CN106554809B - Lighter hydrocarbons sulfur method and device - Google Patents
Lighter hydrocarbons sulfur method and device Download PDFInfo
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- CN106554809B CN106554809B CN201510639849.8A CN201510639849A CN106554809B CN 106554809 B CN106554809 B CN 106554809B CN 201510639849 A CN201510639849 A CN 201510639849A CN 106554809 B CN106554809 B CN 106554809B
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Abstract
A kind of method and apparatus of lighter hydrocarbons desulfurization, sulfur-bearing lighter hydrocarbons and lye are introduced into respectively in two-phase mixtures reactor, lighter hydrocarbons are sufficiently mixed with lye to react, acid sulfur-containing compound in lighter hydrocarbons reacts the salt for generating the sulfur-containing compound being soluble in the aqueous phase with alkali, two-phase mixture after reaction draws reactor through product exit, and desulfurization light hydrocarbon product and sulfur-bearing lye are obtained after water-oil phase separation；The two-phase mixtures reactor includes dispersed phase entrance and the continuous phase entrance (1) being sequentially communicated, two-phase mixtures area, shunting mixed zone and product exit (12)；Wherein, the two-phase mixtures area is made of at least one two-phase mixtures unit.Lighter hydrocarbons sulfur method and device lighter hydrocarbons provided by the invention and lye good mixing effect, mass-transfer efficiency are high, and treating capacity is big, sulfur-containing compound that can be in deep removal lighter hydrocarbons.
Description
Technical field
The present invention relates to refining arts, and in particular, to a kind of desulfurization of hydrocarbon oil method and a kind of lighter hydrocarbons desulphurization reaction dress
It sets.
Background technology
Contain the largely acidity based on hydrogen sulfide and mercaptan in the lighter hydrocarbons such as thick liquefied gas and light petrol that oil plant generates
Sulphur-containing substance industrially generally removes acid sulphur-containing substance by the method for alkali cleaning.
Technology due to carrying out the lighter hydrocarbons desulfurization such as liquefied gas and light petrol by the method for alkali cleaning is related to liquid liquid two-phase mixture
System, therefore used equipment generally comprises several classes such as extraction tower, motionless mixer and fiber film abstractor.
Extraction tower be a kind of continuous flow upstream equipment, it can be achieved that multiple theoretical stages separative efficiency, but its equipment scale compared with
Greatly, operation is more complicated, and since material apparent velocity is slower, mass tranfer coefficient is relatively low.Fiber film abstractor is a kind of cocurrent behaviour
Make equipment, equipment scale is small compared with extraction tower, and provides larger mass transfer area using hydrophilic fibre silk, therefore mass transfer is imitated
Rate is higher, but filament can lose hydrophily after being used for a long time because of contaminated, and mass-transfer efficiency reduces, and is difficult to clear up
Regeneration.The equipment scale of motionless mixer is minimum, is mixed by two-phase flow at high speed and carries out mass transport process, however static mixer
Mixed structure be difficult to realize the high degree of dispersion mixing of liquid liquid system, therefore its there are bottlenecks in terms of mass-transfer efficiency.
The lighter hydrocarbons such as liquefied gas and light petrol after deep desulfuration acid sulphur-containing substance concentration in 10ppm hereinafter, can use
In production clean fuel.But the lighter hydrocarbons desulphurization plant such as conventional liquefied gas and light petrol is the case where operating condition is basically unchanged
Under, it is difficult to overcome the resistance to mass tranfer in deep desulfurization process.
It is full by process intensification therefore, it is necessary to develop the reactor of the lighter hydrocarbons deep desulfuration such as efficient liquefied gas and light petrol
The lighter hydrocarbons deep desulfuration requirements such as liquefied gas and light petrol of the foot under low mass transfer Impetus Condition.
Invention content
It is de- the purpose of the present invention is on the basis of existing technology, providing the lighter hydrocarbons that a kind of mass-transfer efficiency is high, treating capacity is big
Sulphur method, and realize the lighter hydrocarbons desulfurizer of the lighter hydrocarbons sulfur method.
Lighter hydrocarbons sulfur method provided by the invention, using two-phase mixtures reactor, sulfur-bearing lighter hydrocarbons and lye introduce institute respectively
In the two-phase mixtures reactor stated, lighter hydrocarbons are sufficiently mixed with lye to react, and the acid sulfur-containing compound in lighter hydrocarbons reacts life with alkali
At the salt for the sulfur-containing compound being soluble in the aqueous phase, the two-phase mixture after reaction draws reactor, water-oil phase point through product exit
The lye of desulfurization light hydrocarbon product and sulfur-bearing is obtained from after；The two-phase mixtures reactor includes dispersed phase entrance and is sequentially communicated
Continuous phase entrance 1, two-phase mixtures area, shunting mixed zone and product exit 12；Wherein, the two-phase mixtures area is by least one
A two-phase mixtures unit composition, the two-phase mixtures unit include point for mixing runner 5 and being set to 5 side of mixing runner
Dephasing runner 2, the mixing runner 5 is by being set to the distribution hole 3 on the flow path wall 4 of mixing runner 5 and the dispersed phase stream
Road 2 is connected to, and the setting of the entrance of the dispersed phase runner 2 makes in dispersed phase runner 2 fluid flow direction and mixes in runner 5
Fluid flow direction is opposite；The entrance of the continuous phase entrance connection mixing runner.
In lighter hydrocarbons sulfur method provided by the invention, the lighter hydrocarbons are the stone of the C4-C5 containing acid sulfur-containing compound
Petroleum hydrocarbon fraction, wherein the acid sulfur-containing compound is mercaptan, the sulfur content in terms of element sulphur in the lighter hydrocarbons is 50~
2000ppm.The lighter hydrocarbons are liquefied gas and/or light gasoline fraction.The lye is the aqueous solution of NaOH.
Preferably, lighter hydrocarbons sulfur method provided by the invention further includes step (2), step (3)：
(1) above-mentioned lighter hydrocarbons sulfur method is used in caustic wash unit；
(2) lye of sulfur-bearing contacts in oxidation regeneration unit with oxygen-containing gas, the salt of the sulfur-containing compound in lye with
Oxygen reaction generates disulphide, and the lye containing a small amount of disulphide is obtained after isolating disulphide；
(3) lye in step (2) comes into full contact in anti-extraction unit with light hydrocarbon oil, and the disulphide in lye is dissolved in
In light hydrocarbon oil, regeneration lye is obtained after two-phase laminated flow and is recycled back to recycling in step (1).
Realize the lighter hydrocarbons desulfurizer in above-mentioned lighter hydrocarbons sulfur method, including caustic wash unit, sedimentation unit, oxidation regeneration
Unit and anti-extraction unit, the caustic wash unit and/or the anti-extraction unit use the two-phase mixtures reactor.
Lighter hydrocarbons sulfur method and device provided by the invention have the beneficial effect that：
Lighter hydrocarbons sulfur method provided by the invention can obtain higher compared with prior art, in the case of more high throughput
Reaction conversion ratio.The two-phase mixtures reactor that lighter hydrocarbons sulfur method provided by the invention uses has good mixing effect, mass transfer effect
Rate is high, and treating capacity is big, the high feature of desulfuration efficiency.Before two-phase mixtures contact, flow direction of the two-phase in respective runner is
Countercurrent flow can make the pressure difference of each distribution hole both sides be uniformly distributed, and dispersed phase can be equably from each distribution hole stream
Go out and strengthens and pass to the effect that realization multistage cross flow is mixed in two-phase mixtures reactor with the continuous mixing that is in contact
Matter performance is avoided since part distribution hole caused by Pressure difference distribution unevenness can not push fluid out to reduce mass-transfer efficiency
Phenomenon.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the structural schematic diagram of two-phase mixtures reactor.
Fig. 2 is the faces the A-A diagrammatic cross-section of two-phase mixtures reactor.
Fig. 3 is the flow diagram of lighter hydrocarbons sulfur method provided by the invention.
Reference sign
1 continuous phase entrance, 2 dispersed phase runner
3 distribution hole, 4 flow path wall
5 mixing 6 diverter members of runner
7 distributing chamber, 8 distributed component
9 collecting chamber, 10 drop
11 mixing 12 product exits of flow channel entry point
13 sulfur-bearing lighter hydrocarbons, 14 caustic wash unit
15 regeneration 16 sedimentation units of lye
17 oxidation regeneration unit, 18 anti-extraction unit
19 light-end products, 20 oxygen-containing gas
The 22 desulfurization lighter hydrocarbons of light-end products of 21 sulfur compounds
23 mixed alkali liquor, 24 cross-channel
25 dispersed phase entrances
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The method of lighter hydrocarbons desulfurization provided by the invention, using two-phase mixtures reactor, sulfur-bearing lighter hydrocarbons and lye introduce respectively
In the two-phase mixtures reactor, lighter hydrocarbons are sufficiently mixed with lye to react, and the acid sulfur-containing compound in lighter hydrocarbons is reacted with alkali
The salt for generating the sulfur-containing compound being soluble in the aqueous phase, the two-phase mixture after reaction draw reactor, water-oil phase through product exit
The lye of desulfurization light hydrocarbon product and sulfur-bearing is obtained after separation.
Preferably, lighter hydrocarbons sulfur method provided by the invention further includes step (2), step (3)：
(1) above-mentioned lighter hydrocarbons sulfur method is used in caustic wash unit；
(2) lye of sulfur-bearing contacts in oxidation regeneration unit with oxygen-containing gas in step (1), the sulfur-bearing chemical combination in lye
The salt of object is reacted with oxygen generates disulphide, and the lye containing a small amount of disulphide is obtained after isolating disulphide；
(3) lye in step (2) comes into full contact in anti-extraction unit with light hydrocarbon oil, and the disulphide in lye is dissolved in
In light hydrocarbon oil, regeneration lye is obtained after two-phase laminated flow and is recycled back to recycling in step (1).
The lighter hydrocarbons are liquefied gas and/or light gasoline fraction containing acid sulfur-containing compound, the i.e. petroleum hydrocarbon of C4-C5
Fraction, wherein the acid sulfur-containing compound is mercaptan, the sulfur content in terms of element sulphur in the lighter hydrocarbons is 50~
2000ppm.The lye is the aqueous solution of NaOH.
In lighter hydrocarbons sulfur method provided by the invention, preferably in caustic wash unit and the anti-extraction unit of step (3) using tool
There is the two-phase mixtures reactor of special construction.
The two-phase mixtures reactor include dispersed phase entrance and be sequentially communicated continuous phase entrance, two-phase mixtures area,
Shunt mixed zone and product exit 12；Wherein, the two-phase mixtures area is made of at least one two-phase mixtures unit, described
Two-phase mixtures unit includes the dispersed phase runner 2 for mixing runner 5 and being set to 5 side of mixing runner, and the mixing runner 5 is logical
The distribution hole 3 being set on the flow path wall 4 of mixing runner 5 is crossed to be connected to the dispersed phase runner 2, the dispersed phase runner 2
The setting of entrance so that fluid flow direction is opposite with fluid flow direction in mixing runner 5 in dispersed phase runner 2；The company
The entrance of the continuous phase entrance connection mixing runner.
In the two-phase mixtures reactor, it is preferable that one end of the dispersed phase runner 2 is entering for dispersed phase runner
Mouthful, it is communicated with the dispersed phase runner；The other end for being provided with the distribution hole is blind end.
Preferably, the continuous phase entrance 1 is communicated through distributing chamber 7 with the two-phase mixtures area, the distributing chamber
Middle setting fluid distrbution component 8.
Preferably, along fluid flow direction, the length ratio in the two-phase mixtures area and the shunting mixed zone is
0.05~5.The length of the shunting mixed zone is 50~2000mm, more preferable 50~1000mm.
In the two-phase mixtures reactor, multiple diverter members 6 are set, and shape is webbed in the shunting mixed zone
Cross-channel 24.Fluid flows in cross-channel, and continuous shunting, interflow improve liquid-liquid diphase by Surface Renewal effect
Or the mass transport process between gas-liquid two-phase near phase boundary, and then strengthen the mixed effect of two-phase.6 shape of diverter member can be water chestnut
Shape, triangle, sector, rectangle, spindle, aciculiform etc. is variously-shaped or the variously-shaped combination.Preferably, institute
The width for the cross-channel stated is 0.5~5mm, more preferably 1~4mm；The height of the cross-channel is 0.5~5mm, more
Preferably 0.5~3mm.
In the two-phase mixtures reactor, one end of the mixing runner of the two-phase mixtures unit is provided with entrance, separately
One end setting outlet so that a kind of fluid can be introduced into from the entrance of the mixing runner in mixing runner, and with from dividing
The mixture of the one other fluid contact mixing of dephasing runner, two kinds of fluids enters shunting mixing through the outlet of the mixing runner
In the cross-channel in area, it is discharged by the outlet of cross-channel.In the two-phase mixtures unit, in order to avoid to a greater degree by
Part distribution hole can not flow out fluid caused by each distribution hole both ends Pressure difference distribution unevenness, to reduce asking for mass-transfer efficiency
Topic needs to select the cross-sectional area for suitably mixing runner and dispersed phase runner, it is preferable that the cross section of the dispersed phase runner
Product is 1-40mm2, more preferably 2-30mm2.It is preferred that the cross-sectional area of the mixing runner is 0.5-10mm2, more preferably 1-
6mm2。
In the two-phase mixtures unit, dispersed phase runner is not limited along the cross sectional shape perpendicular to fluid flow direction
The cross-sectional shape of system, the dispersed phase runner can be round, ellipse or rectangle.To promote mass transfer, it is preferable that described point
The cross-sectional shape of dephasing runner is rectangle.The present invention does not have mixing runner perpendicular to the cross-sectional shape of fluid flow direction
Limitation, cross-sectional shape can be round, ellipse or rectangle.To promote mass transfer, it is preferable that the cross section of the mixing runner
Shape is rectangle.
In the two-phase mixtures unit, the number of the distribution hole is at least 1, and the number of the preferably described distribution hole is
2-10, more preferably 3-5.In order to be avoided to a greater degree due to portion caused by each distribution hole both ends Pressure difference distribution unevenness
Point distribution hole can not push fluid out, the problem of to reduce efficiency, when distribution hole is multiple, it is preferable that along dispersed phase stream
The aperture of fluid flow direction in road, multiple distribution holes is sequentially increased；It is highly preferred that by upstream to downstream, adjacent distribution hole
Aperture differ 0.05-1mm.
In the two-phase mixtures unit, the depth of the preferably described distribution hole is 0.3-2.5mm, more preferably 0.5-
2mm。
Preferably, the length of the mixing runner is 50-2000mm, more preferably 50-1000mm.The two-phase mixtures
In unit, when the number of the distribution hole is multiple, the aperture of the preferably described distribution hole be each independently 0.1-2mm,
The centre distance of more preferably 0.3-1.2mm, two neighboring distribution hole are 0.5-40mm.
In the two-phase mixtures unit, the folder of the axial direction of the distribution hole and the flow direction of the fluid mixed in runner
Angle can be any angle, and the preferably described angle is 45 ° -90 °, more preferably 90 °.
In the two-phase mixtures unit, it is preferable that be provided with an at least filament in the mixing runner.It is described
Filametntary material can be the inorganic material such as metal, glass, can also be organic material, or the above different materials is compound
Material.Filametntary selection is depending on the property of the fluid in dispersed phase runner, if in dispersed phase runner
Fluid is aqueous solution, and the hydrophilic materials such as stainless steel or glass can be selected in filament；If the stream in dispersed phase runner
Body is oil product, and lipophilic organic material can be selected in filament.It is preferred that described filametntary a diameter of 1 μm to 5mm, more preferably
2-50μm.Filament is added in mixing runner, drop can be formed by by itself and the fluid in dispersed phase runner
Compatibility, forms very thin liquid film in filament surface, increases the interphase mass transfer area in two-phase mixtures unit, shorten mass transfer away from
From raising mixing efficiency.
In the two-phase mixtures reactor, to the filametntary diameter and length, there is no particular limitation, this field
Technical staff can select according to conventional parameter in the art.The filametntary length can be according to the mixed flow
The length in road and be arranged, it is described it is filametntary can run through entire mixing runner, preferably flowed according to the fluid in mixing runner
Direction, the filametntary length are from the central point of the distribution hole of most downstream to the distance of mixing runner exit.The present invention couple
There is no particular limitation for the filametntary shape, can be linear or irregular shape, under preferable case, in institute of the present invention
In the two-phase mixtures unit stated, the filament is linear or helical form.
The two-phase mixtures reactor, the outlet of the shunting mixed zone are connected to the product through collecting chamber 9 and go out
Mouth 12.The two-phase mixtures reactor, under preferable case, in order to ensure that continuous phase can be uniformly across each two-phase mixtures
The distributing chamber containing distributed component is arranged in unit preferably in two-phase mixtures reactor, to ensure that material can be uniformly across
Each two-phase mixtures unit.In two-phase mixtures reactor, after continuous phase enters distributing chamber, distributed component can inhibit placed in the middle
The excessive problem of fluid flow of the mixing runner of two-phase mixtures unit, increases the fluid flow of distributed component both sides, in this way may be used
To realize that the material in each two-phase mixtures unit can be uniformly distributed.The form of distributed component can carry sieve pore, item stitches etc.
Multi-disc distributed component can also be arranged in feature structure, and the shape of distributed component can be the shapes such as rectangle, diamond shape.
The two-phase mixtures reactor further includes collecting chamber preferably in the two-phase mixtures reactor, according to from continuous
The flow direction of the fluid of phase entrance sets gradually distributing chamber, two-phase mixtures area, shunting mixing in the two-phase mixtures reactor
Area and collecting chamber.
In the two-phase mixtures reactor, the fluid being preferred from dispersed phase runner is dispersed phase；From continuous phase
The fluid of entrance is continuous phase.
It, can be mixed to two-phase since the movement velocity of dispersed phase and continuous phase is very high in the two-phase mixtures reactor
The runner for closing reactor is adequately washed away, the problem of avoiding runner blocking during long-term operation.In view of liquid liquid
This higher feature of interfacial tension of system, the mesh for being vigorously mixed realization lighter hydrocarbons deep desulfuration that method of the invention passes through two-phase
, in liquid liquid two-phase contact process and do not use any substance (such as surfactant, alcohols with reduction system tension
Etc.) two-phase mixtures is promoted to contact, therefore the emulsion of system is avoided, split-phase effect is good after two-phase mixtures contact, does not have
There is additional waste material to generate.
In the method for sulfur-bearing lighter hydrocarbons deep desulfuration provided by the invention, in step (1), by lye entering from dispersed phase runner
Mouth is introduced into dispersed phase runner, and the lye is by being arranged the distribution hole on the flow path wall of mixing runner and mixing in runner
Lighter hydrocarbons hybrid reaction, wherein stream of flow direction of the lye in dispersed phase runner with the lighter hydrocarbons in mixing runner
Dynamic direction is opposite.In the liquid liquid two phase flow that lye and lighter hydrocarbons are formed, a phase is as continuous phase, and another phase is as dispersed phase.It is right
In the two-phase mixtures reactor of caustic wash unit, preferably sulfur-bearing lighter hydrocarbons are as continuous phase, and lye is as dispersed phase；And back suction is carried
The two-phase mixtures reactor of unit, preferably lye are continuous phase, and lighter hydrocarbons are dispersed phase.In the caustic wash unit, in lighter hydrocarbons
Acid sulfur-containing compound is reacted with NaOH generates sulfur-bearing sodium salt, and sulfur-bearing sodium salt is dissolved in lye.By desulphurization reaction
Lighter hydrocarbons and lye enter in the precipitation apparatus of caustic wash unit detached after, lighter hydrocarbons enter sedimentation unit and the lye wherein carried secretly
It is sufficiently separated, the lighter hydrocarbons of the abundant desulfurization can enter the processes such as subsequent washing is refined and be continued with.
Preferably, the reaction condition of caustic wash unit is in step (1)：Reaction temperature is 25-80 DEG C, reaction pressure 0.2-
2MPa。
In the method for sulfur-bearing lighter hydrocarbons deep desulfuration provided by the invention, the lye is the aqueous solution of NaOH.Preferred weight
Percent concentration is the NaOH aqueous solutions of 10-20%.Preferably, in caustic wash unit, the lighter hydrocarbons as continuous phase are in mixing runner
The apparent velocity of inlet is 0.5-20m/s, more preferably 4-10m/s.As dispersed phase lye dispersed phase entrance table
Sight flow velocity is 0.2-5m/s, more preferably 0.3-3m/s.
In the method for lighter hydrocarbons deep desulfuration provided by the invention, swiftly flowing liquid liquid two-phase in two-phase mixtures reactor
It is vigorously mixed, the drop that dispersed phase is formed is vigorously mixed with continuous phase, and resistance to mass tranfer is low, enables to the mass transfer mistake between two-phase
Journey fully carries out, and desulfuration efficiency can reach 90% or more, i.e., the contained acidity Containing Sulfur in caustic wash unit can make lighter hydrocarbons
It closes object (such as mercaptan) fully to react with lye, acid sulphur-containing substance removal efficiency is more than 90wt%, acidity sulphur-containing substance in lighter hydrocarbons
Mass concentration can be down to 10ppm hereinafter, realize lighter hydrocarbons deep desulfuration；And lye and lightweight may be implemented in anti-extraction unit
Oil product is sufficiently mixed, and the disulphide of entrained in the lye after desulfurization is extracted in oil phase, the extraction yield of disulphide
More than 90wt%.
The method of lighter hydrocarbons deep desulfuration provided by the invention, preferably continuous phase entrance to product goes out in two-phase mixtures reactor
The pressure drop of mouth is 10-800kPa；More preferably 100-600kPa.Dispersed phase forms drop after distribution hole and continuously mixes
Contact.Since the diameter of distribution hole is smaller, the size of drop is also smaller, can obtain larger interphase mass transfer area.
The method of sulfur-bearing lighter hydrocarbons deep desulfuration provided by the invention, in step (2), sulfur-bearing lye enters oxidation regeneration unit
In, carry out haptoreaction with oxygen-containing gas.The reactor of oxidation regeneration unit typically bubbling bed reactor and/or filler
Bubbling bed reactor.In the reactor of oxidation regeneration unit, the sulfur-bearing sodium salt in sulfur-bearing lye is gone back with oxygen-containing gas in oxidation
It is reacted under the action of raw catalyst, the sulfur-bearing sodium salt in sulfur-bearing lye is converted to disulphide not soluble in water, after separation
Obtain the lye after disulphide and desulfurization.The oxidation reduction catalyst be containing sulfonated phthalocyanine cobalt or it is other have catalysis
The substance of effect.Separation process generally use sedimentation separation in oxidation regeneration unit, due to the density of lye and disulphide
Closely, in the lye obtained through sedimentation separation still contain a small amount of disulphide, need into anti-extraction unit continue into
The separation of lye and disulphide after row desulfurization.
The method of sulfur-bearing lighter hydrocarbons deep desulfuration provided by the invention in step (3), in the anti-extraction unit, will take off
Lye after sulphur and disulphide are soluble in light-end products therein such as gasoline and are contacted in the two-phase mixtures reactor, real
The separation of lye and the disulphide wherein carried secretly after existing desulfurization obtains regeneration lye.Precipitation apparatus through anti-extraction unit,
Regeneration lye is detached with the light-end products containing disulphide, and the regeneration lye, which is recycled back to the caustic wash unit progress lighter hydrocarbons, to be taken off
Sulphur.The operation of the operating method and caustic wash unit of two-phase mixtures reactor of the present invention is used in the anti-extraction unit
Method is similar, and details are not described herein by the present invention.
Preferably, the reaction condition of anti-extraction unit includes in step (3)：Reaction temperature is 25-80 DEG C, and reaction pressure is
0.2-2MPa.Preferably, in step (3) in anti-extraction unit, the lye as continuous phase is in the apparent of mixing flow passage entry
Flow velocity is 0.5-20m/s, more preferably 4-10m/s.As dispersed phase lighter hydrocarbons dispersed phase entrance apparent velocity be 0.2-
5m/s, more preferably 0.3-3m/s.
According to the treating capacity of the concentration and lighter hydrocarbons of the acid sulphur-containing substance in lighter hydrocarbons, two-phase provided by the invention can be mixed
It closes reactor and carries out separate unit or multi-platform combined use.When more two-phase mixtures reactor cascades of use are in use, each
Reaction condition in two-phase mixtures reactor can be identical or different.
The preferred embodiment of lighter hydrocarbons sulfur method and device provided by the invention, this hair are illustrated referring to the drawings
It is bright therefore not any way limited.
Attached drawing 1 is the structural schematic diagram of two-phase mixtures reactor, as shown in Fig. 1, in the two-phase mixtures reactor
Including continuous phase entrance 1, distributing chamber 7, two-phase mixtures area, shunting mixed zone, collecting chamber 9 and the product exit 12 being sequentially communicated,
Further include dispersed phase entrance (not marked in figure), distributed component 8 is set wherein in distributing chamber 7, and the two-phase mixtures area is by 5
Two-phase mixtures unit forms, and the multiple diverter members 6 of setting will be divided in shunting mixed zone in the shunting mixed zone reticulates
Cross-channel.Attached drawing 2 is the sectional view in the faces two-phase mixtures reactor A-A in attached drawing 1, and as shown in Fig. 2, the two-phase is mixed
It includes the mixing runner 5 communicated with continuous phase entrance and the dispersed phase runner 2 for mixing runner side described in being set to close unit,
The mixing runner 5, which is set, to be communicated in the distribution hole 3 on mixing flow path wall 4 with the dispersed phase runner 2, point
The setting of the entrance of dephasing runner 2 so that in dispersed phase runner fluid flow direction with the flow direction that mixes in runner 5 on the contrary,
Diverter member 6 is set in the shunting mixed zone；The outlet of the mixing runner 5 is communicated with the shunting mixed zone, institute
The outlet for stating the cross-channel of shunting mixed zone is communicated with collecting chamber, and collecting chamber is connected to product exit.Two-phase fluid to be mixed
In a phase enter the two-phase mixtures reactor through continuous phase entrance, another phase introduces dispersed phase entrance, and two-phase is described
Two-phase mixtures area in tentatively mix and react after, quickly enter and further mixed in shunting mixed zone, mixed two-phase is mixed
It closes object and enters collecting chamber, and drawn through the product exit.
Attached drawing 3 is the flow diagram of lighter hydrocarbons sulfur method provided by the invention, as shown in figure 3,15 He of lye will be regenerated
Sulfur-bearing lighter hydrocarbons 13 are introduced into caustic wash unit 14, in the caustic wash unit 14, acid sulphur-containing substance in sulfur-bearing lighter hydrocarbons 13 with
NaOH reactions generate sulfur-bearing sodium salt, and sulfur-bearing sodium salt is dissolved in lye.Enter by the sulfur-bearing lighter hydrocarbons 13 of caustic wash unit 14
Sedimentation unit 16 obtains desulfurization lighter hydrocarbons 22 after being sufficiently separated with the lye wherein carried secretly, desulfurization lighter hydrocarbons 22 enter subsequent water
The processes such as refined are washed to be continued with.Lye from caustic wash unit 14 is formed together with the lye being discharged by sedimentation unit 16
Mixed alkali liquor 23 enters in oxidation regeneration unit 17, is contacted with oxygen-containing gas 20.In the reactor of oxidation regeneration unit 17
Interior, the sulfur-bearing sodium salt in lye is reacted with oxygen-containing gas 20, is converted the sulfur-bearing sodium salt in lye to disulphide, is obtained desulfurization
Lye afterwards.Lye after the desulfurization being discharged by oxidation regeneration unit 17 continues the alkali after desulfurization into anti-extraction unit 18
The separation of liquid and disulphide.In the anti-extraction unit 18, the lye after desulfurization is contacted with light-end products 19, realizes desulfurization
The separation of lye and the disulphide wherein carried secretly afterwards, obtains the light-end products 21 of regeneration lye 15 and sulfur compound.By institute
It states regeneration lye 15 and is recycled back to the progress lighter hydrocarbons desulfurization of the caustic wash unit 14.
It should be strongly noted that the enough two-phase mixtures units that the present invention is concomitantly introduced into fresh lye of regenerating alkali liquid energy
In dispersed phase runner, fresh lye is not shown in Fig. 3 of the invention, but this is well known to those skilled in the art.
Lighter hydrocarbons sulfur method and device provided by the invention also have the advantages that following specific：
Liquid liquid two-phase mixed at high speed in two-phase mixtures reactor in lighter hydrocarbons sulfur method provided by the invention, both can be with
Strengthen two alternate mass transfers, and can be with idetified separation process.Lighter hydrocarbons deep desulfuration is realized, it can be by the acid Containing Sulfur in lighter hydrocarbons
It closes object concentration and is down to the even lower levels of 10ppm, desulfurization degree is up to 90% or more.Two-phase apparent velocity in two-phase mixtures reactor
Height is not susceptible to the problem of runner blocks.Utilize the high feature of interface tension, it is not necessary to use surface reactive material, two-phase
Emulsification problem is avoided in mixing reactor, convenient for split-phase after reaction and carries out subsequent processing.In addition, two-phase provided by the invention
Mixing reactor is not easy to plug in use, can be operated for a long time.Lighter hydrocarbons desulfurizer provided by the invention uses two-phase
Mixing reactor has the characteristics that device volume is small, treating capacity is big.
The present invention will be described in detail by way of examples below.In following embodiment, in the feelings being not particularly illustrated
Under condition, used a variety of materials are all from commercially available.
Embodiment 1
Liquefied gas and lye containing mercaptan contact in caustic wash unit, and mercaptan is reacted with NaOH to be generated sodium mercaptides and be dissolved in
In lye.Completion removal of mercaptans after the liquefied gas being discharged by caustic wash unit enters sedimentation unit and detached with the part lye that it is carried secretly
Purpose.The lye being discharged by sedimentation unit enters oxidation regeneration unit, and in filler bubbling bed reactor, lye is contacted with air
Reaction, converts sodium mercaptides to disulphide.Lye after the desulfurization be discharged by oxidation regeneration unit enters anti-extraction unit, with
Gasoline contacts, and removes the disulphide of entrained with, obtains regeneration lye.The regeneration lye being discharged by anti-extraction unit is recycled back to alkali
It washes unit and participates in desulfuration of liquefied gas process.
Selected liquefied gas is derived from Wuhan Branch, Sinopec Corp., volume basis composition such as table 1
It is shown.
1 liquefied gas hydro carbons volume basis of table forms
| N-alkane | Isoparaffin | Alkene | |
| C2 | 2.35 | 0 | 1.05 |
| C3 | 44.66 | 0 | 15.96 |
| C4 | 15.73 | 5.89 | 12.87 |
| C5 | 0 | 1.49 | 0 |
The method analysis that total sulfur content in liquefied gas is provided using SH/T 0222-92, the composition of acid mercaptan use
GC-SCD chromatographies (PONA columns) measure.The quality group of surveyed mercaptan total amount accounts for 70.3% as methyl mercaptan, and ethyl mercaptan accounts for 24.4%,
Propanethiol accounts for 5.3%.
Caustic wash unit and two-phase mixtures reactor used by anti-extraction unit are as shown in Figure 1.In two-phase mixtures reactor
Including 5 two-phase mixtures units, for caustic wash unit, the liquefied gas containing mercaptan enters two-phase mixtures via continuous phase entrance 1
In the distributing chamber 7 containing distributed component 8 of reactor, and mixing runner 5 is entered by mixing flow channel entry point 11.It is a concentration of
The NaOH aqueous solutions of 15wt% form drop through distribution hole 3 by dispersed phase runner and enter mixing runner 5, perpendicular to lye flowing side
To dispersed phase runner cross-sectional area be 15mm2, the cross-sectional area perpendicular to the mixing runner of lighter hydrocarbons flow direction is 3mm2,
The length for mixing runner is 200mm, and the length ratio for shunting mixed zone and two-phase mixtures area is 2：1.The quantity of distribution hole 3 is 4,
Distribution hole depth is 1.0mm, and according to flow direction of the lye in dispersed phase runner, the aperture of each distribution hole is respectively
The centre distance of 0.9mm, 1.0mm, 1.1mm and 1.2mm, two neighboring distribution hole are 23mm.Enter mixing runner 5 it
Before, the flow direction of liquefied gas and lye is adverse current, and one end of dispersed phase runner is blind end.Cross-channel structure size with it is mixed
It is identical to collaborate road.Caustic wash unit is in such a way that two two-phase mixtures reactors are used in series, according to logistics direction, the first order two
It is 50 DEG C to mix the temperature in reactor, pressure 1.2MPa；Temperature in the two-phase mixtures reactor of the second level is 50 DEG C, pressure
Power is 0.8MPa.
Liquefied gas is 6m/s, apparent stream of the lye in dispersed phase flow passage entry in the apparent velocity of mixing flow passage entry
Speed is 0.8m/s, and the content of mercaptan is 1000ppm in liquefied gas.Liquefied gas is sufficiently mixed biography with lye two-phase in mixing runner
After matter, continue hybrid reaction into cross-channel, draws reactor subsequently into collecting chamber 9, and from product exit 12, enter
Subsequent separation equipment is detached.
After being detached by first order two-phase mixtures reactor outflow fluid, liquefied gas enters second level two-phase mixtures reaction
Device continues desulfurization, and by the fluid of second level two-phase mixtures reactor discharge after separation, liquefied gas flows out caustic wash unit.
By in the liquefied gas of caustic wash unit, the content of mercaptan is 7.8ppm, desulfurization degree 99.22wt%.
Also be used in series using two two-phase mixtures reactors in anti-extraction unit, and the structure of two-phase mixtures reactor with
The two-phase mixtures structure of reactor of caustic wash unit is identical.The temperature of first order two-phase mixtures reactor is 50 DEG C, and pressure is
The temperature of 1.0MPa, second level two-phase mixtures reactor are 50 DEG C, pressure 0.6MPa.Table of the lye in mixing flow passage entry
Sight flow velocity is 6m/s, and gasoline is 1.2m/s in the apparent velocity of dispersed phase flow passage entry.It is entrained with two in lye after desulfurization
Sulfide, sulfur content 322ppm.Sulfur content in the regeneration lye obtained after anti-extraction unit is 9ppm.
Due to not adding any surface reactive material that can drop interfacial tension in reaction system, this height of system is utilized
The characteristics of interfacial tension, liquefied gas split-phase can be clarified rapidly with lye in precipitation apparatus, and occur without emulsion layer.
Embodiment 2
Embodiment 2 carries out lighter hydrocarbons desulfurization using two-phase mixtures reactor of the present invention, specifically as follows：
The method of the lighter hydrocarbons desulfurization of embodiment 2 is similar to Example 1, also includes that 5 two-phases are mixed in two-phase mixtures reactor
Unit is closed, except that：
Lighter hydrocarbons in the present embodiment are light petrol, and only there are one two-phase mixtures are anti-in caustic wash unit and anti-extraction unit
Answer device.
Selected light petrol is derived from Jiujiang Branch Company, SINOPEC, and hydro carbons volume basis forms such as
Shown in table 2.
2 light petrol hydro carbons volume basis of table forms
Acid mercaptan total amount in light petrol is measured using the method that GB/T 1792-1988 are provided, the composition of acid mercaptan
It is measured using GC-SCD chromatographies (PONA columns).The quality group of surveyed mercaptan total amount accounts for 8.89% as methyl mercaptan, and ethyl mercaptan accounts for
66.7%, propanethiol accounts for 24.4%.
In caustic wash unit：3 distribution holes are provided in each two-phase mixtures unit, distribution hole depth is 1.1mm, and is pressed
According to flow direction of the lye in dispersed phase runner, the aperture of each distribution hole is 1mm, the centre-to-centre spacing of two neighboring distribution hole
From being 25mm.Cross-sectional area perpendicular to the dispersed phase runner of lye flow direction is 20mm2, perpendicular to lighter hydrocarbons flow direction
Mixing runner cross-sectional area be 6mm2, cross-channel structure size with mixing runner it is identical.Mixing runner length be
The length ratio in 500mm, shunting mixed zone and two-phase mixtures area is 1：1.Temperature in two-phase mixtures reactor is 45 DEG C, and pressure is
1.2MPa.Light petrol is 8m/s, apparent stream of the lye in dispersed phase flow passage entry in the apparent velocity of mixing flow passage entry
Speed is 0.48m/s, and the content of mercaptan is 78ppm in liquefied gas.
By in the liquefied gas of caustic wash unit, the content of mercaptan is 2.4ppm, desulfurization degree 96.9wt%.
In anti-extraction unit：The two-phase mixtures of caustic wash unit in the structure and the present embodiment of two-phase mixtures reactor are anti-
Answer device structure identical.The temperature of two-phase mixtures reactor is 52 DEG C, pressure 1.0MPa.Table of the lye in mixing flow passage entry
Sight flow velocity is 7m/s, and gasoline is 2m/s in the apparent velocity of dispersed phase flow passage entry.Two sulphur are entrained in lye after desulfurization
Compound, sulfur content 40ppm.Sulfur content in the regeneration lye obtained after anti-extraction unit is 4ppm.
Remaining is in the same manner as in Example 1.
Comparative example 1
This comparative example is carried out using method similar to Example 2, the difference is that the two-phase mixtures reaction of this comparative example
Device is concatenated two identical micro- blenders of T-type (i.e. dispersed phase runner and the structure for mixing runner and directly intersecting vertically), often
The mixing runner cross-sectional area of a mixer is 4mm2, dispersed phase flow diameter is 2mm.The processing energy of the micro- blender of each T-type
Power uses the two-phase mixtures unit of two-phase mixtures reactor described in this patent identical with embodiment 2.
Remaining is in the same manner as in Example 1.
As a result：Due to the limitation of the structure and operating condition of T-type micro-mixer, it is more difficult to realize being sufficiently mixed and passing for two-phase
The desulfurization degree of matter, light petrol is 72%, has fully demonstrated two-phase mixtures reactor mass transfer effect provided by the invention in contrast
Rate height and the big feature of processing capacity.
Comparative example 2
This comparative example is carried out using method similar to Example 2, the difference is that the two-phase mixtures reaction of this comparative example
Device is packed extraction tower, and tower diameter 250mm, tower height 2m, bed stuffing height 1.5m, filler is to dissipate heap Raschig ring, Raschig ring
A diameter of 16mm..The processing capacity of packed tower uses the two-phase mixtures reactor described in this patent identical with embodiment 1.
Remaining is in the same manner as in Example 2.
As a result：The separating property data of the extraction tower of the de- and anti-extraction unit of the extraction tower of caustic wash unit compare with implementing 2
It is closer to, but continuous phase load of the two-phase mixtures reactor provided by the invention on unit cross-sectional area is equivalent to extraction tower
1500 times or more, fully demonstrated that two-phase mixtures reactor volume provided by the invention is small, processing capacity is big, passes in contrast
The efficient feature of matter.
From the embodiment of the present invention 1 and 2 and the result of comparative example 1 and 2 to can be seen that two-phase mixtures using the present invention anti-
When device being answered to carry out lighter hydrocarbons desulfurization, the desulfurization effect of acquirement is obviously better than the desulfurization effect of the prior art.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (19)
1. a kind of method of lighter hydrocarbons desulfurization, which is characterized in that sulfur-bearing lighter hydrocarbons and lye are introduced into respectively in two-phase mixtures reactor, gently
Hydrocarbon is sufficiently mixed with lye to react, and the acid sulfur-containing compound in lighter hydrocarbons is reacted with alkali generates the sulfur-containing compound being soluble in the aqueous phase
Salt, the two-phase mixture after reaction draw reactor through product exit, obtain desulfurization light hydrocarbon product after water-oil phase separation and contain
Sulphur lye；
The two-phase mixtures reactor includes dispersed phase entrance and the continuous phase entrance (1) being sequentially communicated, two-phase mixtures area, divides
Flow mixed zone and product exit (12)；Wherein, the two-phase mixtures area is made of at least one two-phase mixtures unit, described
Two-phase mixtures unit includes mixing runner (5) and the dispersed phase runner (2) for being set to mixing runner (5) side, the mixing
Runner (5) is connected to by the distribution hole (3) being set on the flow path wall (4) of mixing runner (5) with the dispersed phase runner (2),
The setting of the entrance of the dispersed phase runner (2) makes in dispersed phase runner (2) fluid flow direction and mixes stream in runner (5)
Body flow direction is opposite；The entrance of the continuous phase entrance connection mixing runner.
2. lighter hydrocarbons sulfur method described in accordance with the claim 1, which is characterized in that further include step (2), step (3)：
(1) lighter hydrocarbons sulfur method described in claim 1 is used in caustic wash unit；
(2) lye of sulfur-bearing contacts in oxidation regeneration unit with oxygen-containing gas, and the salt and oxygen of the sulfur-containing compound in lye are anti-
Disulphide should be generated, the lye containing a small amount of disulphide is obtained after isolating disulphide；
(3) lye in step (2) comes into full contact in anti-extraction unit with light hydrocarbon oil, and the disulphide in lye is dissolved in lightweight
In hydrocarbon ils, regeneration lye is obtained after two-phase laminated flow and is recycled back to recycling in step (1).
3. lighter hydrocarbons sulfur method according to claim 2, which is characterized in that the anti-extraction unit in step (3) uses institute
The two-phase mixtures reactor stated.
4. according to any lighter hydrocarbons sulfur method in claim 1-3, which is characterized in that the continuous phase entrance
(1) it is communicated with the two-phase mixtures area through distributing chamber (7), setting fluid distrbution component (8) in the distributing chamber (7).
5. according to any lighter hydrocarbons sulfur method in claim 1-3, which is characterized in that the two-phase mixtures area with
The length ratio of the shunting mixed zone is 0.05~5.
6. according to any lighter hydrocarbons sulfur method in claim 1-3, which is characterized in that the dispersed phase runner
(2) one end is entrance, and the other end for being provided with the distribution hole is blind end.
7. according to any lighter hydrocarbons sulfur method in claim 1-3, which is characterized in that the dispersed phase runner (2)
Cross-sectional area be 1-40mm2, the cross-sectional area of the mixing runner (5) is 0.5-10mm2, the dispersed phase runner (2) and mixed
The cross-sectional shape for collaborating road (5) is rectangle.
8. according to any lighter hydrocarbons sulfur method in claim 1-3, which is characterized in that the dispersed phase runner (2)
Cross-sectional area be 2-30mm2；The cross-sectional area of the mixing runner (5) is 1-6mm2。
9. according to any lighter hydrocarbons sulfur method in claim 1-3, which is characterized in that of the distribution hole (3)
Number is 1-10.
10. according to any lighter hydrocarbons sulfur method in claim 1-3, which is characterized in that the hole of the distribution hole (3)
Diameter is each independently 0.1-2mm, and the centre distance of two neighboring distribution hole (3) is 0.5-40mm.
11. lighter hydrocarbons sulfur method according to claim 10, which is characterized in that when distribution hole is multiple, along dispersed phase
The aperture of distribution hole described in fluid flow direction is sequentially increased in runner (2), and the aperture of adjacent distribution hole (3) differs 0.01-
1mm。
12. according to any lighter hydrocarbons sulfur method in claim 1-3, which is characterized in that the depth of the distribution hole (3)
Degree is 0.1-3mm.
13. according to any lighter hydrocarbons sulfur method in claim 1-3, which is characterized in that the shunting mixed zone
The interior multiple diverter members (6) of setting, the webbed cross-channel of shape (24).
14. lighter hydrocarbons sulfur method according to claim 13, which is characterized in that the width of the cross-channel (24) is
0.5~5mm is highly 0.5~5mm.
15. according to the lighter hydrocarbons sulfur method described in claims 1 or 2, which is characterized in that the two-phase mixtures reactor
Operating condition：Reaction temperature is 25-80 DEG C, reaction pressure 0.2-2MPa.
16. lighter hydrocarbons sulfur method according to claim 15, which is characterized in that the lighter hydrocarbons as continuous phase are in mixing runner
The apparent velocity of inlet is 0.5-20m/s, and the lye as dispersed phase is 0.2-5m/s in the apparent velocity of dispersed phase entrance.
17. according to lighter hydrocarbons sulfur method according to claim 2 or 3, which is characterized in that the operation item of the anti-extraction unit
Part：Reaction temperature is 25-80 DEG C, reaction pressure 0.2-2MPa.
18. lighter hydrocarbons sulfur method described in accordance with the claim 3, which is characterized in that in anti-extraction unit two-phase mixtures reactor,
Lye as continuous phase is 0.5-20m/s in the apparent velocity of mixing flow passage entry, and the lighter hydrocarbons as dispersed phase are disperseing
The apparent velocity of phase entrance is 0.2-5m/s.
19. realizing the lighter hydrocarbons desulfurizer of any lighter hydrocarbons sulfur method in claim 1-14, including caustic wash unit, sedimentation list
Member, oxidation regeneration unit and anti-extraction unit, which is characterized in that the caustic wash unit and/or the anti-extraction unit are adopted
With the two-phase mixtures reactor.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1693423A (en) * | 2005-04-29 | 2005-11-09 | 清华大学 | Process for treating oil by alkali washing |
| CN103298914A (en) * | 2011-01-31 | 2013-09-11 | 摩瑞奇曼公司 | Hydrocarbon treatment process |
| WO2014039350A1 (en) * | 2012-09-04 | 2014-03-13 | Uop Llc | Process and apparatus for extracting sulfur compounds in a hydrocarbon stream |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1693423A (en) * | 2005-04-29 | 2005-11-09 | 清华大学 | Process for treating oil by alkali washing |
| CN103298914A (en) * | 2011-01-31 | 2013-09-11 | 摩瑞奇曼公司 | Hydrocarbon treatment process |
| WO2014039350A1 (en) * | 2012-09-04 | 2014-03-13 | Uop Llc | Process and apparatus for extracting sulfur compounds in a hydrocarbon stream |
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