
In the Preparation of catalysts process, the mixed impregnant liquor of the second step dipping gets that sulfonated phthalocyanine cobalt is dissolved in 30ml H2O, H2O:CH3CH2OH is among mixed solution, ethanol or the CH3OH of 2:1 by volume, and other preparation process conditions and parameter all conform to example 1.Catalyst reusability data are as follows:
Maceration extract is to the influence of catalyst life
7 example explanation quaternary ammonium salts of embodiment or organic base are to the influence of catalyst activity.
In the Preparation of catalysts process, the mixed impregnant liquor of the second step dipping is got sulfonated phthalocyanine cobalt 0.3g C
12H
28BrN, CTAB, cetyl ammonium bromide, octadecyl diethyl benzylic hydrogens amine-oxides, octadecyl dimethyl benzyl ammonium hydroxide, trihydroxyethyl benzylic hydrogens amine-oxides, octadecyl dihydroxy ethyl benzylic hydrogens amine-oxides or hydroxyl sulfoacid naphthalene 0.2g are dissolved in the 30ml water jointly, and other preparation process conditions and parameter all conform to example 1.Removal of mercaptans activity analysis data are as follows:
The influence of quaternary ammonium salt or organic base
Reaction time 20min,
8 examples of embodiment illustrate the reusability of catalyst provided by the invention.
The use of institute's controlling catalyst repeatability data are as follows in the example 1:
The catalyst access times are to the influence of yield
Reaction time: 30min
9 examples of embodiment illustrate the removal of mercaptans activity of this catalyst to different petroleum liquid components.
Catalyst is as follows to the desulphurizing activated data of different oil products in the example 1:
Claims (6)
1, a kind of solid catalyst for petroleum liquid component sweetening is characterized in that its composition and prescription are as follows:
It is the mixture of A, B, C and D; The A:B:C:D mass ratio is 10-20:10-30:5-15:0.1-1:0.1-0.5;
A is through dried γ-Al
2O
3
B is Mg (NO
3)
26H
2O;
C is co-catalyst Ni (NO
3)
26H
2O, Fe (NO
3)
3, Co (NO
3)
3, Cu (NO
3)
2, Na (NO
3) or K (NO
3);
D is a sulfonated phthalocyanine cobalt;
E is quaternary ammonium salt or organic base, and preferred quaternary ammonium salt is for being dodecyl bromination ammonium, cetyl ammonium bromide, octadecyl diethyl benzylic hydrogens amine-oxides, octadecyl dimethyl benzyl ammonium hydroxide, trihydroxyethyl benzylic hydrogens amine-oxides or octadecyl dihydroxy ethyl benzylic hydrogens amine-oxides.
2, the method for making of a kind of solid catalyst for petroleum liquid component sweetening as claimed in claim 1 is characterized in that step and condition are as follows:
γ-Al
2O
3It in vacuum vacuum drying under the condition of 0.08Mpa-0.1MPa; Get dried γ-Al by proportioning
2O, Mg (NO
3)
26H
2O and co-catalyst are with they common maceration extracts of making soluble in water, dry γ-Al
2O
3: water quality is than being 1:1-3;
Described co-catalyst comprises: Ni (NO
3)
26H
2O, Fe (NO
3)
3, Co (NO
3)
3, Cu (NO
3)
2, Na (NO
3) or K (NO
3);
First step dipping: with γ-Al
2O
3Be immersed in the above-mentioned maceration extract, in the dipping process, adopt supersonic oscillations, frequency of ultrasonic is 40KHz, and dipping temperature is 10-50 ℃, dip time 1-30 hour;
Take out the γ-Al after flooding
2O
3, be to carry out roasting after the vacuum drying under the condition of 0.08Mpa-0.1MPa in vacuum, sintering temperature is 400-800 ℃, roasting time is 1-10 hour, obtains the base catalysis agent carrier behind the calcination activation;
The second step dipping: sulfonated phthalocyanine cobalt and quaternary ammonium salt are dissolved in ethanol: water volume ratio is that be made into mixed impregnant liquor, sulfonated phthalocyanine cobalt: the mass ratio of quaternary ammonium salt is 1-10:1-5 in the mixed solution of second alcohol and water of 6-2:1; The quaternary ammonium salt that uses is dodecyl bromination ammonium, cetyl ammonium bromide, octadecyl diethyl benzylic hydrogens amine-oxides, octadecyl dimethyl benzyl ammonium hydroxide, trihydroxyethyl benzylic hydrogens amine-oxides or octadecyl dihydroxy ethyl benzylic hydrogens amine-oxides;
The base catalysis agent carrier behind the above-mentioned calcination activation, put into above-mentioned mixed impregnant liquor and carry out dip loading; Dipping temperature is 10-30 ℃, and dip time is 12-48 hour, is vacuum drying 24 hours under the condition of 0.08Mpa-0.1MPa in vacuum after the load, obtains a kind of solid catalyst for petroleum liquid component sweetening.
3, the method for making of a kind of solid catalyst for petroleum liquid component sweetening as claimed in claim 1 is characterized in that, the dipping temperature of described first step dipping is 20-30 ℃.
4, the method for making of a kind of solid catalyst for petroleum liquid component sweetening as claimed in claim 1 is characterized in that, first step dipping takes out the γ-Al after flooding
2O
3The temperature of carrying out roasting under condition after the vacuum drying is 500-600 ℃.
5, the method for making of a kind of solid catalyst for petroleum liquid component sweetening as claimed in claim 1 is characterized in that, the described second step dipping the base catalysis agent carrier behind the described calcination activation, is put into above-mentioned mixed impregnant liquor and carried out dip loading; Dipping temperature is 15-20 ℃.
6, the method for making of a kind of solid catalyst for petroleum liquid component sweetening as claimed in claim 1, it is characterized in that, the described second step dipping the base catalysis agent carrier behind the described calcination activation, is put into described mixed impregnant liquor and is carried out dip loading; Dip time is 20-30 hour.
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|---|---|---|---|
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|---|---|---|---|
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| CN101474574B CN101474574B (en) | 2012-08-22 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101705108B (en) * | 2009-12-11 | 2012-09-05 | 郝天臻 | Liquid hydrocarbon mercaptan removal technique capable of deeply removing total sulfur |
| CN103170363A (en) * | 2011-12-21 | 2013-06-26 | 冯良荣 | Catalyst for preparing chloroethylene by acetylene hydrochlorination |
| CN103170364A (en) * | 2011-12-21 | 2013-06-26 | 冯良荣 | Catalyst for preparing chloroethylene through acetylene hydrochlorination |
| CN103965984A (en) * | 2013-02-04 | 2014-08-06 | 中国石油大学(北京) | Method for removing mercaptan in liquefied petroleum gas through catalysis |
| CN104841484A (en) * | 2015-04-02 | 2015-08-19 | 中国石油大学(华东) | Method for preparing mercaptan conversion catalyst in petroleum |
| CN104549337B (en) * | 2013-10-15 | 2017-01-25 | 中国石油化工股份有限公司 | Oxidation catalyst for mercaptan in light oil, as well as preparation method and application of mercaptan oxidation catalyst |
| CN108014786A (en) * | 2017-12-08 | 2018-05-11 | 中国石油大学(北京) | A kind of high metal dispersion degree catalyst and preparation method and application |
| CN110064422A (en) * | 2018-01-23 | 2019-07-30 | 中国石油天然气股份有限公司 | Multi-metal continuous reforming catalyst and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074313C (en) * | 1997-06-04 | 2001-11-07 | 中国石油化工总公司 | Supported phthalocyaanine cobalt mercaptan oxidation catalyst |
| US20050284794A1 (en) * | 2004-06-23 | 2005-12-29 | Davis Timothy J | Naphtha hydroprocessing with mercaptan removal |
-
2008
- 2008-10-24 CN CN2008100513261A patent/CN101474574B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101705108B (en) * | 2009-12-11 | 2012-09-05 | 郝天臻 | Liquid hydrocarbon mercaptan removal technique capable of deeply removing total sulfur |
| CN103170363A (en) * | 2011-12-21 | 2013-06-26 | 冯良荣 | Catalyst for preparing chloroethylene by acetylene hydrochlorination |
| CN103170364A (en) * | 2011-12-21 | 2013-06-26 | 冯良荣 | Catalyst for preparing chloroethylene through acetylene hydrochlorination |
| CN103965984A (en) * | 2013-02-04 | 2014-08-06 | 中国石油大学(北京) | Method for removing mercaptan in liquefied petroleum gas through catalysis |
| CN104549337B (en) * | 2013-10-15 | 2017-01-25 | 中国石油化工股份有限公司 | Oxidation catalyst for mercaptan in light oil, as well as preparation method and application of mercaptan oxidation catalyst |
| CN104841484A (en) * | 2015-04-02 | 2015-08-19 | 中国石油大学(华东) | Method for preparing mercaptan conversion catalyst in petroleum |
| CN108014786A (en) * | 2017-12-08 | 2018-05-11 | 中国石油大学(北京) | A kind of high metal dispersion degree catalyst and preparation method and application |
| CN110064422A (en) * | 2018-01-23 | 2019-07-30 | 中国石油天然气股份有限公司 | Multi-metal continuous reforming catalyst and preparation method thereof |
| CN110064422B (en) * | 2018-01-23 | 2022-01-04 | 中国石油天然气股份有限公司 | Multi-metal continuous reforming catalyst and preparation method thereof |
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