CN1699518A - Process for desulfurization of oil products by electrochemical catalytic oxidation - Google Patents
Process for desulfurization of oil products by electrochemical catalytic oxidation Download PDFInfo
- Publication number
- CN1699518A CN1699518A CN 200410042517 CN200410042517A CN1699518A CN 1699518 A CN1699518 A CN 1699518A CN 200410042517 CN200410042517 CN 200410042517 CN 200410042517 A CN200410042517 A CN 200410042517A CN 1699518 A CN1699518 A CN 1699518A
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- water
- salt
- oil
- desulfurization
- 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.)
- Pending
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a process for desulfurization of oil products which comprises using water-soluble medium or certain modified ionic liquid as supporting electrolyte, using own made porous carbon fiber composite material with specific surface area and high absorbability property as the anode, carrying out electrochemical oxidation treatment to the oil, removing the sulfides in the oil by transforming them into water-soluble sulfides.
Description
Technical field
The present invention relates to a kind of method of desulfurizing oil.The porous material that specifically is employing self-control bigger serface high absorption property is a composite anode, in the presence of ionogen, by electrochemical catalytic oxidation oil product is carried out desulfurization.
Background technology
The countries in the world expanding economy all be unable to do without the production and the consumption of oil.Since oneth century, the high speed development of petroleum industry and automotive industry is human civilization and social progress, has made huge contribution, but the burning of the sulfide that (mainly refers to gasoline and diesel oil here) in the oil product, the SO of generation
2, SO
3Be one of principal pollutant of environment.Along with the enhancing of environmental consciousness in the world wide, various countries have taked a series of measures in succession, and are more and more harsher to the requirement of sulphur content in the oil product.In new edition " world fuel charter ", 2, No. 3 standard-requireds of motor spirit standard are respectively less than 200ppm with less than 30ppm; 2, No. 3 standard-requireds of derv fuel oil standard are respectively less than 300ppm with less than 30ppm.China's content of sulfur in gasoline is controlled at 800ppm at present, and the diesel oil sulphur content is controlled at the top grade product and is not more than 2000ppm, and first grade is not more than 5000ppm, and salable product are not more than 10000ppm, and also there is a big difference apart from new standard.Therefore the oil product deep desulfuration seems particularly important concerning China.
Sulfide in the oil product mainly refers to sulfur-containing organic compounds such as thio-alcohol, thioether class, disulfides and thiophene-based.Sulfur method mainly is divided into hydrogenation and non-hydrogenation two big classes.Present commonplace employing be hydrogenating desulfurization, this method is to utilize in the oil product sulfide under the effect of certain temperature, pressure and catalyzer, the element sulphur in the sulfide is generated hydrogen sulfide by hydrogenation reaction remove.Non-hydrodesulfurizationprocess process mainly contains adsorption desulfurize, soda finishing desulfurization, biological desulphurization, abstraction desulfurization, complexing desulfurization etc., and main employing is adsorption desulfurize and soda finishing desulfurization at present.Adsorption desulfurize mainly is to utilize sulfide to have polar group, and the character that can adsorb on some material removes sulfide.What the soda finishing desulfurization then utilized is the acidity of mercaptan, because the ionic dissociation energy of sulphur hydrogen bond is littler than corresponding oxygen hydrogen bond ionic dissociation energy, the acidity of mercaptan is acid stronger than pure and mild phenol, so mercaptan easily and alkali reaction, is created on insoluble salt in the water and removes.
CN1335360 discloses a kind of method and Preparation of catalysts of gasoline hydrofinishing, and this hydrorefined technology and catalyzer have stronger hydrogenating desulfurization ability, and sweet gasoline has little loss of octane number, has excellent catalytic activity, satisfactory stability.But this method in actual production process, exist complex process, facility investment big, need hydrogen source supply, the high defective that can't overcome of desulphurization cost.
CN1217268 discloses a kind of method and technology of adsorption desulfurize, and the activated carbon fiber that it is good with absorption property, intensity is higher replaces gac as carrier, and loading metal-salt is made catalyzer, can carry out desulfurization to catalytically cracked gasoline and handle.But this method has the aftertreatment problem that the unvanquishable defective of all adsorption desulfurizes is a sorbent material, as regenerates that then energy consumption is bigger, then causes solid pollution as not regenerating.
CN1082094 discloses a kind of method of desulfurizing oil.This method is to use biological catalyst, the C-S key in the selective splitting heterocycle.Make between this biological catalyst and the liquid petroleum and form emulsion.The present invention is particularly suitable for containing a large amount of relatively not tractable organosulfur molecules, as dibenzothiophene etc.But the speed of biological desulphurization is slow, is difficult to satisfy the requirement of industrialization high throughput.
Through experimental studies have found that, the Applied Electrochemistry catalyzed oxidation carries out desulfurizing oil, have following superiority with respect to traditional oil product desulfurization method: 1. electrochemical reaction gets the betatopic realization by reactant on electrode, do not need in principle to add other chemical reagent, reduced the consumption of material, and reduced side reaction, improved reaction efficiency, simplified sepn process,, thereby reduced the pollution of environment because electronics is the cleanest reagent.2. the electrochemistry desulphurization reaction carries out at normal temperatures and pressures, and this is very favourable for save energy, reduction facility investment, simplification production process.3. the electrochemistry desulfuration reaction device simply is easy to realize automatic control.
Summary of the invention
Purpose of the present invention is exactly to utilize the advantage of electrochemical catalytic oxidation desulfurization, and it is few to develop a kind of facility investment, and operating process is simple, desulfuration efficiency height, the novel method of free of contamination desulfurizing oil.
Innovation part of the present invention is:
1. prepared and be suitable for the anode that the Applied Electrochemistry catalytic oxidation carries out the novel bigger serface high absorption capacity of desulfurizing oil,
2. the electrolysis system that is suitable for the desulfurization of oil product electrochemical catalytic oxidation has been prepared in research and screening.
Electrochemical catalytic oxidation method described here is exactly that to select the electron carrier with catalytic oxidation activity for use be the medium ionogen, the electron carrier that makes organic sulfide be had catalytic oxidation activity is oxidized to sulfide soluble in water and removes, and this electron carrier with catalytic oxidation activity itself then correspondingly becomes the electron carrier with reducing activity.The electron carrier of this reducing activity is changed into the electron carrier with oxidation activity by Catalytic Oxygen on anode, recycle.Sulfide in the oil product constantly is oxidized to the sulfide that is easy for water and removes like this.
Anode described here is the composite porous electrode of homemade bigger serface high absorption property, and it is made behind supported catalyst by the electrode precast body.
Ionogen described here comprises two kinds:
1. certain had both played electric action, had the metal salt solution of catalytic activity again;
2. non-water-soluble modification ionic liquid.
Embodiment of the present invention
1. the preparation of composite anode
A. the preparation of electrode precast body
The step of preparation is as follows:
(1). the carbon fiber of selecting (comprising one of polyacrylonitrile carbon fiber, asphalt base carbon fiber, micella base carbon fibre or its blend fiber material) is carried out an activation treatment (chemical activation processing), activator can be selected alkali, salt and acid, as sodium hydroxide, potassium hydroxide, zinc chloride, phosphoric acid, one time activatory chemical activating agent consumption is the 10%-50% of carbon fiber weight; The chemical activation temperature is 700-900 ℃; The chemical activation time is 0.5-1h; Chemical activation atmosphere is nitrogen atmosphere, and activation finishes with distilled water the activator eccysis.
(2). the re-activation of process again after will once activating is handled (physically activated processing), selects iron trichloride to make catalyzer in the re-activation process, and treatment temp is 700-900 ℃; Time is 0.5-1h; Atmosphere is steam atmosphere, and activation finishes and with distilled water catalyst wash removed.
(3). the carbon fiber filament weak point is cut to 3-25mm, and carbon fiber is long, drags in the system process in making beating that flocculation is agglomerating easily, can not homodisperse in paper pulp, the electrode precast body of making is inhomogeneous, and carbon fiber is too short, and the intensity of electrode precast body is relatively poor.
(4). the short carbon fiber of cutting put into hollander and add dispersion agent disperse to stir, dispersion agent can be selected polyoxyethylene, amination epoxies, polyacrylamide and Fatty Alcohol(C12-C14 and C12-C18) ethers dispersion agent, the dispersion agent add-on is the 0.1-1% of the prefabricated body weight of electrode, and the concentration of carbon fiber in aqueous dispersant is 1-6% (wt).
(5). with cellulose slurry commonly used in the papermaking, under suitable beating process condition, carry out mechanical dispersion, make beating degree and be 18-25 ° paper pulp as wood pulp, cotton pulp, jute pulp, man-made fiber etc.
(6). with carbon fiber dispersion liquid and slurries according to 2: 1-4: 1 mixed, add the hydrophilic or hydrophobic surfactant of 1% (wt), put into stirrer and mix and stir, both can obtain mixed slurry.
(7). the wet papermaking technology is made required carbon fibre composite paper with the papermaking mixed slurry routinely.
(8). 60-120 ℃ of oven dry promptly gets the electrode precast body of composite anode in loft drier.
B. the load of catalyzer
(1). preparation 0.01molL
-1-2.0molL
-1The salts solution that contains certain metal of concentration, this salt can be molysite, lead salt, manganese salt, cerium salt etc.;
(2). the electrode precast body be impregnated in this salts solution 1-48 hour;
(3). the body material after will flooding is put into loft drier 60-120 ℃ oven dry, carries out carbonizing treatment after the oven dry, and Jin Zi salt is oxidized to oxide grain simultaneously, and this oxide content is 2%-50% (wt), and sintering temperature is 400-1200 ℃;
(4). with supported catalyst and two good materials of carbonizing treatment, the centre adds a wire netting, this metal can be iron, lead, manganese, platinum etc., with the 0.1%-5%CMC aqueous solution and the 10%-80%PTFE aqueous solution by 1: 10-1: the tackiness agent that 2 volume ratios are mixed and made into sticks together and promptly gets this electrode.
The different metal oxide of this body material load can satisfy the requirement of different electrolysis systems.
2. be applied to the preparation of electrochemical catalytic oxidation desulfurization electrolysis system
The electrolysis system here comprises two big classes
(1). water-soluble salt solution electrolysis system: will contain Mn
2+, Fe
2+, Ce
4+, Cl
-It is 0.01molL that isoionic salt is mixed with concentration with deionized water
-1-1.0molL
-1Solution, add 1 again: 20-1: the corresponding acid of 2 volume ratios and concentration are 0.01molL
-1-0.10molL
-1Phase-transfer catalyst get final product, this phase-transfer catalyst can be any liquid phase transfer catalyst.
(2). water-insoluble ionic liquid electrolysis system: ionic liquid BminBF
4(Tetrafluoroboric acid 1-butyl-3-Methylimidazole), BminPF
6(hexafluoro boric acid 1-butyl-3-Methylimidazole), BpyBF
4, (Tetrafluoroboric acid pyridine) BpyPF
6(hexafluoro boric acid pyridine) etc. adds the salt that contains certain metal ion species of 2%-50% (wt) in the process of preparation, this salt can be to contain Mn
2+, Fe
2+, Ce
4+, pb
2+Salt, prepare modification ionic liquid with catalysis, add 1 in this ionic liquid: 10-1: the water of 2 volume ratios and concentration are 0.01molL
-1-0.10molL
-1Phase-transfer catalyst get final product.This phase-transfer catalyst can be any liquid phase transfer catalyst.
3. electrolytic reaction
The condition of electrolysis desulfurization is:
Stock oil: sulphur content is at 10-2500ppm, 60 ℃-350 ℃ fraction oil, comprise straight run and catalytic gasoline,
Straight run and catalytic diesel oil
Electrode: anode-self-made electrode; Negative electrode-copper, lead, graphite etc.
Voltage: 0.2V-4.0V
Electrolysis system: 1. the water-soluble salt solution electrolysis system is 0.01molL
-1-1.0molL
-1Certain salts solution;
2. water-insoluble ionic liquid electrolysis system is 1 for add volume ratio in ionic liquid: 10-1: 2
Deionized water;
3. the concentration of phase-transfer catalyst is 0.01molL
-1-0.10molL
-1
Fluid volume ratio: 1: 10-1: 1
The desulfurization degree of electrochemical catalytic oxidation desulfurization can reach 10%-90%.
The embodiment of the invention
Embodiment 1
In closed cell, add 200mL, 0.1molL
-1The electrolyte system of certain salt, magnetic agitation evenly back add 40mL stock oil (catalytic gasoline), and the electrode that the present invention is prepared is an anode, and graphite is that negative electrode is formed electricity to putting into electrolyzer, and making alive 2.4V electrolysis is 3 hours then.Sampling in static 30 minutes is carried out analysis of total sulfur with microcoulomb sulphur blood urea/nitrogen analyzer after the electrolysis.Other condition is constant, changes electrolyte concentration and is respectively 0.13molL
-1, 0.15molL
-1, 0.18molL
-1, 0.20molL
-1Experimentize.Experimental result sees Table 1.
The desulfurization situation of the different electrolyte concentrations of table 1 catalytic gasoline
| Electrolyte concentration molL -1 | 0.10 | ?0.13 | ?0.15 | ?0.18 | ?0.20 |
| Sulphur content ppm | 74.881 | ?71.551 | ?50.802 | ?73.551 | ?74.674 |
| Desulfurization degree % | 18.03 | ?21.68 | ?44.39 | ?19.49 | ?18.26 |
Annotate: stock oil sulphur content 91.357ppm.
Embodiment 2
In closed cell, add 200mL, 0.15molL
-1The electrolyte system of certain salt, magnetic agitation evenly back adds 40mL stock oil (catalytic gasoline), is anode with the electrode of the present invention's preparation, copper sheet is that negative electrode is formed electricity to putting into electrolyzer, making alive 1.6V electrolysis is 3 hours then.Sampling in static 30 minutes is carried out analysis of total sulfur with microcoulomb sulphur blood urea/nitrogen analyzer after the electrolysis.Other condition is constant, and the change electrolysis voltage is that 2.0V, 2.4V, 2.8V, 3.2V experimentize.Experimental result sees Table 2.
Desulfurization situation during table 2 catalytic gasoline difference voltage
| Voltage V | ?1.6 | ?2.0 | ?2.4 | ?2.8 | ＞4.0 |
| Sulphur content ppm | ?80.654 | ?76.559 | ?30.392 | ?64.748 | Raw material is oxidized |
| Desulfurization degree % | ?12.17 | ?16.63 | ?66.90 | ?29.49 |
Annotate: stock oil sulphur content 91.832ppm.
Embodiment 3
In closed cell, add 200mL, 0.15molL
-1The electrolyte system of certain salt, magnetic agitation evenly back add 30mL stock oil (catalytic gasoline), and the electrode that the present invention is prepared is an anode, and stereotype is that negative electrode is formed electricity to putting into electrolyzer, and making alive 2.4V electrolysis is 3 hours then.Sampling in static 30 minutes is carried out analysis of total sulfur with microcoulomb sulphur blood urea/nitrogen analyzer after the electrolysis.Other condition is constant, changes the stock oil add-on and be 35mL, 40mL, 45mL, 50mL, 60mL experimentizes.Experimental result sees Table 3.
Desulfurization situation during table 3 catalytic gasoline difference fluid volume ratio
| The fluid volume ratio | 35/210 | ?40/210 | ?45/210 | ?50/210 | ?60/210 |
| Sulphur content ppm | 61.842 | ?60.567 | ?54.764 | ?63.474 | ?70.683 |
| Desulfurization degree % | 32.49 | ?33.89 | ?40.22 | ?30.72 | ?22.85 |
Annotate: stock oil sulphur content 91.615ppm.
Embodiment 4
In closed cell, add 200mL, 0.15molL
-1The electrolyte system of certain salt, magnetic agitation evenly back add 30mL stock oil (catalytic diesel oil), and the electrode that the present invention is prepared is an anode, and platinum is that negative electrode is formed electricity to putting into electrolyzer, and making alive 2.4V electrolysis is 3 hours then.Sampling in static 30 minutes is carried out analysis of total sulfur with the sulphur blood urea/nitrogen analyzer after the electrolysis.Other condition is constant, changes the stock oil add-on and be 35mL, 40mL, 45mL, 50mL, 60mL experimentizes.Experimental result sees Table 4.
Desulfurization situation during table 4 catalytic diesel oil diesel oil difference fluid volume ratio
| The fluid volume ratio | 35/210 | ?40/210 | ?45/210 | ?50/210 | ?60/210 |
| Sulphur content ppm | 191 | ?190 | ?181 | ?360 | ?378 |
| Desulfurization degree % | 88.12 | ?88.18 | ?88.74 | ?77.61 | ?76.49 |
Annotate: stock oil sulphur content 1608ppm.
Claims (14)
1. the method for a desulfurizing oil, it is characterized in that adopting the electrochemical catalytic oxidation method, with the composite porous of homemade bigger serface high absorption property is anode, is supporting electrolyte with water-soluble salt solution or modification ionic liquid, and oil product is carried out the electrochemical catalysis desulfurization.
2. electrochemical catalytic oxidation method according to claim 1 is characterized in that the anode that described electrochemical catalytic oxidation method is adopted, and is that the anode electrode precast body is composited by catalyst cupport and inner liner metal net.
3. anode electrode precast body according to claim 2 is characterized in that its procedure of processing is:
(1). the carbon fiber of selecting (comprising one of polyacrylonitrile carbon fiber, asphalt base carbon fiber, micella base carbon fibre or its blend fiber material) is carried out an activation treatment (chemical activation processing), activator can be selected alkali, salt and acid, as sodium hydroxide, potassium hydroxide, zinc chloride, phosphoric acid, the chemical activating agent consumption of an activating chemical processing is the 10%-50% of carbon fiber weight; The chemical activation temperature is 700-900 ℃; The chemical activation time is 0.5-1h; Chemical activation atmosphere is nitrogen atmosphere, and activation finishes with distilled water the activator eccysis.
(2). the re-activation of process again after will once activating is handled (physically activated processing), selects iron trichloride to make catalyzer in the re-activation process, and treatment temp is 700-900 ℃; Time is 0.5-1h; Atmosphere is steam atmosphere, and activation finishes and with distilled water catalyst wash removed.
(3). the carbon fiber filament weak point is cut to 3-25mm.Carbon fiber is long, drags in the system process in making beating that flocculation is agglomerating easily, can not homodisperse in paper pulp, and the electrode precast body of making is inhomogeneous, and carbon fiber is too short, and the intensity of electrode precast body is relatively poor.
(4). the short carbon fiber of cutting put into hollander and add dispersion agent disperse to stir, dispersion agent can be selected polyoxyethylene, amination epoxies, polyacrylamide and Fatty Alcohol(C12-C14 and C12-C18) ethers dispersion agent, the dispersion agent add-on is the 0.1-1% of the prefabricated body weight of electrode, and the concentration of carbon fiber in aqueous dispersant is 1-6% (wt).
(5). with cellulose slurry commonly used in the papermaking, under suitable beating process condition, carry out mechanical dispersion, make beating degree and be 18-25 ° paper pulp as wood pulp, cotton pulp, jute pulp, man-made fiber etc.
(6). with carbon fiber dispersion liquid and slurries according to 2: 1-4: 1 mixed, add the hydrophilic or hydrophobic surfactant of 1% (wt), put into stirrer and mix and stir, both can obtain mixed slurry.
(7). the wet papermaking technology is made required carbon fibre composite paper with the papermaking mixed slurry routinely.
(8). 60-120 ℃ of oven dry promptly gets anodic electrode precast body in loft drier.
4. catalyst cupport according to claim 2 is characterized in that adopting the impregnation sintering method.
5. according to the described impregnation sintering method of claim 4, it is characterized in that steeping fluid is 0.01molL
-1-2.0molL
-1Molysite or lead salt, manganese salt, cerium salt etc.; Dipping time is 1-48 hour.
6. impregnation sintering method according to claim 4 is characterized in that sintering temperature is 400-1200 ℃.
7. according to claim 2,4,5,6 described catalyst cupports, the catalyzer that it is characterized in that being carried on the anode electrode precast body are the oxide compound of molysite or lead salt, manganese salt, cerium salt.
8. according to claim 2,4,5,6,7 described catalyst cupports, the amount that it is characterized in that being carried on the catalyzer on the anode electrode precast body is 2%-50% (wt).
9. the tackiness agent that inner liner metal net according to claim 2 uses, it is characterized in that adopting 0.1%-5% (wt) the CMC aqueous solution and 30%-80% (wt) the PTFE aqueous solution by 1: 10-1: 2 mixed are made.
10. inner liner metal net according to claim 2 is characterized in that described metal is iron, lead, manganese, platinum etc.
11. supporting electrolyte according to claim 1 is characterized in that described supporting electrolyte is water-soluble electrolysis system and non-water-soluble electrolysis system.
12. water-soluble support electrolysis system according to claim 11 is characterized in that described water-soluble support electrolysis system is that concentration is 0.01molL
-1-1.0molL
-1, contain Mn
2+, Fe
2+, Ce
4+, Cl
-Isoionic salts solution, with 1: 20-1: the corresponding acid of 2 volume ratios and concentration are 0.01molL
-1-0.10molL
-1Phase-transfer catalyst be mixed and made into.
13. non-water-soluble support electrolysis system according to claim 11 is characterized in that described non-water-soluble support electrolysis system is ionic liquid BmimBF
4, BmimPF
6, BpyBF
4, BpyPF
6, EmimBF
4Deng, adding mass ratio in the process of preparation is the Mn that contains of 2%-50% (wt)
2+, Fe
2+, Ce
4+, Pb
2+Salt, the modification ionic liquid of preparing with catalysis adds 1: 10-1: the water of 2 volume ratios and 1: 50-1: the phase-transfer catalyst of 5 volume ratios again in above-mentioned ionic liquid.
14. electrochemical catalytic oxidation method according to claim 1 is characterized in that electrolysis voltage is 0.2V-4.0V; The fluid volume ratio is 1: 10-1: 1; Stock oil is sulfur-bearing 10-2500ppm, and the fraction oil that boiling range is 60 ℃-350 ℃ comprises straight run and catalytic gasoline, straight run and catalytic diesel oil, and the desulfurization degree of electrochemical catalytic oxidation desulfurization can reach 10%-90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410042517 CN1699518A (en) | 2004-05-20 | 2004-05-20 | Process for desulfurization of oil products by electrochemical catalytic oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410042517 CN1699518A (en) | 2004-05-20 | 2004-05-20 | Process for desulfurization of oil products by electrochemical catalytic oxidation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1699518A true CN1699518A (en) | 2005-11-23 |
Family
ID=35475767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410042517 Pending CN1699518A (en) | 2004-05-20 | 2004-05-20 | Process for desulfurization of oil products by electrochemical catalytic oxidation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1699518A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618319A (en) * | 2012-04-01 | 2012-08-01 | 中国石油大学(华东) | Pre-desulfuration method for high-sulfur crude oil |
| CN102925202A (en) * | 2012-11-30 | 2013-02-13 | 辽宁大学 | FCC gasoline electrochemical desulfurization method based on ionic liquid |
| CN105820832A (en) * | 2016-01-18 | 2016-08-03 | 许裕金 | Electrochemical catalysis diesel oil desulphurization method at normal temperature and pressure |
| CN107916129A (en) * | 2017-12-14 | 2018-04-17 | 三峡大学 | A kind of method of oxidative desulfurization of fuel oils |
| CN109082880A (en) * | 2018-07-05 | 2018-12-25 | 王伟霞 | Functional activity carbon fiber, preparation method and applications |
| CN114752403A (en) * | 2021-10-29 | 2022-07-15 | 中国石油大学(华东) | Method for electrocatalytic oxidation of desulfurized alcohol and by-product hydrogen by using light petroleum component |
-
2004
- 2004-05-20 CN CN 200410042517 patent/CN1699518A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618319A (en) * | 2012-04-01 | 2012-08-01 | 中国石油大学(华东) | Pre-desulfuration method for high-sulfur crude oil |
| CN102618319B (en) * | 2012-04-01 | 2014-03-19 | 中国石油大学(华东) | Pre-desulfuration method for high-sulfur crude oil |
| CN102925202A (en) * | 2012-11-30 | 2013-02-13 | 辽宁大学 | FCC gasoline electrochemical desulfurization method based on ionic liquid |
| CN102925202B (en) * | 2012-11-30 | 2015-03-11 | 辽宁大学 | FCC gasoline electrochemical desulfurization method based on ionic liquid |
| CN105820832A (en) * | 2016-01-18 | 2016-08-03 | 许裕金 | Electrochemical catalysis diesel oil desulphurization method at normal temperature and pressure |
| CN107916129A (en) * | 2017-12-14 | 2018-04-17 | 三峡大学 | A kind of method of oxidative desulfurization of fuel oils |
| CN107916129B (en) * | 2017-12-14 | 2020-09-01 | 三峡大学 | Method for oxidative desulfurization of fuel oil |
| CN109082880A (en) * | 2018-07-05 | 2018-12-25 | 王伟霞 | Functional activity carbon fiber, preparation method and applications |
| CN114752403A (en) * | 2021-10-29 | 2022-07-15 | 中国石油大学(华东) | Method for electrocatalytic oxidation of desulfurized alcohol and by-product hydrogen by using light petroleum component |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100337747C (en) | Coal tar hydrogenating modification catalyst and its prepn and application | |
| JP2011093774A (en) | Activated carbon, process for producing the same, method of refining liquid using the same, and fuel cell system | |
| CN106669761A (en) | Nitrogen-doped titanium dioxide/attapulgite/graphene compound desulphurization photo-catalyst and preparation method thereof | |
| CN103877943A (en) | Activated carbon supported nano copper desulfurizing agent and preparation method and application thereof | |
| CN1699519A (en) | Process for desulfurization of oil products by electrochemical catalytic reduction | |
| CN1699518A (en) | Process for desulfurization of oil products by electrochemical catalytic oxidation | |
| CN1253536C (en) | Catalysis, oxidation sweetening method for distillate oil of petroleum | |
| CN1990827A (en) | Catalytic cracking desulfurizing assistant agent | |
| CN1317364C (en) | Catalyst for gasoline heavy fraction pyrolysis and selective hydrogenation, process for preparation and use thereof | |
| CN1206158C (en) | Fractional oil desulfurizing and adsorption agent and its preparation method | |
| CN1714926A (en) | Molecular sieve for removing sulfur containing organic compound in oil by adsorption and its producing method | |
| JP2008272646A (en) | Hydrogenation catalyst re-activation method and manufacturing method of hydrogenation catalyst | |
| CN1211157C (en) | Hydrocracking after-treatment catalyst and preparing method thereof | |
| CN1233791C (en) | Gasoline oxidative desulfurizing method with metal ionic modified titanium silicon molecular sieve as catalyst | |
| CN1255513C (en) | Isomerization catalyst and preparation thereof | |
| CN109046318A (en) | Preparation method of calcium-promoted molybdenum-aluminum composite oxide catalytic oxidation desulfurization catalyst | |
| CN101525549B (en) | Hydrocracking tail oil ultra-deep adsorbent desulfurizing and denitrifying method | |
| CN1778465A (en) | Regeneration of desulfurizing adsorbent | |
| CN115707653A (en) | Preparation method and application of sulfur-nitrogen-boron-doped petroleum coke-based activated carbon | |
| CN1158133C (en) | Biochemical iron-alkali solution catalyzing process for desulfurizing gas | |
| CN1323872A (en) | Dearsenicating catalyst | |
| CN105694950B (en) | Photocatalytic real-time liquid phase adsorption desulfurization method | |
| CN110975856B (en) | Titanium oxide/conductive potassium titanate composite desulfurization photocatalytic material and preparation method thereof | |
| CN1183229C (en) | Octane value recovering catalyst and its use | |
| CN110885696B (en) | Sulfur-containing fuel oil desulfurization method of supported molybdenum oxide quantum dot catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |