CN104694160B - 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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- CN104694160B CN104694160B CN201310655994.6A CN201310655994A CN104694160B CN 104694160 B CN104694160 B CN 104694160B CN 201310655994 A CN201310655994 A CN 201310655994A CN 104694160 B CN104694160 B CN 104694160B
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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
-
- 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 light petrol sulfur removal technology, specifically refer to using sulfur component reality in alkali lye removing light petrol
Existing alkali liquid regeneration and the group technology reducing pollutant emission.
Background technology
Environmental protection is increasingly subject to the concern of the public, and countries in the world have formulated strict vehicle fuel standard in succession, automobile-used
Gasoline quality index progressively develops to the direction of super-low sulfur.Gasoline desulfurization has hydrogenation and non-hydrogenation two schemes, and wherein gasoline adds
Hydrogen desulfurization has become common recognition substantially as cost-effective means.But because in China's gasoline pool, catalytically cracked gasoline accounts for main portion
Point, the C5-C8 olefin(e) centent of catalytically cracked gasoline is high, can lead to a large amount of alkene saturations using hydrogenation scheme, octane number is tight
Lose again.Concentrate on high boiling fraction for sulfide in petrol and alkene concentrates on this feature of low boiler cut, select to close
Gasoline is divided into light petrol and heavy petrol by suitable cut point, and only to the hydrogen addition technology desulfurization of heavy petrol product, light petrol adopts alkali cleaning
Etc. non-hydrogenation scheme, or even do not deal with the case that light petrol sulfur content is relatively low, it is possible to achieve total sulfur meets gasoline sulfur and contains
This requirement of amount standard.The PrimeG+ technique of French Axens company, the OCT-MD technique of Fu Yan institute, Chinese patent
CN200710123546.6 all comprises this technical characteristic, it has also become the common technology in gasoline desulfurization.
In light petrol, sulphur is many is existed with thioalcohol form, the also non-mercaptan sulfur such as a small amount of thiophene.The extracting and oxidizing of Merox technique
Method is the main method of the non-hydrodesulfurization of gasoline, using the mercaptan in caustic extraction gasoline, is allowed to reaction and generates sodium mercaptides molten
Alkali lye removes, then air is passed through in sulfur-bearing alcoholic lye, make sodium mercaptides be oxidized to disulphide, alkali lye is able to simultaneously again
Raw.Including liquefied gas and full distillation gasoline, Merox technique desulfurization all can be used.This technique is there is problems that oxidation regeneration
In alkali lye, disulphide is difficult to separate totally, and the disulphide carrying in circulation alkali liquor can be stripped in gasoline, leads to desulfurization
Effect is deteriorated, and does not reach gasoline quality standard, also creates a large amount of discharges subtracting slag and sulfur-bearing air containing disulphide simultaneously.
The method that Chinese patent CN200910250279.8 discloses liquid hydrocarbon deep desulfurization, with the addition of in NaOH alkali lye
Function intensified auxiliary agent, compares single NaOH alkali lye effect more preferable.Chinese patent CN200710100287.5 proposes using not high
It is stripped in 120 DEG C of thermokalites, cos can be removed and do not need oxidation catalyst, save cost.Chinese patent
The gradient that CN201010296540.0 discloses a kind of alkali lye utilizes, and the alkali lye after desulfuration of liquefied gas is used for gasoline desulfurization, alkali
Liquid change in concentration just mates liquefied gas and the desulfurization of gasoline requires, and has saved cost.Said method and similar techniques are only to alkali
Liquid extraction unit technology is improved, and the separation problem of alkali liquid regeneration and disulphide does not solve, circulation alkali liquor sulfur content
Higher, alkali lye consumption is big, and not, disulphide is also easy to produce secondary pollution to light petrol desulfurization depth.
Chinese patent CN201210276509.x, CN200810162140.3, CN201220012653.8 disclose one kind
Can be used for the caustic wash desulfuration method of liquefied gas and gasoline light fraction, and liquid film alkali cleaning reactor assembly.The method adopts liquid film
Alkali cleaning reactor realizes lye extraction desulfurization process, using oxidation knockout tower, sodium mercaptides is oxidized to disulphide, disulphide
With the hydrophilic coalescent pack initial gross separation in the separated area of alkali lye, then through liquid film extract contactor naphtha extraction curing
Thing, realizes efficiently separating of disulphide.The naphtha extraction method that the method proposes solves alkali lye and two sulphur in original process
The separation problem of compound, and reduce the discharge subtracting slag containing disulphide, but oxidation separates and still adopts original process, separating effect
Do not properly settle with sulfur-bearing air emission problem.
Content of the invention
It is an object of the invention to provide a kind of method of light petrol caustic wash desulfuration, including light petrol caustic wash desulfuration, alkali lye oxygen
Change regeneration, the process such as disulphide absorption, realize the deep removal of sulphur and reduce secondary pollution.
The purpose of the present invention is combination by the following method to be reached：
（1）Light petrol contacts mixing two-phase laminated flow with the alkali lye containing NaOH, and the sulphur-containing substance in light petrol is taken out
Mention in alkali lye；
（2）In supergravity reactor, the alkali lye to be generated after extracting is contacted with oxygen-containing gas mixing, discharges and contain curing
The waste gas of thing and regeneration alkali lye；
（3）Absorb the disulphide in the waste gas containing disulphide using diesel oil；
（4）Regeneration alkali lye circulation, continues to serve as the extractive process of light petrol.
The combined method of light petrol deep desulfuration proposed by the present invention, is taken off using the method that alkali lye extracts to light petrol two-stage
Sulphur, described light petrol refer to full distillation gasoline through weight cutting after light fraction, its end point of distillation at 65～135 DEG C, according to
Full distillation gasoline desulfurization program determines.Using the combined method of the present invention, light petrol raw material is preferably after caustic prescrub, in advance
Alkali cleaning technology belongs to known technology in this area, and the alkali lye of caustic prescrub is not made regeneration and processed, independent of subsequent combination method.
In combined method proposed by the present invention, light petrol contacts extracting with the alkali lye containing NaOH, can be by light petrol
Sulfide, mainly mercaptan, be transformed into sodium mercaptides and be dissolved in alkali lye, thus realizing desulfurized effect.The present invention preferably two
Level caustic extraction.1st grade of extracting preferably uses extraction tower, light petrol and the alkali lye counter current contacting containing NaOH, alkali lye with light
The scope of quality of gasoline ratio is 0.2～1.2,20～60 DEG C of temperature, not control pressure.2nd grade of extracting preferably uses static mixing
Clutch.In the alkali lye that two-stage extracting uses, not higher than the 1st grade charging alkali lye of sulfur content of the 2nd grade of charging alkali lye.Specifically,
Preferably the 1st grade and the 2nd grade extracting of the method for the present invention is all using the alkali lye after regeneration it is also possible to select going out the 2nd grade of extracting
Mouth alkali lye is incorporated into the charging alkali lye in the 1st grade of extracting as the 1st grade of extracting.
In the combined method of the present invention, the important step realizing technique effect is alkali liquid regeneration, i.e. the hypergravity of sodium mercaptides
Oxidizing process.High gravity rotating packed bed reactor has been a kind of common reactor types in chemical process at present, using height
The centrifugal force that speed rotation produces can promote gas-liquid contact to mix, the oxidation reaction of oxygen in sodium mercaptides and gas phase in strengthening alkali lye,
Sodium mercaptides conversion ratio is more than 99%, and the gas liquid ratio operation of achievable relative broad range, is conducive to aoxidizing the two of generation in removing alkali lye
Sulfide.In supergravity reactor, preferred range of reaction temperature is 35～70 DEG C, and pressure limit is 0.12～0.3MPa, charging
Middle oxygen-containing gas is 5～500 with the volume range of alkali lye to be generated.
It is used oxygen volume content in the oxygen-containing gas of 10-90% as oxidant in the hypergravity oxidation reaction of sodium mercaptides,
Preferably use air under normal circumstances.In the case that condition is suitable, the oxygen rich gas that more preferably oxygen volume content is more than 21%,
Oxygen concentration improves the carrying out being conducive to oxidation reaction.
Alkali lye quality after regeneration has direct relation to the degree of light petrol deep desulfuration, and alkali lye quality mainly includes alkali
Degree, sulfur content etc., common technology can realize basicity regeneration, disulphide in the regeneration alkali lye that preferred cycle of the present invention uses
Content be less than 10ppmw, in light petrol after achievable deep desulfuration mercaptans content be less than 2ppmw.
In the combined method of the present invention, the disulphide overwhelming majority that in alkali lye, sodium mercaptides are oxidized to enters hypergravity reaction
In the waste gas of device discharge, being absorbed using diesel oil to make the sulfur content of exhaust emissions meet relevant criterion.Preferably use in the present invention
High gravity rotating packed bed carries out absorption operation, or uses ventional absorption tower, and undesulfured for refinery diesel oil is used as absorbent,
The diesel oil rich in disulphide that absorption tower is discharged is as the raw material of diesel hydrotreating unit.
The light petrol deep desulfuration combined method that the present invention provides, hinge structure has the advantage that：
（1）Pollutant emission is few.Sodium mercaptides method is aoxidized using hypergravity, can be by the sodium mercaptides in alkali lye close to completely
Change into NaOH and disulphide, close to regenerating completely, impurities are relatively low, can recycle, substantially reduce for alkali lye
The discharge capacity of the consumption of total system alkali lye and waste soda residue.Before disulphide in waste gas after oxidation is further using hydrogenation
Diesel oil absorbs, and diesel oil containing disulphide is pressed refinery and entered desulfurization in diesel hydrotreating unit in the original plan, and this part sulphur enters eventually into
Sulfur recovery unit makes sulphur or sulfuric acid, greatly reduces the discharge of sulfur-containing waste water and waste gas, realizes the mistake of clear gusoline production
Journey cleans.
（2）Light petrol desulfurization depth is high.Using the circulation alkali liquor after hypergravity oxidation regeneration, can be by disulphide therein
Content is down to 10ppmw, and close to regenerating completely, property, close to fresh alkali lye, extracts situation using this circulation alkali liquor in two-stage to basicity
Under, after achievable desulfurization, mercaptans content is not higher than the desulfurized effect of 2ppmw.In light petrol, sulfur speciation is mainly mercaptan, and few
Measure non-mercaptan sulfur, the combined method of the present invention can achieve that total desulfurized effect is de- rear light petrol sulfur content for not higher than（2+A）
Ppmw, wherein A are non-mercaptan sulfur contents in raw material light petrol.
（3）Investment is low, simple to operate.This combined method is that the operating condition on the basis of former desulfurization process of gasoline is excellent
Change, and increase hypergravity oxidation and tail gas diesel oil absorption step, super-gravity device compact conformation takes up an area space very little, tail gas diesel oil
Absorb optional absorption tower and scale is less, be in the routine operation under normal temperature, condition of normal pressure.
Brief description
Fig. 1 light petrol deep desulfuration group technology schematic flow sheet
1- light petrol, 2- extraction tower, light petrol after the extracting of 3- one-level, 4- static mixer, 5- settling tank, 6- alkali lye is caught
Collection, light petrol after 7- alkali cleaning, 8- one-level extracts alkali lye to be generated, 9- surge tank, and 10- treats coldly raw alkali lye, 11- heat alkali lye to be generated, 12-
Hypergravity oxidation reactor, 13- oxygen-containing gas, 14 oxidation gaseous effluents, 15- alkali lye trap, 16- dealkalize liquid oxidation tail gas, 17-
Diesel oil, 18- tail gas absorber, 19- desulfidation tail gas, 20- is rich to absorb diesel oil, and 21- regenerates alkali liquor storage tank, and 22- supplements fresh alkali lye,
23- spent lye, 24- extracting alkali lye charging, 25- alkali lye
Fig. 2 deep desulfurization of gasoline group technology schematic flow sheet
1- light petrol, 2- extraction tower, light petrol after the extracting of 3- one-level, 4- static mixer, 5- settling tank, 6- alkali lye is caught
Collection, light petrol after 7- alkali cleaning, 8- one-level extracts alkali lye to be generated, 9- surge tank, and 10- treats coldly raw alkali lye, 11- heat alkali lye to be generated, 12-
Hypergravity oxidation reactor, 13- compressed 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- is rich to absorb diesel oil, and 21- regenerates alkali liquor storage tank, and 22- supplements fresh alkali lye,
23- spent lye, bis- grades of extracting charging alkali lye of 24-, 25- alkali lye
Specific embodiment
Schematic flow sheet is shown in accompanying drawing 1, and the light petrol 1 after caustic prescrub is pumped into extraction tower 2, heavy with from the 2nd grade of extracting
Alkali lye 25 counter current contacting of fall knockout drum 5, in light petrol, mercaptan enters in alkali lye, desulfurization light petrol 3 with from regeneration alkali lye
The regeneration alkali lye 24 of storage tank 21 enters the raw 2nd grade of extracting of static mixer 4 hybrid concurrency, and mixed liquor two-phase in settling tank 5 is divided
From upper strata light petrol obtains the light petrol product 7 of deep desulfuration after removing, in 6, the alkali lye carried secretly further.Extraction tower 2 bottom
The 1 grade of extracting alkali lye 8 to be generated flowing out enters surge tank 9, needs bottom to drain waste soda residue 23 by production.To be generated in surge tank 9
Depletion 10 enters hypergravity oxidation reactor 12 after heat exchanger 11 heating, wherein with oxygen-containing gas 13 hybrid reaction, surpasses
The oxidation gaseous effluent 14 that gravity oxidation reactor 12 is discharged 16 removes diesel oil absorption plant after trap 15 alkali lye carried secretly of removing, surpasses
The regeneration alkali lye that gravity oxidation reactor 12 is discharged enters regeneration alkali liquor storage tank 21, and regeneration alkali lye therein recycles, by life
Product demand supplements fresh alkali lye 22 in regeneration alkali liquor storage tank 21.Dealkalize liquid oxidation waste gas 16 with before refinery's hydrotreating
Diesel oil 17 contacts mixing in absorption plant 18, and in gas phase, disulphide is transferred in diesel oil, and the rich of discharge absorbs diesel oil 20
Send to diesel hydrotreating unit according to refinery's plan to process further, after absorption, tail gas reclaims through trap and is met tail gas after diesel oil
The air 19 of middle hydro carbons and sulfur content emission request, is directly vented.
Light petrol and a kind of preferred method such as Fig. 2 of alkali lye two-stage extraction steps, distinguish and general step shown in Fig. 1,
1st grade of extracting does not use the alkali lye discharged in 5, and directly using regeneration cycle alkali lye 24, the 2nd grade of extracting equally uses regenerating alkali
Liquid 24, is equivalent to regeneration alkali lye cocurrent and is extracted by two-stage, the alkali lye to be generated that two-stage extracting produces is discharged into surge tank 9, then goes
Supergravity reactor regenerates.Remaining step is identical with Fig. 1.
Embodiment 1
Certain refinery catalytic cracking gasoline is separated with 105 DEG C for cut point weight, gained light petrol sulfur content after caustic prescrub
For 82ppmw, wherein mercaptan sulfur is 78ppmw, non-mercaptan sulfur 4ppmw.Using conventional alkali lye deodorizing technology, NaOH content in alkali lye
For 9.5wt%, two-stage extracting, the 1st grade is extraction tower, and the 2nd grade is static mixer, and alkali lye and quality of gasoline flow-rate ratio are 1：2,
The mixed oxidization regeneration at 45 DEG C of alkali lye air after extracting, after oxidation regeneration, alkali lye and disulphide are in storage tank sedimentation point
From tank deck disulphide is not stratified, discharges alkali lye by some cycles and supplements fresh alkali lye.The sulfur content of gained light petrol product
For 25ppm；The basicity of circulation alkali liquor maintains 9.5wt%, and disulphide content is 18ppmw；In air tail gas after oxidation two
Sulfide content about 0.5wt% is it is difficult to process, alkali lye consumption amount average out to 1.2kg/t gasoline in certain cycle.
Embodiment 2
Raw material after light petrol caustic prescrub same as Example 1, in the light petrol alkali cleaning experimental provision of 10kg/h scale
Test deep desulfuration combined method proposed by the present invention.Using fresh alkali lye same as Example 1, wherein NaOH content is
9.5wt%, and the auxiliary agent such as micro-oxidation catalyst.Extracting adopts extraction tower, and alkali lye and quality of gasoline ratio is for 1：2, vapour after extracting
Directly as product, extraction tower bottom alkali lye enters the regeneration of hypergravity oxidation reactor, 55 DEG C of regeneration temperature, regeneration air and alkali to oil
Liquid volume ratio is 50：1, supergravity reactor outlet air enters loading pipe and removes sulfur-bearing thing therein with diesel oil counter current contacting
Matter, the liquid of supergravity reactor outlet enters extraction tower and recycles.System keeps pressure-fired, and the flow satisfaction of related logistics sets
Evaluation.Collect light petrol, air, diesel samples measurement total sulfur and sulfur speciation, sampling in the middle of circulation alkali liquor, measurement sodium mercaptides contain
Sulphur determined by amount, extraction disulphide therein.Average result is as follows：Light petrol total sulfur after deep desulfuration is 9ppmw, wherein mercaptan
Sulphur 5ppmw, in circulation alkali liquor, more than 99%, disulphide content is 15ppmw to sodium mercaptides conversion ratio, total in air tail gas before absorption
Sulphur 0.3%, after diesel oil absorbs, in the air total sulfur is less than 20ppmw.The continuous operation of system is more than 50h, and alkali lye quality keeps stable, no
Fresh alkali lye need to be added.
Embodiment 3
Raw material after light petrol caustic prescrub same as Example 1, in the light petrol alkali cleaning experimental provision of 10kg/h scale
Test deep desulfuration combined method proposed by the present invention.Using fresh alkali lye same as Example 1, wherein NaOH content is
9.5wt%, and the auxiliary agent such as micro-oxidation catalyst.Two-stage extraction steps are as shown in figure 1, alkali lye and quality of gasoline are than for 1：2,
Normal temperature alkali lye adverse current is extracted by two-stage, afterwards enter hypergravity oxidation reactor regeneration, 55 DEG C of regeneration temperature, regeneration air with
Alkali lye volume ratio is 300：1.Diesel oil absorbs and adopts hypergravity absorption plant, and air off gas and diesel fuel volume ratio is for 500：1.System
Keep pressure-fired, the flow of related logistics meets design load.Collect light petrol, air, diesel samples measurement total sulfur and sulfur speciation,
Sampling in the middle of circulation alkali liquor, sulphur determined by measurement mercaptan sodium content, extraction disulphide therein.Average measurement result is as follows：Depth
Light petrol total sulfur after desulfurization is 6ppmw, wherein mercaptan sulfur 2ppmw, and in circulation alkali liquor, sodium mercaptides conversion ratio is more than 99%, two sulphur
Compound content is 8ppmw, total sulfur 500ppmw in air tail gas before absorption, and after diesel oil absorbs, in the air total sulfur is less than 25ppmw.System
System is continuous to run 48h, and alkali lye quality keeps stable, need not add fresh alkali lye.
Embodiment 4
Raw material after light petrol caustic prescrub same as Example 1, in the light petrol alkali cleaning experimental provision of 10kg/h scale
Test deep desulfuration combined method proposed by the present invention.Using fresh alkali lye same as Example 1, wherein NaOH content is
9.5wt%, and the auxiliary agent such as micro-oxidation catalyst.Two-stage extraction steps are as shown in Fig. 2 normal temperature alkali lye cocurrent is taken out by two-stage
Carry, the 1st grade of alkali lye and quality of gasoline are than for 1：2, the 2nd grade of alkali lye compares 1 with quality of gasoline：3, after extracting, alkali lye enters hypergravity oxygen
Change reactor regeneration, 60 DEG C of regeneration temperature, regeneration oxygen-containing gas is the oxygen-enriched air of oxygen content 27%, oxygenous and alkali lye volume
Than for 60：1.Diesel oil absorbs and adopts loading pipe.System keeps pressure-fired, and the flow of related logistics meets design load.Collect light vapour
Oily, oxygenous, diesel samples measure sampling in the middle of total sulfur and sulfur speciation, circulation alkali liquor, and measurement mercaptan sodium content, extraction are therein
Sulphur determined by disulphide.Measurement result is as follows：Light petrol total sulfur after deep desulfuration is 5ppmw, wherein mercaptan sulfur 1ppmw, circulation
In alkali lye, more than 99%, disulphide content is 8ppmw to sodium mercaptides conversion ratio, total sulfur 2500ppmw in waste gas before absorption, and diesel oil is inhaled
Total sulfur 30ppmw in tail gas after receipts.System continuously runs 48h, and alkali lye quality keeps stable, need not add fresh alkali lye.
Claims (6)
1. a kind of method of light petrol caustic wash desulfuration, comprises the steps of：
(1) light petrol contacts mixing two-phase laminated flow with the alkali lye containing NaOH, and the sulphur-containing substance in light petrol is extracted to be arrived
In alkali lye；
(2) in supergravity reactor, the alkali lye to be generated after extracting is contacted with oxygen-containing gas mixing, discharges containing disulphide
Waste gas and regeneration alkali lye；
(3) diesel oil is used to absorb the disulphide in the waste gas containing disulphide；
(4) circulation of regeneration alkali lye, continues to serve as the extractive process of light petrol,
In supergravity reactor, range of reaction temperature is 35～70 DEG C, and pressure limit is 0.12～0.3MPa, contains in reaction feed
Carrier of oxygen is 5～500 with the volume range of alkali lye to be generated,
Oxygen volume content 10～90% in oxygen-containing gas.
2. light petrol caustic wash desulfuration according to claim 1 method it is characterised in that light petrol with containing NaOH
Alkali lye mixing extractive process is divided into 2 grades, and the light petrol after the 1st grade of extracting is contacted with the alkali lye containing NaOH again, carries out the 2nd
Level extracting.
3. the method for light petrol caustic wash desulfuration according to claim 2 is it is characterised in that the 1st grade of extracting adopts extraction tower,
Light petrol and the alkali lye counter current contacting containing NaOH, alkali lye is 0.2～1.2 with the scope of the mass ratio of light petrol, temperature 20
～60 DEG C.
4. the method for light petrol caustic wash desulfuration according to claim 2 is it is characterised in that the 2nd grade of extracting is using static mixed
Clutch.
5. the method for light petrol caustic wash desulfuration according to claim 2 is it is characterised in that the 1st grade and the 2nd grade of extracting are all adopted
With regenerating alkali lye.
6. the method for light petrol caustic wash desulfuration according to claim 1 is it is characterised in that diesel oil absorbs two sulphur in waste gas
Compound is carried out in high gravity rotating packed bed or absorption tower, and the diesel oil rich in disulphide of discharge is as diesel hydrotreating unit
Raw material.
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| 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 |
| CN105462607B (en) * | 2016-01-13 | 2017-09-12 | 山东联星能源集团有限公司 | The group technology of catalytically cracked gasoline desulfurization |
| CN108067089B (en) * | 2016-11-11 | 2019-08-06 | 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 producing NaHS |
| FR3063496B1 (en) * | 2017-03-01 | 2019-04-05 | Axens | IMPROVED METHOD FOR REGENERATING AN ALKALINE SOLUTION USED IN A PROCESS FOR EXTRACTING SULFUR COMPOUNDS WITH NO WASHING STEP |
| CN106799122B (en) * | 2017-03-17 | 2023-08-01 | 北京沃尔福环保科技有限公司 | Supergravity ammonium salt removal device and process |
| 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 |
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| 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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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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