CN104694160A - A combined method of light gasoline desulphurization by alkali washing - Google Patents
A combined method of light gasoline desulphurization by alkali washing Download PDFInfo
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- CN104694160A CN104694160A CN201310655994.6A CN201310655994A CN104694160A CN 104694160 A CN104694160 A CN 104694160A CN 201310655994 A CN201310655994 A CN 201310655994A CN 104694160 A CN104694160 A CN 104694160A
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- alkali lye
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- 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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/12—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one alkaline treatment step
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- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
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- 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
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method of light gasoline desulphurization by alkali washing. The method includes: (1) bringing light gasoline and an alkali solution containing sodium hydroxide into contact, mixing and performing two-phase separation so that sulfur-containing compounds in the light gasoline are extracted into the alkali solution; (2) in a supergravity reactor, mixing the extracted alkali solution to be regenerated and an oxygen-containing gas, and discharging waste gas containing disulfide and the regenerated alkali solution; (3) absorbing the disulfide in the waste gas containing the disulfide by using diesel oil; and (4) circulating the regenerated alkali solution for the extraction process of the light gasoline. The method combines and optimizes a conventional alkali liquid extraction technique, a supergravity reaction technique and a tail gas absorption technique. The regenerated alkali solution is high in quality, thus improving the desulfurization percent and reducing the discharge amount of waste alkali residue. The air waste gas absorption step reduces discharge of the sulfur-containing gas, so that the whole process meets requirements on environment protection, and a desulphurization effect that a thiol content after desulphurization is not higher than 2 ppmw is achieved.
Description
Technical field
The present invention relates to a kind of petroleum naphtha sulfur removal technology, specifically refer to and utilize alkali lye to remove sulfur component in petroleum naphtha and the combination process realizing alkali liquid regeneration and the discharge of decreasing pollution thing.
Background technology
Environment protection receives the concern of the public day by day, and countries in the world have formulated strict vehicle fuel standard in succession, and motor spirit quality index is progressively to the future development of super low sulfur.Gasoline desulfur has hydrogenation and non-hydrogenation two schemes, and wherein gasoline hydrodesulfurizationmethod becomes common recognition substantially as cost-effective means.But because in China's gasoline pool, catalytically cracked gasoline accounts for major portion, the C5-C8 olefin(e) centent of catalytically cracked gasoline is high, adopt hydrogenation scheme can cause a large amount of olefin saturated, gasoline octane rating heavy losses.High boiling fraction is concentrated on and alkene concentrates on this feature of low boiler cut for sulfide in petrol, select suitable cut point that gasoline is divided into petroleum naphtha and heavy petrol, only to the hydrogen addition technology desulfurization of heavy petrol product, petroleum naphtha adopts the non-hydrogenation schemes such as alkali cleaning, even do not deal with when petroleum naphtha sulphur content is lower, total sulfur can be realized and meet this requirement of content of sulfur in gasoline standard.The PrimeG+ technique of Axens company of France, the OCT-MD technique of Fu Yan institute, Chinese patent CN200710123546.6 all comprises this technical characteristic, has become the common technology in gasoline desulfur.
In petroleum naphtha, sulphur exists mainly with thioalcohol form, also has the non-mercaptan sulfurs such as a small amount of thiophene.The extracting and oxidizing method of Merox technique is the main method of the non-hydrogenating desulfurization of gasoline, utilize the mercaptan in caustic extraction gasoline, make it reaction generation sodium mercaptides and be dissolved in alkali lye to remove, then air is passed in sulfur-bearing alcoholic lye, make sodium mercaptides be oxidized to disulphide, alkali lye is regenerated simultaneously.Comprise liquefied gas and full distillation gasoline, all can use the desulfurization of Merox technique.This technique Problems existing is that in the alkali lye of oxidation regeneration, disulphide is difficult to be separated totally, the disulphide carried in circulation alkali liquor can be stripped in gasoline, sweetening effectiveness is caused to be deteriorated, do not reach gasoline quality standard, also create a large amount of discharges subtracting slag and sulfur-bearing air containing disulphide simultaneously.
Chinese patent CN200910250279.8 discloses the method for liquid hydrocarbon deep desulfuration, in NaOH alkali lye, with the addition of function intensified auxiliary agent, compares single NaOH alkali lye better effects if.Chinese patent CN200710100287.5 proposes to use and does not carry out extracting higher than the thermokalite of 120 DEG C, can remove carbonylsulfide and not need oxide catalyst, having saved cost.The gradient that Chinese patent CN201010296540.0 discloses a kind of alkali lye utilizes, and the alkali lye after desulfuration of liquefied gas is used for gasoline desulfur, and the desulfurization requirement of liquefied gas and gasoline is just mated in concentration of lye change, has saved cost.Aforesaid method and similar techniques are only improved caustic extraction monotechnics, and the separation problem of alkali liquid regeneration and disulphide does not solve, and circulation alkali liquor sulphur content is higher, and alkali lye consumption is large, and petroleum naphtha desulfurization depth is inadequate, and disulphide easily produces secondary pollution.
Chinese patent CN201210276509.x, CN200810162140.3, CN201220012653.8 disclose a kind of caustic wash desulfuration method that can be used for liquefied gas and gasoline lighting end, and liquid film alkali cleaning reactor assembly.The method adopts liquid film alkali cleaning reactor to realize lye extraction desulfurization process, adopt oxidation knockout tower that sodium mercaptides is oxidized to disulphide, disulphide and the hydrophilic coalescent pack initial gross separation of alkali lye through disengaging zone, again through liquid film extracting contactor naphtha extraction disulphide, realize the high efficiency separation of disulphide.The naphtha extraction method that the method proposes solves the separation problem of alkali lye and disulphide in original process, and reduces the discharge subtracting slag containing disulphide, but oxidation separation still adopts original process, and separating effect and sulfur-bearing air venting problem are not properly settled.
Summary of the invention
The object of this invention is to provide a kind of method of petroleum naphtha caustic wash desulfuration, comprise petroleum naphtha caustic wash desulfuration, alkali liquor oxidized regeneration, the processes such as disulphide absorption, realize the deep removal of sulphur and reduce secondary pollution.
The combination that the object of the invention is by the following method reaches:
(1) petroleum naphtha contact with containing the alkali lye of sodium hydroxide and mixes also two-phase laminated flow, the S-contained substance in petroleum naphtha by extracting in alkali lye;
(2) in supergravity reactor, the alkali lye to be generated after extracting is mixed with oxygen-containing gas and contacts, discharge the waste gas containing disulphide and regeneration alkali lye;
(3) diesel oil is used to absorb containing the disulphide in the waste gas of disulphide;
(4) regenerate alkali lye circulation, continue to serve as the extractive process of petroleum naphtha.
The combined method of the petroleum naphtha deep desulfuration that the present invention proposes, adopt alkali lye to the method desulfurization of petroleum naphtha two-stage extracting, described petroleum naphtha refers to the lighting end of full distillation gasoline after weight cutting, and its final boiling point, at 65 ~ 135 DEG C, is determined according to full distillation gasoline desulfurization program.Adopt combined method of the present invention, petroleum naphtha raw material is preferably after caustic prescrub, and caustic prescrub technology belongs to known technology in this area, and the alkali lye of caustic prescrub does not make manipulation of regeneration, independent of subsequent combination method.
In the combined method that the present invention proposes, petroleum naphtha contacts extracting with the alkali lye containing sodium hydroxide, can by the sulfide in petroleum naphtha, and mainly mercaptan, is transformed into sodium mercaptides and is dissolved in alkali lye, thus realizing sweetening effectiveness.The preferred two-stage caustic extraction of the present invention.1st grade of extracting preferably uses extraction tower, and petroleum naphtha and the alkali lye counter current contact containing sodium hydroxide, the scope of the mass ratio of alkali lye and petroleum naphtha is 0.2 ~ 1.2, temperature 20 ~ 60 DEG C, not control pressure.2nd grade of extracting preferably uses static mixer.In the alkali lye that two-stage extracting uses, the sulphur content of the 2nd grade of charging alkali lye is not higher than the 1st grade of charging alkali lye.Specifically, method of the present invention preferably the 1st grade and the 2nd grade of extracting all adopts the alkali lye after regeneration, also can select the charging alkali lye be incorporated into by the outlet alkali lye of the 2nd grade of extracting as the 1st grade of extracting in the 1st grade of extracting.
In combined method of the present invention, the important step of actualizing technology effect is alkali liquid regeneration, i.e. the hypergravity oxidising process of sodium mercaptides.High gravity rotating packed bed reactor has been a kind of common reactor types in chemical process at present, the centrifugal force utilizing high speed rotating to produce can promote that gas-to-liquid contact mixes, the oxidizing reaction of oxygen in sodium mercaptides and gas phase in strengthening alkali lye, sodium mercaptides transformation efficiency is greater than 99%, and the vapour-liquid ratio operation of relative broad range can be realized, be conducive to removing in alkali lye the disulphide being oxidized generation.In supergravity reactor, preferred range of reaction temperature is 35 ~ 70 DEG C, and pressure range is 0.12 ~ 0.3MPa, and in charging, the volume range of oxygen-containing gas and alkali lye to be generated is 5 ~ 500.
Use oxygen volume content in the hypergravity oxidizing reaction of sodium mercaptides at the oxygen-containing gas of 10-90% as oxygenant, preferably use air under normal circumstances.When condition is suitable for, the more preferably oxygen volume content oxygen rich gas that is greater than 21%, oxygen concentration improves the carrying out being conducive to oxidizing reaction.
The degree of alkali lye quality to petroleum naphtha deep desulfuration after regeneration has direct relation, alkali lye quality mainly comprises basicity, sulphur content etc., common technology can realize basicity regeneration, in the regeneration alkali lye that preferred cycle of the present invention uses, the content of disulphide is less than 10ppmw, and after can realizing deep desulfuration, in petroleum naphtha, mercaptans content is less than 2ppmw.
In combined method of the present invention, the disulphide overwhelming majority that in alkali lye, sodium mercaptides is oxidized to enters in the waste gas of supergravity reactor discharge, adopts diesel oil to absorb and the sulphur content of exhaust emissions can be made to meet relevant criterion.Preferably use high gravity rotating packed bed to carry out absorption operation in the present invention, or use ventional absorption tower, undesulfured for refinery diesel oil is used as absorption agent, the raw material of diesel oil as diesel hydrotreating unit being rich in disulphide that absorption tower is discharged.
Petroleum naphtha deep desulfuration combined method provided by the invention, hinge structure tool has the following advantages:
(1) pollutant emission is few.Adopt hypergravity sulfur oxide sodium alkoxide method, can by the sodium mercaptides in alkali lye close to changing into sodium hydroxide and disulphide completely, alkali lye is close to holomorphosis, and impurities is lower, can recycle, greatly reduce the consumption of total system alkali lye and the quantity discharged of waste soda residue.Disulphide after oxidation in waste gas uses the diesel oil before hydrogenation to absorb further, desulfurization in diesel hydrotreating unit is entered in the original plan by refinery containing disulphide diesel oil, this part sulphur finally enters into sulfur recovery unit and makes sulphur or sulfuric acid, greatly reduce the discharge of sulfur-containing waste water and waste gas, realize the process cleans that clear gusoline is produced.
(2) petroleum naphtha desulfurization depth is high.Adopt the circulation alkali liquor after hypergravity oxidation regeneration, disulphide content wherein can be down to 10ppmw, basicity is close to holomorphosis, and character is close to fresh alkali lye, utilize this circulation alkali liquor in two-stage extracting situation, after can realizing desulfurization, mercaptans content is not higher than the sweetening effectiveness of 2ppmw.Sulfur speciation mainly mercaptan in petroleum naphtha, and a small amount of non-mercaptan sulfur, it is that after taking off, petroleum naphtha sulphur content is that wherein A is non-mercaptan sulfur content in raw material petroleum naphtha not higher than (2+A) ppmw that combined method of the present invention can realize total sweetening effectiveness.
(3) invest low, simple to operate.This combined method is the optimization of operating condition on the basis of former desulfurization process of gasoline, and increase hypergravity oxidation and tail gas diesel oil absorption step, it is very little that super-gravity device compact construction takes up an area space, tail gas diesel oil absorbs optional absorption tower and scale is less, is all in close to the routine operation under normal temperature, condition of normal pressure.
Accompanying drawing explanation
Fig. 1 petroleum naphtha deep desulfuration combination process schematic flow sheet
1-petroleum naphtha, 2-extraction tower, petroleum naphtha after the extracting of 3-one-level, 4-static mixer, 5-slurry tank, 6-alkali lye traps, petroleum naphtha after 7-alkali cleaning, 8-one-level extracting alkali lye to be generated, 9-surge tank, 10-treats coldly raw alkali lye, 11-heat alkali lye to be generated, 12-hypergravity oxidation reactor, 13-oxygen-containing gas, 14-oxidation gaseous effluent, 15-alkali lye trap, 16-dealkalize liquid oxidation tail gas, 17-diesel oil, 18-tail gas absorber, 19-desulfidation tail gas, 20-richness absorbs diesel oil, 21-regenerating alkali liquid storage tank, 22-supplements fresh alkali lye, 23-waste lye, the charging of 24-extracting alkali lye, 25-alkali lye
Fig. 2 deep desulfurization of gasoline combination process schematic flow sheet
1-petroleum naphtha, 2-extraction tower, petroleum naphtha after the extracting of 3-one-level, 4-static mixer, 5-slurry tank, 6-alkali lye traps, petroleum naphtha after 7-alkali cleaning, 8-one-level extracting alkali lye to be generated, 9-surge tank, 10-treats coldly raw alkali lye, 11-heat alkali lye to be generated, 12-hypergravity oxidation reactor, 13-pressurized air, 14-oxidized tail gas, 15-alkali lye trap, 16-dealkalize liquid oxidation tail gas, 17-diesel oil, 18-tail gas absorber, 19-desulfidation tail gas, 20-richness absorbs diesel oil, 21-regenerating alkali liquid storage tank, 22-supplements fresh alkali lye, 23-waste lye, 24-secondary extracting charging alkali lye, 25-alkali lye
Embodiment
Schematic flow sheet is shown in accompanying drawing 1, petroleum naphtha 1 pumping after caustic prescrub enters extraction tower 2, with alkali lye 25 counter current contact from the 2nd grade of extracting settlement separation tank 5, in petroleum naphtha, mercaptan enters into alkali lye, desulfurization petroleum naphtha 3 and the regeneration alkali lye 24 from regenerating alkali liquid storage tank 21 enter the raw 2nd grade of extracting of static mixer 4 hybrid concurrency, mixed solution is two-phase laminated flow in slurry tank 5, and upper strata petroleum naphtha obtains the petroleum naphtha product 7 of deep desulfuration remove the alkali lye carried secretly further in 6 after.The 1 grade of extracting alkali lye 8 to be generated flowed out bottom extraction tower 2 enters surge tank 9, by draining waste soda residue 23 bottom need of production.Depletion to be generated 10 in surge tank 9 through interchanger 11 heat laggard enter hypergravity oxidation reactor 12, wherein with oxygen-containing gas 13 hybrid reaction, the oxidation gaseous effluent 14 that hypergravity oxidation reactor 12 is discharged to remove after the alkali lye carried secretly 16 through trap 15 and removes diesel oil absorption unit, the regeneration alkali lye that hypergravity oxidation reactor 12 is discharged enters regenerating alkali liquid storage tank 21, regeneration alkali lye wherein recycles, and supplements fresh alkali lye 22 by Production requirement in regenerating alkali liquid storage tank 21.Dealkalize liquid oxidation waste gas 16 mixes with contacting in absorption unit 18 from the diesel oil 17 before refinery's hydrotreatment, in gas phase, disulphide is transferred in diesel oil, the richness absorption diesel oil 20 of discharging is sent to diesel hydrotreating unit according to refinery's plan and is processed further, after absorbing, tail gas reclaims through trap the air 19 being met hydro carbons and sulphur content emission request in tail gas after diesel oil, direct emptying.
The preferred method of one of petroleum naphtha and alkali lye two-stage extraction steps is as Fig. 2, difference and general step shown in Fig. 1,1st grade of extracting does not use the alkali lye of discharging in 5, and directly use reprocessing cycle alkali lye 24,2nd grade of extracting uses regeneration alkali lye 24 equally, be equivalent to regeneration alkali lye and flow through two-stage extracting, the alkali lye to be generated that two-stage extracting produces all enters surge tank 9, then goes supergravity reactor to regenerate.All the other steps are identical with Fig. 1.
Embodiment 1
Certain refinery catalytic cracking gasoline is with 105 DEG C for cut point weight is separated, and gained petroleum naphtha sulphur content after caustic prescrub is 82ppmw, and wherein mercaptan sulfur is 78ppmw, non-mercaptan sulfur 4ppmw.Adopt conventional alkali lye deodorizing technology, in alkali lye, NaOH content is 9.5wt%, two-stage extracting, 1st grade is extraction tower, and the 2nd grade is static mixer, and alkali lye and quality of gasoline throughput ratio are 1:2, alkali lye air after extracting is mixed oxidization regeneration at 45 DEG C, after oxidation regeneration alkali lye and disulphide settlement separate at storage tank, tank deck disulphide is not stratified, by some cycles discharge alkali lye and supplement fresh alkali lye.The sulphur content of gained petroleum naphtha product is 25ppm; The basicity of circulation alkali liquor maintains 9.5wt%, and disulphide content is 18ppmw; Disulphide content after oxidation in air tail gas is about 0.5wt%, is difficult to process, alkali lye consumption average out to 1.2kg/t gasoline in certain cycle.
Embodiment 2
Raw material after the petroleum naphtha caustic prescrub identical with embodiment 1, tests the deep desulfuration combined method that the present invention proposes in the petroleum naphtha alkali cleaning experimental installation of 10kg/h scale.Adopt the fresh alkali lye identical with embodiment 1, wherein NaOH content is the auxiliary agents such as 9.5wt%, and micro-oxidation catalyzer.Extracting adopts extraction tower, alkali lye and quality of gasoline are than being 1:2, after extracting, gasoline is directly as product, alkali lye at the bottom of extraction tower enters the regeneration of hypergravity oxidation reactor, regeneration temperature 55 DEG C, regeneration air and alkali lye volume ratio are 50:1, and supergravity reactor outlet air enters filling tube and diesel oil counter current contact and removes S-contained substance wherein, and the liquid of supergravity reactor outlet enters extraction tower and recycles.System keeps pressure-fired, and the flow of relevant logistics meets design load.Collect petroleum naphtha, air, diesel samples measurement total sulfur and sulfur speciation, sampling in the middle of circulation alkali liquor, measure sodium mercaptides content, sulphur determined by extraction disulphide wherein.Average result is as follows: the petroleum naphtha total sulfur after deep desulfuration is 9ppmw, wherein mercaptan sulfur 5ppmw, in circulation alkali liquor, sodium mercaptides transformation efficiency is more than 99%, and disulphide content is 15ppmw, total sulfur 0.3% in air tail gas before absorbing, after diesel oil absorbs, in air, total sulfur is less than 20ppmw.System is run continuously and is greater than 50h, and alkali lye quality keeps stable, without the need to adding fresh alkali lye.
Embodiment 3
Raw material after the petroleum naphtha caustic prescrub identical with embodiment 1, tests the deep desulfuration combined method that the present invention proposes in the petroleum naphtha alkali cleaning experimental installation of 10kg/h scale.Adopt the fresh alkali lye identical with embodiment 1, wherein NaOH content is the auxiliary agents such as 9.5wt%, and micro-oxidation catalyzer.As shown in Figure 1, alkali lye and quality of gasoline are than being 1:2, and normal temperature alkali lye adverse current is by two-stage extracting, and enter the regeneration of hypergravity oxidation reactor afterwards, regeneration temperature 55 DEG C, regeneration air and alkali lye volume ratio are 300:1 for two-stage extraction steps.Diesel oil absorbs and adopts hypergravity absorption unit, and air off gas and diesel fuel volume are than being 500:1.System keeps pressure-fired, and the flow of relevant logistics meets design load.Collect petroleum naphtha, air, diesel samples measurement total sulfur and sulfur speciation, sampling in the middle of circulation alkali liquor, measure sodium mercaptides content, sulphur determined by extraction disulphide wherein.Average measurement result is as follows: the petroleum naphtha total sulfur after deep desulfuration is 6ppmw, wherein mercaptan sulfur 2ppmw, in circulation alkali liquor, sodium mercaptides transformation efficiency is more than 99%, and disulphide content is 8ppmw, total sulfur 500ppmw in air tail gas before absorbing, after diesel oil absorbs, in air, total sulfur is less than 25ppmw.System runs 48h continuously, and alkali lye quality keeps stable, without the need to adding fresh alkali lye.
Embodiment 4
Raw material after the petroleum naphtha caustic prescrub identical with embodiment 1, tests the deep desulfuration combined method that the present invention proposes in the petroleum naphtha alkali cleaning experimental installation of 10kg/h scale.Adopt the fresh alkali lye identical with embodiment 1, wherein NaOH content is the auxiliary agents such as 9.5wt%, and micro-oxidation catalyzer.Two-stage extraction steps as shown in Figure 2, normal temperature alkali lye also flows through two-stage extracting, 1st grade of alkali lye is 1:2 with quality of gasoline ratio, 2nd grade of alkali lye compares 1:3 with quality of gasoline, after extracting, alkali lye enters the regeneration of hypergravity oxidation reactor, regeneration temperature 60 DEG C, regeneration oxygen-containing gas is the oxygen-rich air of oxygen level 27%, and oxygenous is 60:1 with alkali lye volume ratio.Diesel oil absorbs and adopts filling tube.System keeps pressure-fired, and the flow of relevant logistics meets design load.Collect petroleum naphtha, oxygenous, diesel samples measures total sulfur and sulfur speciation, sampling in the middle of circulation alkali liquor, measure sodium mercaptides content, sulphur determined by extraction disulphide wherein.Measurement result is as follows: the petroleum naphtha total sulfur after deep desulfuration is 5ppmw, wherein mercaptan sulfur 1ppmw, in circulation alkali liquor, sodium mercaptides transformation efficiency is more than 99%, and disulphide content is 8ppmw, total sulfur 2500ppmw in waste gas before absorbing, total sulfur 30ppmw in tail gas after diesel oil absorbs.System runs 48h continuously, and alkali lye quality keeps stable, without the need to adding fresh alkali lye.
Claims (8)
1. a method for petroleum naphtha caustic wash desulfuration, comprises following steps:
(1) petroleum naphtha contact with containing the alkali lye of sodium hydroxide and mixes also two-phase laminated flow, the S-contained substance in petroleum naphtha by extracting in alkali lye;
(2) in supergravity reactor, the alkali lye to be generated after extracting is mixed with oxygen-containing gas and contacts, discharge the waste gas containing disulphide and regeneration alkali lye;
(3) diesel oil is used to absorb containing the disulphide in the waste gas of disulphide;
(4) regenerate alkali lye circulation, continue to serve as the extractive process of petroleum naphtha.
2. the method for petroleum naphtha caustic wash desulfuration according to claim 1, is characterized in that, petroleum naphtha mixes extractive process with the alkali lye containing sodium hydroxide and is divided into 2 grades, and the petroleum naphtha after the 1st grade of extracting contacts with the alkali lye containing sodium hydroxide again, carries out the 2nd grade of extracting.
3. the method for petroleum naphtha caustic wash desulfuration according to claim 2, is characterized in that, the 1st grade of extracting adopts extraction tower, and petroleum naphtha and the alkali lye counter current contact containing sodium hydroxide, the scope of the mass ratio of alkali lye and petroleum naphtha is 0.2 ~ 1.2, temperature 20 ~ 60 DEG C.
4. the method for petroleum naphtha caustic wash desulfuration according to claim 2, is characterized in that, the 2nd grade of extracting adopts static mixer.
5. the method for petroleum naphtha caustic wash desulfuration according to claim 2, is characterized in that, the 1st grade and the 2nd grade of extracting all adopt regeneration alkali lye.
6. the method for petroleum naphtha caustic wash desulfuration according to claim 1, it is characterized in that, in supergravity reactor, range of reaction temperature is 35 ~ 70 DEG C, and pressure range is 0.12 ~ 0.3MPa, and in reaction feed, the volume range of oxygen-containing gas and alkali lye to be generated is 5 ~ 500.
7. the method for petroleum naphtha caustic wash desulfuration according to claim 1, is characterized in that, oxygen volume content 10 ~ 90% in oxygen-containing gas.
8. the method for petroleum naphtha caustic wash desulfuration according to claim 1, is characterized in that, the disulphide that diesel oil absorbs in waste gas carries out in high gravity rotating packed bed or absorption tower, the raw material of diesel oil as diesel hydrotreating unit being rich in disulphide of discharge.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105462607A (en) * | 2016-01-13 | 2016-04-06 | 山东联星能源集团有限公司 | Combined process for catalytic and cracked gasoline desulfurization |
| CN106799122A (en) * | 2017-03-17 | 2017-06-06 | 北京沃尔福环保科技有限公司 | A kind of hypergravity takes off ammonium salt device and technique |
| CN106939172A (en) * | 2016-01-05 | 2017-07-11 | 中国石油天然气股份有限公司 | A kind of oxidized regenerating method of sulfur-bearing alkali lye |
| CN108067089A (en) * | 2016-11-11 | 2018-05-25 | 中国石油化工股份有限公司抚顺石油化工研究院 | A kind of method and apparatus for producing NaHS |
| CN108531212A (en) * | 2017-03-01 | 2018-09-14 | 阿克森斯公司 | The regenerated ameliorative way for not including washing step of alkaline solution that will be used in the method for extraction sulfur-containing compound |
| CN110387258A (en) * | 2018-04-19 | 2019-10-29 | 中国石油化工股份有限公司 | A kind of method of inorganic sulfur in cleaning hydrogasoline |
| CN115261066A (en) * | 2022-07-15 | 2022-11-01 | 陕西理工大学 | Fuel oil ultra-deep desulfurization system and method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049171A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for reclaiming and treating hydrocarbon-containing waste gas |
| CN102851068A (en) * | 2011-06-29 | 2013-01-02 | 中国石油化工股份有限公司 | Gasoline desulfurization method |
| CN103146416A (en) * | 2011-12-06 | 2013-06-12 | 中国石油天然气股份有限公司 | Method of separating disulfide from lye |
-
2013
- 2013-12-06 CN CN201310655994.6A patent/CN104694160B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049171A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for reclaiming and treating hydrocarbon-containing waste gas |
| CN102851068A (en) * | 2011-06-29 | 2013-01-02 | 中国石油化工股份有限公司 | Gasoline desulfurization method |
| CN103146416A (en) * | 2011-12-06 | 2013-06-12 | 中国石油天然气股份有限公司 | Method of separating disulfide from lye |
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