CN101333454B - Desulphurization process of gasoline by catalytic oxidation and adsorption - Google Patents
Desulphurization process of gasoline by catalytic oxidation and adsorption Download PDFInfo
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Abstract
The invention provides a catalytic oxidation desulfurization method of gasoline, the method comprises: adding an oxidation catalyst and a phase-transfer catalyst into water, mixing the catalyst and water evenly to get an aqueous solution, mixing the aqueous solution with gasoline, implementing the oxidation treatment by taking oxygen as an oxidizing agent, then carrying out the adsorption treatment to remove sulfide for obtaining the sweet gasoline; and the method mainly has the advantages that: the cost is low by taking oxygen having extensive sources as the oxidizing agent; and the desulfurization efficiency is high by combining the catalytic oxidation treatment with the adsorption treatment.
Description
(1) technical field
The present invention relates to a kind of sulfur method of gasoline, specifically be a kind of under oxide catalyst and phase-transfer catalyst catalysis, with oxygen, be that oxygenant carries out oxide treatment to gasoline, carry out the sulfur method that adsorption treatment is removed sulfide again.
(2) background technology
The continuous reinforcement of Along with people's environmental protection consciousness, refining of petroleum industry are faced with the challenge that reduces content of sulfur in gasoline.The method of gasoline desulfur generally can be divided into two types of hydrogenating desulfurization and non-hydrogenating desulfurizations, and the non-hydrodesulfurizationprocess process of gasoline mainly comprises adsorption desulfurize, abstraction desulfurization, complexing desulfurization, biological desulphurization, oxidation sweetening, photochemistry desulfurization.People such as He En disclose in CN 1047788C (1999) patent alkene and mercaptan reaction in first reaction fractionating system have been generated sulfide, and hydrogenating desulfurization in second reaction separation column is converted into H with sulfide
2S, and remove.Disclose load bimetal promotor on zinc oxide in the CN1382199A of Philips Petroleum Co. (2002) patent, prepared sorbent material, be used for the adsorption desulfurize of catalytically cracked gasoline.People such as Li Chunyi disclose in CN 2521218Y (2002) patent on the basis of exploitation desulfurization catalyst, set up a kind of gasoline catalyzing cracking desulphurization circulating fluidized-bed reaction regenerating unit, and the fluidisation thing in the gasoline is converted into H
2S.People such as Zhang Jijun have introduced petrol molecule sieve desulfurizing method by adsorption in CN 1393511A (2003) patent.In CN1429884A (2003) patent, the good people of grade of high step makes mercaptan and diolefine reaction generate high boiling sulfide, then heavy petrol carried out selective hydrodesulfurization reactor drum of gasoline entering.In CN 1465668A (2004) patent, people such as Li Dadong with gasoline stocks be cut into gently, last running, lighting end is through the sodafining mercaptan removal, selective hydrogenation is carried out in last running.In CN 1478866A (2004) patent, people such as stone Yulin with gasoline stocks be cut into gently, heavy naphtha; Heavy naphtha is further sloughed mercaptan through hydro-sweetening again through hydrodesulfurization reaction.
(3) summary of the invention
The object of the invention provides that a kind of to be oxygenant with wide material sources, oxygen that cost is low carry out oxide treatment, remove the sulfur method of sulfide through adsorption treatment again gasoline.
The technical scheme that the present invention adopts is:
A kind of catalyzed oxidation desulfurizing method by adsorption of gasoline, said method comprises: the mixture of phase-transfer catalyst or phase-transfer catalyst and oxide catalyst is added in the entry, mix and obtain the aqueous solution; The said aqueous solution is mixed with gasoline; For oxygenant carries out oxide treatment, adopt sorbent material with oxygen (direct aerating oxygen, but also bubbling air) at last; Under 0～150 ℃, 0.1～5.0MPa condition, oxidized gasoline is carried out adsorption treatment and remove sulfide, obtain sweet gasoline;
Said oxide treatment condition is: gasoline and aqueous solution volume ratio are 1: 0.1～5.0,50 ℃～200 ℃ of temperature, oxygen partial pressure 0.05MPa～5.0MPa, oxidization time 2.0min～120min;
Oxide catalyst quality addition is that 0.1～10% (being that 100g water adds 0.1～10g oxide catalyst), phase-transfer catalyst quality addition are 0.01～10% (being that 100g water adds 0.01～10g phase-transfer catalyst) in the said aqueous solution;
Said oxide catalyst is one of following or wherein two or more mixture: wolframic acid, tungstate, boric acid, cerium oxide, sodium tetraborate, Sodium peroxoborate, manganous carbonate, zinc oxide, molybdic oxide, Xiao Suangu, sodium metavanadate, phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid; Said oxide catalyst is preferably boric acid, manganous carbonate or zinc oxide, and its quality addition is preferably 1.0～5.0%.
Said phase-transfer catalyst is one of following or wherein two or more mixture: Tetrabutyl amonium bromide, four octyl group brometo de amonios, cetyl trimethylammonium bromide, 4 bromide, tetraethylammonium bromide, Trimethyllaurylammonium bromide, tetrabutylammonium iodide, TBAH; Said phase-transfer catalyst is preferably Tetrabutyl amonium bromide, and its addition is preferably 0.1～3.0%;
Said sorbent material is one of following or wherein two or more mixture: gac, atlapulgite, aluminum oxide, quicklime, Y zeolite, X type molecular sieve, zinc oxide.Said sorbent material is preferably atlapulgite.
Said absorption can be carried out in adsorption bed, at 0～150 ℃ of temperature, 0.1～5.0MPa, mass space velocity 0.2～10.0h
-1Under the condition oxidized gasoline is carried out adsorption treatment.
Said absorption also can be adopted the whip attachment mode of mixing, the adsorbent mass consumption be the oxidized gasoline quality 2～50%, adsorption time 1.0min～60.0min, 0～150 ℃ of adsorption temp, adsorptive pressure 0.1～5.0MPa.
Can carry out steam purging to used sorbent material, and air purge, remove adsorptive, so that sorbent material is reused.
After said oxide treatment finished, oxidized gasoline was carried out adsorption treatment again and is removed sulfide after water washing; Said washing is carried out under 1 ℃～90 ℃, the condition of 0.1MPa～5.0MPa, and oxidized gasoline and water volume ratio are 1: 0.1～5.0.
Can directly feed oxygen-containing gas with the aqueous mixture of oxide catalyst and carry out gasoline oxidation processing with containing phase-transfer catalyst or contain phase-transfer catalyst to gasoline; Also can feed oxygen-containing gas toward the aqueous solution earlier and (be generally air; Also direct aerating oxygen); The aqueous solution with dissolved oxygen contacts with gasoline then, and gasoline is carried out oxide treatment.
Organic sulfide is compared with the hydro carbons with analog structure in the gasoline; The polarity difference is little; And the polarity of the sulfide of oxidation such as sulfone or sulfoxide is much larger than unoxidized sulfide polarity, so the abundant oxidation of organic sulfide is the key of gasoline oxidation and adsorption desulfurize in the gasoline.Generally adopt ydrogen peroxide 50 as oxygenant at present both at home and abroad, carry out the oil fuel oxidation, and desulfurization research.The present invention adopts the low molecular oxygen of wide material sources, cost as oxygenant; Under the effect of oxide catalyst and/or phase-transfer catalyst, gasoline being carried out selective oxidation handles; Improve the polarity of sulfide; Through adsorption treatment, polarity sulfide is separated from gasoline then, realized gasoline oxidation and adsorption desulfurize.In the gasoline selective oxidising process, the effect of adding phase-transfer catalyst is to promote fully contacting of water and organic phase, improves the oxidizing reaction rate of organic sulfide, finds through experiment, adds phase-transfer catalyst separately and also can reach sweetening effectiveness preferably.
Concrete, said method is following:
(1) oxide catalyst and phase-transfer catalyst are added in the entry, mix and obtain the aqueous solution; Oxide catalyst quality addition is 1.0～5.0% in the said aqueous solution, phase-transfer catalyst quality addition is 0.1～3.0%;
(2) step (1) aqueous solution and gasoline are mixed; Gasoline and aqueous solution volume ratio are 1: 0.2～2.0, and in 120 ℃～180 ℃ following bubbling airs of temperature or oxygen, the control oxygen partial pressure is 0.3MPa～3.0MPa; Carry out oxide treatment 10min～80min; Oil reservoir is got in layering, obtains oxidized gasoline;
(3) step (2) oxidized gasoline is washed 2min～60min under the condition of 5 ℃～90 ℃ of temperature, 0.1MPa～5.0MPa, oxidized gasoline and water volume ratio are 1: 0.2～2.0, and oil reservoir is got in layering, obtains washing gasoline;
(4) in step (3) washing gasoline, add sorbent material, adsorbent mass is 2～10% of the washing quality of gasoline, under 0～150 ℃ of temperature, 0.1～5.0MPa, washing gasoline is carried out adsorption treatment 1min～60min, leaves standstill, and is settlement separate, obtains sweet gasoline.
Perhaps, said method is following:
(1) oxide catalyst and phase-transfer catalyst are added in the entry, mix and obtain the aqueous solution; Oxide catalyst quality addition is 1.0～5.0% in the said aqueous solution, phase-transfer catalyst quality addition is 0.1～3.0%;
(2) step (1) aqueous solution and gasoline are mixed; Gasoline and aqueous solution volume ratio are 1: 0.2～2.0, and in 120 ℃～180 ℃ following bubbling airs of temperature or oxygen, the control oxygen partial pressure is 0.3MPa～3.0MPa; Carry out oxide treatment 10min～80min; Oil reservoir is got in layering, obtains oxidized gasoline;
(3) step (2) oxidized gasoline is washed 2min～60min under the condition of 5 ℃～90 ℃ of temperature, 0.1MPa～5.0MPa, oxidized gasoline and water volume ratio are 1: 0.2～2.0, and oil reservoir is got in layering, obtains washing gasoline;
(4) adopt adsorption bed, at 0～150 ℃, 0.1～5.0MPa, mass space velocity 0.2～10.0h
-1Condition
Down step (3) washing gasoline is carried out adsorption treatment, obtain sweet gasoline.
Beneficial effect of the present invention is mainly reflected in: oxygen is oxygenant to originate widely, and cost is low; Combine adsorption treatment with catalytic oxidation treatment, desulfuration efficiency is high, and desulfuration efficiency can reach more than 90%.
(4) embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this:
Handled gasoline is catalytically cracked gasoline among the embodiment, and sulphur content is 139.58 μ g/g, with the sulphur content of RPA-200 type microcoulomb analysis-e/or determining gasoline.Poor by sulfur content of catalytic cracking gasoline and sweet gasoline sulphur content divided by sulfur content of catalytic cracking gasoline, calculated the gasoline desulfur rate.
Embodiment 1～14: the oxidation sweetening effect of investigating different oxide catalysts
Take by weighing 2g oxide catalyst and 0.6g cetyl trimethylammonium bromide phase-transfer catalyst, add reaction kettle, measure 400mL gasoline then, the 200mL deionized water adds in the reaction kettle respectively.At the reaction kettle mixing speed is under the 600r/min condition reactant to be warming up to 140 ℃, and aerating oxygen, oxygen partial pressure are 1.0MPa, reaction 60min.Reaction stops aerating oxygen after finishing immediately, opens water of condensation and is cooled to 25 ℃.Reactant is discharged reaction kettle, pour separating funnel into, leave standstill the 10min layering, obtain oxidation of gasoline.Be to wash 10min under the condition of 1: 1 (volume ratio of oxidation of gasoline and water, down with) in room temperature, profit volume ratio, settlement separate, obtain washing oxidation of gasoline.Then, under room temperature, oxidation of gasoline and 20: 1 condition of HY type adsorbent of molecular sieve mass ratio, whip attachment 20min; Separate through standing sedimentation; Obtain sweet gasoline, and measure the gasoline desulfur rate, the gasoline desulfur experimental result of different oxide catalysts is listed in table 1.
Table 1
| Embodiment | Oxide catalyst | Desulfurization degree, % |
| Embodiment 1 | Wolframic acid | 60.16 |
| Embodiment 2 | Sodium wolframate | 59.29 |
| Embodiment 3 | Boric acid | 53.43 |
| Embodiment 4 | Cerium oxide | 58.38 |
| Embodiment 5 | Sodium tetraborate | 55.56 |
| Embodiment 6 | Sodium peroxoborate | 54.25 |
| Embodiment 7 | Manganous carbonate | 55.43 |
| Embodiment 8 | Zinc oxide | 55.61 |
| Embodiment 9 | Molybdic oxide | 54.15 |
| Embodiment 10 | Xiao Suangu | 55.09 |
| Embodiment 11 | Sodium metavanadate | 53.15 |
| Embodiment 12 | Phospho-wolframic acid | 50.46 |
| Embodiment 13 | Phospho-molybdic acid | 48.28 |
| Embodiment 14 | Silicotungstic acid | 49.53 |
Embodiment 15～22: the sweetening effectiveness of investigating different phase-transfer catalysts
Take by weighing 3g manganous carbonate catalyzer and 0.6g phase-transfer catalyst, add reaction kettle, measure 400mL gasoline then, the 200mL deionized water adds in the reaction kettle respectively.At the reaction kettle mixing speed is under the 600r/min condition reactant to be warming up to 140 ℃, and aerating oxygen, oxygen partial pressure are 1.0MPa, reaction 60min.Reaction stops aerating oxygen after finishing immediately, opens water of condensation and is cooled to 25 ℃.Reactant is discharged reaction kettle, pour separating funnel into, leave standstill the 10min layering, obtain oxidation of gasoline.Be to wash 10min under 1: 1 the condition in room temperature, profit volume ratio, settlement separate, obtain washing gasoline.Then, under room temperature, oxidation of gasoline and 20: 1 condition of atlapulgite absorbent mass ratio, whip attachment 20min; Separate through standing sedimentation; Obtain sweet gasoline, and measure the gasoline desulfur rate, the gasoline desulfur experimental result of different phase-transfer catalysts is listed in table 2.
Table 2
| Embodiment | Phase-transfer catalyst | Desulfurization degree, % |
| Embodiment 15 | Tetrabutyl amonium bromide | 69.28 |
| Embodiment 16 | Four octyl group amine bromides | 67.31 |
| Embodiment 17 | CTAB | 65.82 |
| Embodiment 18 | 4 bromide | 62.64 |
| Embodiment 19 | Tetraethylammonium bromide | 65.17 |
| Embodiment 20 | Trimethyllaurylammonium bromide | 62.81 |
| Embodiment 21 | Tetrabutylammonium iodide | 61.35 |
| Embodiment 22 | TBAH | 59.23 |
Embodiment 23～32: investigate the influence of oxidizing condition to gasoline desulfur
400mL gasoline, Zinc oxide catalytic, Tetrabutyl amonium bromide and deionized water are added in the reaction kettle.At the reaction kettle mixing speed is under the 600r/min condition, and aerating oxygen carries out the oxidizing reaction of different condition.Reaction stops aerating oxygen after finishing immediately, opens water of condensation and is cooled to 25 ℃.Reactant is discharged reaction kettle, pour separating funnel into, leave standstill the 10min layering, obtain oxidation of gasoline.Be to wash 10min under 1: 1 the condition in room temperature, profit volume ratio, settlement separate, obtain washing gasoline.Then; Under room temperature, oxidation of gasoline and 20: 1 condition of atlapulgite absorbent mass ratio; Whip attachment 20min separates through standing sedimentation, obtains sweet gasoline; And measure the gasoline desulfur rate, different oxide catalysts and phase-transfer catalyst account for the gasoline desulfur experimental result of the oxidizing conditions such as mass concentration of water and list in table 3.
Table 3
| Embodiment | The profit volume ratio | The oxidation catalysis agent concentration, % | Consisting of phase-transferring agent concentration, % | Oxidizing temperature, ℃ | Oxygen partial pressure, MPa | Oxidization time, min | Desulfurization degree, % |
| Embodiment 23 | 2.0 | 2.0 | 0.2 | 140 | 1.0 | 60 | 60.34 |
| Embodiment 24 | 2.0 | 5.0 | 0.3 | 140 | 1.0 | 60 | 64.27 |
| Embodiment 25 | 2.0 | 1.0 | 0.3 | 150 | 1.0 | 30 | 58.35 |
| Embodiment 26 | 2.0 | 1.0 | 0.3 | 130 | 1.0 | 30 | 63.61 |
| Embodiment 27 | 2.0 | 1.0 | 0.3 | 110 | 1.0 | 30 | 39.06 |
| Embodiment 28 | 2.0 | 1.0 | 0.3 | 140 | 2.0 | 30 | 63.18 |
| Embodiment 29 | 2.0 | 1.0 | 0.3 | 140 | 3.0 | 30 | 65.32 |
| Embodiment 30 | 5.0 | 1.0 | 0.1 | 160 | 2.0 | 15 | 56.39 |
| Embodiment 31 | 1.0 | 1.0 | 0.2 | 160 | 2.0 | 15 | 69.27 |
| Embodiment 32 | 0.5 | 1.0 | 0.3 | 160 | 2.0 | 15 | 73.16 |
Embodiment 33: with the desulfurization of air to the gasoline oxidation processing
Take by weighing 3.0g manganous carbonate catalyzer and 0.8g cetyl trimethylammonium bromide phase-transfer catalyst, add reaction kettle, measure 400mL gasoline then, 200mL goes zero(ppm) water to add in the reaction kettle respectively.At the reaction kettle mixing speed is under the 600r/min condition reactant to be warming up to 140 ℃, and bubbling air makes system pressure reach 5.0MPa, reaction 30min.Reaction stops bubbling air after finishing immediately, opens water of condensation and is cooled to 25 ℃.Reactant is discharged reaction kettle, pour separating funnel into, leave standstill the 10min layering, obtain oxidation of gasoline.Then, under room temperature, oxidation of gasoline and 20: 1 condition of atlapulgite absorbent mass ratio, whip attachment 20min separates through standing sedimentation, obtains sweet gasoline, and the desulfurization degree result is 66.88%.
Embodiment 34～42: investigate the influence of adsorption operations condition to gasoline desulfur
Take by weighing 3.0g manganous carbonate catalyzer and 1.0g Tetrabutyl amonium bromide, add reaction kettle, measure 400mL gasoline then, the 200mL deionized water adds in the reaction kettle respectively.At the reaction kettle mixing speed is under the 600r/min condition reactant to be warming up to 140 ℃, and aerating oxygen, oxygen partial pressure are 1.0MPa, reaction 60min.Reaction stops aerating oxygen after finishing immediately, opens water of condensation and is cooled to 25 ℃.Reactant is discharged reaction kettle, pour separating funnel into, leave standstill the 10min layering, obtain oxidation of gasoline.Be to wash 10min under 1: 1 the condition in room temperature, profit volume ratio, settlement separate, obtain washing gasoline.Then, oxidation of gasoline is carried out adsorption treatment, obtain sweet gasoline, and measure the gasoline desulfur rate with various sorbent materials.The gasoline desulfur experimental result of different adsorption conditionses is listed in table 4.
Table 4
| Embodiment | Sorbent material | Agent oil quality ratio | Adsorption temp, ℃ | Adsorption time, min | Desulfurization degree, % |
| Embodiment 34 | Gac | 1∶20 | 30 | 30 | 57.23 |
| Embodiment 35 | Atlapulgite | 1∶20 | 30 | 30 | 59.45 |
| Embodiment 36 | Aluminum oxide, | 1∶20 | 30 | 30 | 58.22 |
| Embodiment 37 | Quicklime | 1∶20 | 30 | 30 | 52.31 |
| Embodiment 38 | HY type molecular sieve | 1∶20 | 30 | 30 | 59.26 |
| Embodiment 39 | Atlapulgite | 1∶10 | 40 | 20 | 65.32 |
| Embodiment 40 | Atlapulgite | 1∶10 | 50 | 20 | 67.53 |
| Embodiment 41 | X type molecular sieve | 1∶10 | 50 | 20 | 60.22 |
| Embodiment 42 | Zinc oxide | 1∶10 | 50 | 20 | 61.58 |
Embodiment 43～46: the ADSORPTION IN A FIXED BED desulfurization
With 300mL manganous carbonate mass content be 2.0% and with the Tetrabutyl amonium bromide mass content be 0.5% the aqueous solution and 400mL gasoline adding reaction kettle; At the reaction kettle mixing speed is with reaction mass heated to 150 ℃ under the 600r/min condition; Bubbling air; Make system pressure reach 5.0MPa, reaction 30min.Reaction stops bubbling air after finishing immediately, opens water of condensation and is cooled to 25 ℃.Reactant is discharged reaction kettle, pour separating funnel into, leave standstill the 10min layering, obtain oxidation of gasoline.As sorbent material, on the ADSORPTION IN A FIXED BED device, oxidation of gasoline is carried out adsorption treatment with atlapulgite, the gasoline absorbing desulfurization rate experimental result of different condition is listed in table 5.
Table 5
| Embodiment | Adsorption temp, ℃ | Adsorptive pressure, MPa | Mass space velocity, h -1 | Desulfurization degree, % |
| Embodiment 43 | 20 | 0.1 | ?0.5 | 85.64 |
| Embodiment 44 | 50 | 0.5 | ?1.0 | 86.35 |
| Embodiment 45 | 80 | 1.0 | ?3.0 | 84.23 |
| Embodiment 46 | 120 | 2.0 | ?5.0 | 83.12 |
Embodiment 47～54: consisting of phase-transferring agent catalyzed oxidation and ADSORPTION IN A FIXED BED desulfurization
Take by weighing the 3g phase-transfer catalyst and add reaction kettle, measure 200mL gasoline then, 200mL zero(ppm) water adds in the reaction kettle respectively.When rotating speed is 600r/min, reactant is warming up to 140 ℃, aerating oxygen makes the reaction kettle oxygen partial pressure reach 2.0MPa, reaction 40min.Stop logical oxygen after reaction finishes immediately, open water of condensation and be cooled to 25 ℃.Reactant is discharged reaction kettle, pour separating funnel into, leave standstill the 10min layering, obtain oxidation of gasoline.Then, be to oxidation of gasoline washing 10min under 1: 1 the condition in room temperature, profit volume ratio.Then, with atlapulgite as sorbent material, at 80 ℃ of adsorption temps, pressure 1.0MPa, mass space velocity 1.0h
-1Under the condition, on the ADSORPTION IN A FIXED BED device, oxidation of gasoline is carried out adsorption treatment, obtain sweet gasoline, measure the gasoline desulfur rate, the desulfurization result of several kinds of phase-transfer catalysts lists in table 6.
Table 6
| Embodiment | Phase-transfer catalyst | Desulfurization degree, % |
| Embodiment 47 | Tetrabutyl amonium bromide | 90.38 |
| Embodiment 48 | Four octyl group brometo de amonios | 90.21 |
| Embodiment 49 | Cetyl trimethylammonium bromide | 90.10 |
| Embodiment 50 | 4 bromide | 85.64 |
| Embodiment 51 | Tetraethylammonium bromide | 88.27 |
| Embodiment 52 | Trimethyllaurylammonium bromide | 84.56 |
| Embodiment 53 | Tetrabutylammonium iodide | 83.15 |
| Embodiment 54 | TBAH | 81.49 |
Above-mentioned experimental result shows, adopts molecular oxygen as oxygenant, and gasoline is carried out oxide treatment, then carries out adsorption treatment, can realize gasoline desulfur, and this sulfur method has a good application prospect.
Claims (6)
1. the catalyzed oxidation desulfurizing method by adsorption of a gasoline; Said method comprises: the mixture of phase-transfer catalyst or phase-transfer catalyst and oxide catalyst is added in the entry, mix and obtain the aqueous solution, the said aqueous solution is mixed with gasoline; With oxygen is that oxygenant carries out oxide treatment; After said oxide treatment finished, oxidized gasoline was carried out adsorption treatment again and is removed sulfide after water washing, obtain sweet gasoline;
Said oxide treatment condition is: gasoline and aqueous solution volume ratio are 1: 0.1～5.0,50 ℃～200 ℃ of temperature, oxygen partial pressure 0.05MPa～5.0MPa, oxidization time 2.0min～120min;
Oxide catalyst quality addition is 0.1～10% in the said aqueous solution, phase-transfer catalyst quality addition is 0.01～10%;
Said oxide catalyst is one of following or wherein two or more mixture: wolframic acid, tungstate, boric acid, cerium oxide, sodium tetraborate, Sodium peroxoborate, manganous carbonate, zinc oxide, molybdic oxide, Xiao Suangu, sodium metavanadate, phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid;
Said phase-transfer catalyst is one of following or wherein two or more mixture: Tetrabutyl amonium bromide, four octyl group brometo de amonios, cetyl trimethylammonium bromide, 4 bromide, tetraethylammonium bromide, Trimethyllaurylammonium bromide, tetrabutylammonium iodide, TBAH;
Said sorbent material is one of following or wherein two or more mixture: gac, atlapulgite, aluminum oxide, quicklime, Y zeolite, X type molecular sieve, zinc oxide;
Said washing is carried out under 1 ℃～90 ℃, the condition of 0.1MPa～5.0MPa, and oxidized gasoline and water volume ratio are 1: 0.1～5.0;
Said adsorption treatment is carried out in adsorption bed, at 0～150 ℃ of temperature, 0.1～5.0MPa, mass space velocity 0.2～10.0h
-1Under the condition oxidized gasoline is carried out adsorption treatment; Perhaps, said adsorption treatment adopts the whip attachment mode of mixing, said adsorbent mass consumption be the oxidized gasoline quality 2～50%, adsorption time 1.0min～60.0min, 0～150 ℃ of adsorption temp, adsorptive pressure 0.1～5.0MPa.
2. the method for claim 1, it is characterized in that said oxide catalyst is one of following: boric acid, manganous carbonate or zinc oxide, oxide catalyst quality addition is 1.0～5.0% in the said aqueous solution.
3. the method for claim 1 is characterized in that said phase-transfer catalyst is a Tetrabutyl amonium bromide, and oxide catalyst quality addition is 0.1～3.0% in the said aqueous solution.
4. the method for claim 1 is characterized in that said sorbent material is an atlapulgite.
5. the method for claim 1 is characterized in that said method is following:
(1) oxide catalyst and phase-transfer catalyst are added in the entry, mix and obtain the aqueous solution; Oxide catalyst quality addition is 1.0～5.0% in the said aqueous solution, phase-transfer catalyst quality addition is 0.1～3.0%;
(2) step (1) aqueous solution and gasoline are mixed; Gasoline and aqueous solution volume ratio are 1: 0.2～2.0, and in 120 ℃～180 ℃ following bubbling airs of temperature or oxygen, the control oxygen partial pressure is 0.3MPa～3.0MPa; Carry out oxide treatment 10min～80min; Oil reservoir is got in layering, obtains oxidized gasoline;
(3) with step (2) oxidized gasoline water washing 2min～60min under the condition of 5 ℃～90 ℃ of temperature, 0.1MPa～5.0MPa, oxidized gasoline and water volume ratio are 1: 0.2～2.0, and oil reservoir is got in layering, obtains washing gasoline;
(4) in step (3) washing gasoline, add sorbent material, adsorbent mass is 2～10% of the washing quality of gasoline, under 0～150 ℃ of temperature, 0.1～5.0MPa, washing gasoline is carried out adsorption treatment 1min～60min, leaves standstill, and is settlement separate, obtains sweet gasoline.
6. the method for claim 1 is characterized in that said method is following:
(1) oxide catalyst and phase-transfer catalyst are added in the entry, mix and obtain the aqueous solution; Oxide catalyst quality addition is 1.0～5.0% in the said aqueous solution, phase-transfer catalyst quality addition is 0.1～3.0%;
(2) step (1) aqueous solution and gasoline are mixed; Gasoline and aqueous solution volume ratio are 1: 0.2～2.0, and in 120 ℃～180 ℃ following bubbling airs of temperature or oxygen, the control oxygen partial pressure is 0.3MPa～3.0MPa; Carry out oxide treatment 10min～80min; Oil reservoir is got in layering, obtains oxidized gasoline;
(3) with step (2) oxidized gasoline water washing 2min～60min under the condition of 5 ℃～90 ℃ of temperature, 0.1MPa～5.0MPa, oxidized gasoline and water volume ratio are 1: 0.2～2.0, and oil reservoir is got in layering, obtains washing gasoline;
(4) adopt adsorption bed, at 0～150 ℃, 0.1～5.0MPa, mass space velocity 0.2～10.0h
-1Under the condition step (3) washing gasoline is carried out adsorption treatment, obtain sweet gasoline.
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| CN102311779A (en) * | 2011-08-22 | 2012-01-11 | 浙江工业大学 | Method of peroxyformic acid of gasoline oxidation extraction and desulfurization |
| US9827551B2 (en) * | 2015-02-27 | 2017-11-28 | W. L. Gore & Associates, Inc. | Flue gas purification system and process using a sorbent polymer composite material |
| CN105861031A (en) * | 2016-04-25 | 2016-08-17 | 宁波章甫能源科技有限公司 | Water-phase mixture for removing carbonyl sulfide in liquid hydrocarbon |
| CN108219831A (en) * | 2018-03-28 | 2018-06-29 | 山东联星能源集团有限公司 | A kind of petrol and diesel oil adsorbs desulphurization production technology |
| CN110252413A (en) * | 2019-06-27 | 2019-09-20 | 石河子开发区汇智元科技有限责任公司 | One kind being used for C9 resin raw material oil oxidation desulfurization catalyst |
| CN110898807A (en) * | 2019-12-09 | 2020-03-24 | 安徽省睿斯达石油有限公司 | Petroleum desulfurization adsorbent |
| CN111004644A (en) * | 2019-12-16 | 2020-04-14 | 冯炳焕 | Efficient and environment-friendly oil refining method |
| CN112264111B (en) * | 2020-11-25 | 2024-04-05 | 浙江华康药业股份有限公司 | System and method for recovering activity of glucose hydrogenation catalyst |
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| CN1563284A (en) * | 2004-03-24 | 2005-01-12 | 华东理工大学 | Catalysis, oxidation sweetening method for distillate oil of petroleum |
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