CN106552523B - Two-phase mixtures unit and two-phase mixtures reactor and its application - Google Patents
Two-phase mixtures unit and two-phase mixtures reactor and its application Download PDFInfo
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- CN106552523B CN106552523B CN201510640035.6A CN201510640035A CN106552523B CN 106552523 B CN106552523 B CN 106552523B CN 201510640035 A CN201510640035 A CN 201510640035A CN 106552523 B CN106552523 B CN 106552523B
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Abstract
The present invention relates to refining arts, disclose a kind of two-phase mixtures unit and a kind of two-phase mixtures reactor and its application, the two-phase mixtures unit includes mixing runner (5) and the dispersed phase runner (2) for being set to mixing runner (5) side, mixing runner (5) passes through the distribution hole (3) being set on the flow path wall (4) of mixing runner (5) and is connected to the dispersed phase runner (2), wherein, the setting of the entrance of the dispersed phase runner (2) is so that fluid is opposite with the flow direction in mixing runner (5) in the flow direction in dispersed phase runner (2).Reaction process can be strengthened when carrying out lighter hydrocarbons desulfurization using two-phase mixtures reactor of the present invention, the requirement of the deep desulfuration of sulfur-bearing lighter hydrocarbons is met under low mass transfer Impetus Condition.
Description
Technical field
The present invention relates to refining arts, and in particular, to a kind of two-phase mixtures unit, a kind of two-phase mixtures reactor and its
Using.
Background technique
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, the industrial general method by alkali cleaning remove acid sulphur-containing substance.
Since the technology that the method by alkali cleaning carries out the lighter hydrocarbons desulfurization such as liquefied gas and light petrol 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 lower.Fiber film abstractor is a kind of cocurrent behaviour
Make equipment, equipment scale is small compared with extraction tower, and provides biggish mass transfer area using hydrophilic fibre silk, therefore mass transfer is imitated
Rate is higher, but fiber filament can lose hydrophily because of contaminated after being used for a long time, and mass-transfer efficiency reduces, and is difficult to clear up
Regeneration.The equipment scale of motionless mixer is minimum, mixes 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.
Summary of the invention
It is suitable under low mass transfer Impetus Condition the purpose of the present invention is on the basis of existing technology, providing a kind of satisfaction
The two-phase mixtures unit and two-phase mixtures reactor mixed for liquid-liquid diphase or gas-liquid two-phase.
To achieve the goals above, on the one hand, the present invention provides a kind of two-phase mixtures unit, which includes
Mixing runner and the dispersed phase runner for being set to the mixing runner side, the mixing runner pass through the stream for being set to mixing runner
Distribution hole on road wall is connected to the dispersed phase runner, wherein the setting of the entrance of the dispersed phase runner is so that fluid exists
Flow direction in dispersed phase runner is opposite with the flow direction in mixing runner.
Second aspect, the present invention provide a kind of two-phase mixtures reactor, the two-phase mixtures reactor include continuous phase entrance,
Dispersed phase entrance, at least one two-phase mixtures unit and product exit, the two-phase mixtures unit are two-phase of the present invention
Mixed cell, the entrance of the continuous phase entrance connection mixing runner, the dispersed phase entrance is connected to described
The entrance of dispersed phase runner, the outlet of the product exit connection mixing runner.
The third aspect, the present invention provide the two-phase mixtures reactor in liquid-liquid diphase or gas-liquid two-phase mixing and reaction
Application.
Two-phase mixtures unit provided by the invention, two-phase mixtures reactor and its application have the beneficial effect that
Using two-phase mixtures reactor of the present invention carry out lighter hydrocarbons desulfurization when can under low mass transfer Impetus Condition,
Strengthen reaction process, reactor for treatment amount is big, and structure is simple, and size is small, is easily installed and safeguards.
Two-phase mixtures reactor provided by the invention, before two-phase mixtures contact, flowing side of the two-phase in respective runner
To preferably countercurrent flow, reflux type can make the pressure difference of each distribution hole two sides be uniformly distributed, and a phase can be equably
From each distribution hole flow out and with another mixing that is in contact, thus in two-phase mixtures reactor realization multistage cross flow be mixed
Effect, strengthen mass-transfer performance, avoiding the part distribution hole as caused by Pressure difference distribution is uneven can not push fluid out, thus
The phenomenon that reducing mass-transfer efficiency.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, 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 unit of the invention.
Fig. 2 is the structural schematic diagram of two-phase mixtures reactor of the invention.
Fig. 3 is the flow chart of the method for lighter hydrocarbons deep desulfuration of the invention.
Description of symbols
1 mixing 2 dispersed phase runner of flow channel entry point
3 distribution hole, 4 flow path wall
5 mixing 6 fiber filaments of runner
7 distributing chamber, 8 distributed component
9 collecting chamber, 10 drop
11 continuous phase entrance, 12 product exit
13 sulfur-bearing lighter hydrocarbons, 14 caustic wash unit
15 regeneration 16 sedimentation units of lye
The anti-extraction unit of 17 oxidation regeneration unit 18
19 light-end products, 20 oxygen-containing gas
The 22 desulfurization lighter hydrocarbons of light-end products of 21 sulfur compounds
23 mixed alkali liquors
Specific embodiment
Detailed description of the preferred embodiments 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.
On the one hand, the present invention provides a kind of two-phase mixtures unit, which includes mixing runner and setting
Dispersed phase runner in the mixing runner side, the mixing runner pass through the distribution hole being set on the flow path wall of mixing runner
Be connected to the dispersed phase runner, wherein the setting of the entrance of the dispersed phase runner so that fluid in dispersed phase runner
Flow direction is opposite with the flow direction in mixing runner.
One end of the preferably described dispersed phase runner of two-phase mixtures unit of the invention is entrance, is provided with the distribution hole
The other end be closed end.
In two-phase mixtures unit provided by the invention, one end of the mixing runner is provided with entrance, other end setting
Outlet enables a kind of fluid to be introduced into mixing runner from the entrance of the mixing runner, and with from dispersed phase runner
One other fluid contact mixing, two-phase mixtures unit is discharged through the outlet of the mixing runner in the mixtures of two kinds of fluids.
Two-phase mixtures unit according to the present invention, in order to be avoided as caused by Pressure difference distribution unevenness to a greater degree
Part distribution hole can not push fluid out the problem of reducing mass-transfer efficiency, vertical in the preferably described dispersed phase runner of the present invention
In fluid flow direction cross-sectional area be 1-40mm2, more preferably 2-30mm2。
Two-phase mixtures unit according to the present invention, the shape to dispersed phase runner along fluid flow direction do not limit
System, it is preferable that the dispersed phase runner is cylindrical shape, Elliptic Cylinder shape or rectangular-shape, more preferably rectangular-shape.
In two-phase mixtures unit of the present invention, it was found by the inventors of the present invention that when vertical in the mixing runner
In fluid flow direction cross-sectional area be 0.5-10mm2When, more preferably 1-6mm2When, using containing of the present invention
When the two-phase mixtures reactor of two-phase mixtures unit carries out lighter hydrocarbons desulphurization reaction, higher desulfuration efficiency can be obtained.To mixing
There is no limit along the shape of fluid flow direction for runner, it is preferable that the mixing runner can be cylindrical shape, Elliptic Cylinder shape
Or rectangular-shape, preferably rectangular-shape.
In two-phase mixtures unit of the invention, the length of the preferably described mixing runner is 50-2000mm, more preferably
200-1000mm。
In two-phase mixtures unit of the present invention, the number of the distribution hole is at least 1.It is preferred that the distribution hole
Number be 2-10, more preferably 3-5.
Two-phase mixtures unit according to the present invention, the flowing of the axial direction of the distribution hole and the fluid mixed in runner
The angle in direction is any angle, and the preferably described angle is 45-90 degree, more preferably 90 degree.
Two-phase mixtures unit according to the present invention, wherein the aperture of multiple distribution holes can be identical or different,
It is preferred that being each independently 0.1-2mm；More preferably 0.3-1.2mm.
Two-phase mixtures unit according to the present invention, in order to be avoided as caused by Pressure difference distribution unevenness to a greater degree
Part distribution hole can not push fluid out, thus the problem of reducing efficiency, according to the flow direction of the fluid in dispersed phase runner,
By upstream to downstream, the aperture of the preferably described distribution hole is sequentially increased.
In two-phase mixtures unit of the present invention, according to the flow direction of the fluid in dispersed phase runner, preferably on
The small 0.01-1mm in aperture of the adjacent distribution hole in the aperture ratio downstream of the distribution hole of trip；More preferable small 0.05-1mm.
In two-phase mixtures unit of the present invention, the preferably described distribution hole is along the fluid in the dispersed phase runner
Flow direction is point-blank set gradually.But the setting of the distribution hole is not limited thereto, when the distribution hole
When number is more than one, the distribution hole can not also be along the straight line parallel with the fluid flow direction in dispersed phase runner
Setting.
Two-phase mixtures unit according to the present invention, wherein the centre distance of preferred two neighboring distribution hole is 0.5-
40mm；More preferably 10-30mm.The centre distance of the two neighboring distribution hole refers to perpendicular in the dispersed phase runner
Fluid flow direction and respectively pass through two neighboring distribution hole the distance between the straight line at center.
Two-phase mixtures unit according to the present invention, wherein the depth of the distribution hole can be 0.1-3mm；It is preferred that
The depth of the distribution hole is 0.3-2.5mm；More preferably 0.5-2mm.
In two-phase mixtures unit of the present invention, it is preferable that be provided with fiber filament in the mixing runner.
In two-phase mixtures unit of the present invention, at least one fiber filament can be set in the mixing runner.Institute
Stating filametntary material can be the inorganic material such as metal, glass, be also possible to organic material, or the above different materials are answered
Condensation material.Filametntary selection is depending on the property of the fluid in dispersed phase runner, if in dispersed phase runner
Fluid be aqueous solution, the hydrophilic materials such as stainless steel or glass can be selected in fiber filament；If in dispersed phase runner
Fluid is oil product, and lipophilic organic material can be selected in fiber filament.It is preferred that the filametntary diameter is 1 μm to 5mm, more preferably
It is 2-50 μm.Fiber filament is added in mixing runner, drop can be formed by with the fluid in dispersed phase runner by it
Compatibility, form very thin liquid film in filament surface, increase the interphase mass transfer area in two-phase mixtures unit, shorten mass transfer
Distance improves mixing efficiency.
In two-phase mixtures unit of the present invention, to the filametntary diameter and length, there is no particular limitation,
Those skilled in the art can select according to conventional parameter in the art.The filametntary length can be according to described
Mix the length of runner and be arranged, it is described it is filametntary can be through entire mixing runner, preferably according to the stream in mixing runner
Body flow direction, the filametntary length are from the central point of the distribution hole of most downstream to the distance of mixing runner exit.
Under preferable case, in two-phase mixtures unit of the present invention, the fiber filament is linear or helical form.
A kind of preferred embodiment according to the present invention, the structure of two-phase mixtures unit of the present invention is as schemed
Shown in 1, specifically:
Two-phase mixtures unit includes the dispersed phase runner 2 for mixing runner 5 and being set to 5 side of mixing runner, described mixed
Interflow road 5 passes through the distribution hole 3 being set on the flow path wall 4 of mixing runner 5 and is connected to the dispersed phase runner 2, wherein described
The setting of the entrance of dispersed phase runner 2 so that fluid in dispersed phase runner 2 flow direction with mixing the flowing in runner 5
It is contrary.One end of the mixing runner 5 is provided with mixing flow channel entry point 1, and fiber filament 6 is set in the mixing runner 5,
Fluid from dispersed phase runner 2 is mixed with from the fluid for mixing flow channel entry point 1 in mixing runner 5 in the form of drop 10
It closes.
Second aspect includes continuous phase in the two-phase mixtures reactor the present invention provides a kind of two-phase mixtures reactor
Entrance, dispersed phase entrance, at least one two-phase mixtures unit and product exit, the two-phase mixtures unit are of the present invention
Two-phase mixtures unit, the entrance of the continuous phase entrance connection mixing runner, the dispersed phase entrance are connected to institute
The entrance for the dispersed phase runner stated, the outlet of the product exit connection mixing runner.
In the present invention, it should be strongly noted that the two-phase mixtures unit in two-phase mixtures reactor is the present invention
Two-phase mixtures unit above-mentioned, therefore, the arbitrary characteristics in aforementioned two-phase mixtures unit are reacted in two-phase mixtures of the invention
In the range of two-phase mixtures unit in device, the present invention is in order to avoid repeating, and this is no longer going to repeat them, those skilled in the art
It should not be construed as limiting the invention.
Two-phase mixtures reactor according to the present invention preferably further includes collecting chamber in the two-phase mixtures reactor and is contained
It is distributed the distributing chamber of component, and according to the flow direction of the fluid in the mixing runner, the two-phase mixtures reaction
Distributing chamber, two-phase mixtures unit and collecting chamber are set gradually in device.
In two-phase mixtures reactor of the present invention, the fluid being preferred from dispersed phase runner is dispersed phase；Come
It is continuous phase from the fluid of continuous phase entrance.
Two-phase mixtures reactor according to the present invention, under preferable case, in order to guarantee that continuous phase can equably lead to
Each two-phase mixtures unit is crossed, the distributing chamber containing distributed component is set preferably in two-phase mixtures reactor, to guarantee material
It can be uniformly across each two-phase mixtures unit.In two-phase mixtures reactor, after continuous phase enters distributing chamber, distributed component
It is able to suppress the excessive problem of the fluid flow of the mixing runner of two-phase mixtures unit placed in the middle, increases the stream of distributed component two sides
Body flow, the material that may be implemented in each two-phase mixtures unit in this way can be uniformly distributed.The form of distributed component can band
There are the feature structures such as sieve pore, item seam, multi-disc distributed component also can be set, the shape of distributed component can be rectangle, diamond shape etc.
Shape.
A kind of preferred embodiment according to the present invention, the structure of two-phase mixtures reactor of the present invention is such as
Shown in Fig. 2, specifically: include in the two-phase mixtures reactor continuous phase entrance 11, product exit 12, collecting chamber 9, containing being distributed
The distributing chamber 7 of component 8 and 5 two-phase mixtures units, wherein each two-phase mixtures unit include mixing flow channel entry point,
Dispersed phase runner (not shown), distribution hole 3, flow path wall 4, mixing runner 5 and fiber filament 6, wherein dispersed phase runner and mixed flow
Road 5 is arranged in parallel in the two sides of flow path wall 4, and distribution hole 3 is set on flow path wall 4, and the dispersed phase runner and mixing runner 5 are logical
It crosses the distribution hole 3 and keeps connection；The setting of dispersed phase entrance so that flow direction of the dispersed phase in dispersed phase runner with from
Flow direction of the continuous phase that continuous phase entrance is introduced into mixing runner 5 is opposite；The fiber filament 6 is arranged in the mixed flow
In road 5, wherein outside introduces continuous phase into two-phase mixtures reactor by continuous phase entrance 11, and passes through product exit
12 draw reaction product from the two-phase mixtures reactor.
The third aspect, the present invention provides the two-phase mixtures reactors in liquid-liquid diphase or gas-liquid two-phase mixing and reaction
In application.Hybrid reaction process including water phase with oily phase, the hybrid extraction process of water phase and oily phase, gas phase and liquid phase are mixed
Reaction process etc. is closed, specifically, such as can be used for solvent deasphalting process or aqueous solution absorption H2The soluble gas such as S
Process.
Under preferable case, two-phase mixtures reactor provided by the invention is used for lighter hydrocarbons deep desulfurization process.The lighter hydrocarbons
For the petroleum hydrocarbon-fraction of the C4-C5 containing acid sulphur-containing substance, wherein the acid sulphur-containing substance is mercaptan, in terms of element sulphur
Sulfur content in the lighter hydrocarbons is 50-2000ppm.
Specifically, a kind of method of lighter hydrocarbons deep desulfuration, including caustic wash unit, sedimentation unit, oxidation regeneration unit and anti-
Extraction unit, lighter hydrocarbons are by caustic wash unit and the contained acid sulphur-containing substance of sedimentation unit removal, and lye passes through oxidation regeneration
Unit and anti-extraction unit realize regeneration.
In the present invention, it includes at least one two-phase mixtures unit that the caustic wash unit, which may include of the present invention,
Two-phase mixtures reactor, the two-phase mixtures unit include the dispersed phase stream for mixing runner and being set to the mixing runner side
Road, the mixing runner pass through the distribution hole being set on the flow path wall of mixing runner and are connected to the dispersed phase runner, wherein
The setting of the entrance of the dispersed phase runner so that flow direction of the fluid in dispersed phase runner with mixing the stream in runner
It moves contrary.If the treating capacity of lighter hydrocarbons is low, lighter hydrocarbons sweetening process directly can also be carried out using individual two-phase mixtures unit.
In the present invention, it should be strongly noted that the two-phase mixtures reactor in method of the invention is the present invention
Two-phase mixtures reactor above-mentioned, and wherein contain two-phase mixtures unit, therefore, aforementioned two-phase mixtures unit and two-phase mixtures
In the range of method of the invention, present invention's arbitrary characteristics in reactor no longer goes to live in the household of one's in-laws on getting married one by one herein in order to avoid repeating
It states, those skilled in the art should not be construed as limiting the invention.
The step of caustic wash unit in the method for lighter hydrocarbons deep desulfuration of the invention includes: by lye from dispersed phase runner
Entrance is introduced into dispersed phase runner, the lye pass through be arranged in mixing runner flow path wall on distribution hole with mix in runner
Lighter hydrocarbons hybrid reaction, wherein flow direction of the lye in dispersed phase runner is with the lighter hydrocarbons in mixing runner
Flow direction is opposite.
In the method for lighter hydrocarbons deep desulfuration of the present invention, in the liquid liquid two phase flow that lye and lighter hydrocarbons are formed, one
It is mutually used as continuous phase, another phase is as dispersed phase.For the two-phase mixtures reactor of caustic wash unit, preferably sulfur-bearing lighter hydrocarbons are as company
Continuous phase, lye is as dispersed phase；And for the two-phase mixtures reactor of anti-extraction unit, preferably lye is continuous phase, lightweight vapour
Oil is dispersed phase.In the present invention, the petroleum benzin as dispersed phase can be conventional use of various gasoline in the art, preferably
In the case of be the lower gasoline of sulfur content.
In the method for lighter hydrocarbons deep desulfuration of the present invention, NaOH can be contained in the lye, preferably NaOH's
Concentration is 10-20% (w/w).In the caustic wash unit, the acid sulphur-containing substance in lighter hydrocarbons is reacted with NaOH generates sulfur-bearing sodium
Salt, and sulfur-bearing sodium salt is dissolved in lye.Enter in the precipitation apparatus of caustic wash unit by the lighter hydrocarbons and lye of desulphurization reaction
After being separated, after lighter hydrocarbons enter sedimentation unit and are sufficiently separated with the lye wherein carried secretly, the lighter hydrocarbons of the desulfurization can be with
It is continued with into processes such as subsequent washing purifications.
In the method for lighter hydrocarbons deep desulfuration of the present invention, the sulfur-bearing lye and sedimentation unit that are discharged by caustic wash unit
Discharge sulfur-bearing lye mixing after enter oxidation regeneration unit in, with oxygen-containing gas (typically air, oxygen rich gas or
Oxygen) it is contacted.The reactor of oxidation regeneration unit typically bubbling bed reactor and/or the reaction of filler bubbling bed
Device.In the reactor of oxidation regeneration unit, sulfur-bearing sodium salt and oxygen-containing gas in sulfur-bearing lye (contain sulfonation phthalein in catalyst
The ARI 100EXL catalyst of cyanines cobalt or other substances with catalytic action) under the action of react, by containing in sulfur-bearing lye
Sulphur sodium salt is converted into disulphide not soluble in water, the lye after obtaining desulfurization.
In the method for lighter hydrocarbons deep desulfuration of the present invention, disulphide does not dissolve in lye, therefore again by oxidation
The precipitation apparatus in unit is given birth to separate the lye after disulphide and desulfurization.Since the density of lye and disulphide connects very much
Closely, it still containing a large amount of disulphide in the lye after the desulfurization being discharged by oxidation regeneration unit, needs to enter anti-extraction unit
The separation of lye and disulphide after continuing desulfurization.Under preferable case, institute of the present invention is used in the anti-extraction unit
The two-phase mixtures reactor stated.
In the method for lighter hydrocarbons deep desulfuration of the present invention, in the anti-extraction unit, by the lye after desulfurization
It is soluble in light-end products therein such as gasoline in the two-phase mixtures reactor with disulphide to contact, after realizing desulfurization
The separation of lye and the disulphide wherein carried secretly obtains regeneration lye.Precipitation apparatus through anti-extraction unit, regeneration lye with
Light-end products separation containing disulphide, is recycled back to the caustic wash unit for the regeneration lye and carries out lighter hydrocarbons desulfurization.Described
It is similar to the operating method of caustic wash unit using the operating method of two-phase mixtures reactor of the present invention in anti-extraction unit,
Details are not described herein by the present invention.
In the method for lighter hydrocarbons deep desulfuration of the present invention, the reaction condition of the preferably described caustic wash unit includes: anti-
Answering temperature is 25-80 DEG C, reaction pressure 0.2-2MPa.
The method of lighter hydrocarbons deep desulfuration according to the present invention, preferably apparent velocity of the dispersed phase in dispersed phase inlet
For 0.2-5m/s, more preferably 0.3-3m/s.
In the method for lighter hydrocarbons deep desulfuration of the present invention, the reaction condition of the preferably described anti-extraction unit includes:
Reaction temperature is 25-80 DEG C, reaction pressure 0.2-2MPa.
The apparent stream of the method for lighter hydrocarbons deep desulfuration according to the present invention, preferably continuous phase in mixing flow passage entry
Speed is 0.5-20m/s, more preferably 4-10m/s.
In the method for lighter hydrocarbons deep desulfuration of the present invention, swiftly flowing liquid liquid two in two-phase mixtures reactor
It is mutually vigorously mixed, the drop and continuous mix that dispersed phase is formed acutely reach turbulence state, and resistance to mass tranfer is low, enables to two
Mass transport process between phase sufficiently carries out, and desulfuration efficiency can reach 90% or more, that is to say, that can make in caustic wash unit
Contained acidity sulphur-containing substance (such as mercaptan) is sufficiently reacted with lye in lighter hydrocarbons, realizes the deep desulfuration of lighter hydrocarbons, acid sulfur-bearing object
Matter removal efficiency is greater than 90% (w/w), and the mass concentration of acid sulphur-containing substance can be down to 10ppm or less in lighter hydrocarbons；And it is mentioned in back suction
Being sufficiently mixed for lye and light-end products may be implemented in unit, and the disulphide of entrained in the lye after desulfurization is extracted to oil
The extraction yield of Xiang Zhong, disulphide are greater than 90% (w/w).
In the method for lighter hydrocarbons deep desulfuration of the present invention, the pressure drop preferably in two-phase mixtures reactor is 10-
800kPa；More preferably 100-600kPa.Dispersed phase forms drop after distribution hole and is mixed with continuous phase.Due to distribution
The diameter in hole is smaller, therefore the size of drop is also smaller, can obtain biggish interphase mass transfer area.
Two-phase mixtures reactor provided by the invention can be to two since the movement velocity of dispersed phase and continuous phase is very high
The runner for mixing reactor is adequately washed away, and the problem of runner blocks during long-term operation is avoided.It considers
This higher feature of the interfacial tension of liquid liquid system, method of the invention realize that lighter hydrocarbons depth is de- by being vigorously mixed for two-phase
The purpose of sulphur in liquid liquid two-phase contact process and does not use any substance (such as surface-active with reduction system tension
Agent, alcohols etc.) promote two-phase mixtures to contact, therefore avoid the emulsion of system, split-phase is imitated after two-phase mixtures contact
Fruit is good, and not additional waste material generates.
In two-phase mixtures reactor of the present invention, by anti-extraction unit be discharged regeneration lye in sulfur content compared with
It is low, sulfur content, therefore institute in the regeneration lye of return caustic wash unit can hardly be further decreased using other extraction steps
The sulphur contained will not be extracted substantially by lighter hydrocarbons in alkaline cleaning procedure and be impacted to the desulfurization degree in lighter hydrocarbons.
According to the treating capacity of the concentration of the acid sulphur-containing substance in lighter hydrocarbons and lighter hydrocarbons, two-phase provided by the invention can be mixed
It closes reactor and carries out separate unit or multi-platform combined use.
Preferred embodiment according to the present invention invents the two-phase mixtures reactor of offer using more series connection shapes
Formula uses, and the reaction condition in each two-phase mixtures reactor can be identical or different, each independently includes: reaction temperature
Degree is 25-80 DEG C, reaction pressure 0.2-2MPa.
The method of a kind of preferred embodiment according to the present invention, lighter hydrocarbons deep desulfuration of the present invention uses
Technique in flow chart shown in Fig. 3 carries out, specifically:
In the method for lighter hydrocarbons deep desulfuration of the present invention, regeneration lye 15 and sulfur-bearing lighter hydrocarbons 13 are introduced into alkali cleaning list
In member 14, in the caustic wash unit 14, the acid sulphur-containing substance in sulfur-bearing lighter hydrocarbons 13 is reacted with NaOH generates sulfur-bearing sodium salt, and
And sulfur-bearing sodium salt is dissolved in lye.The alkali for entering sedimentation unit 16 by the sulfur-bearing lighter hydrocarbons 13 of caustic wash unit 14 and wherein carrying secretly
Liquid obtains desulfurization lighter hydrocarbons 22 after being sufficiently separated, desulfurization lighter hydrocarbons 22, which enter the processes such as subsequent washing purification, to carry out continuing to locate
Reason.The lye and the lye from caustic wash unit 14 being discharged by sedimentation unit 16 are formed together mixed alkali liquor 23 into oxidation regeneration
In unit 17, contacted with oxygen-containing gas 20.In the reactor of oxidation regeneration unit 17, sulfur-bearing sodium salt in lye with contain
Carrier of oxygen 20 reacts, and converts disulphide for the sulfur-bearing sodium salt in lye, the lye after obtaining desulfurization.By oxidation regeneration unit
Lye after the desulfurization of 17 discharges enters the separation that anti-extraction unit 18 continues lye and disulphide after desulfurization.Institute
State in anti-extraction unit 18, the lye after desulfurization is contacted with light-end products 19, realize desulfurization after lye with wherein carry secretly two
The separation of sulfide obtains the light-end products 21 of regeneration lye 15 and sulfur compound.The regeneration lye 15 is recycled back to described
Caustic wash unit 14 carries out lighter hydrocarbons desulfurization.
In the present invention, it should be strongly noted that regeneration lye can be concomitantly introduced into of the invention two with fresh lye
It mixes in the dispersed phase runner of unit, fresh lye is not shown in Fig. 3 of the invention, but this is those skilled in the art's public affairs
Know.
Two-phase mixtures unit, two-phase mixtures reactor and its application provided by the invention also have the advantages that following specific:
Two-phase mixtures reactor is coupled in lighter hydrocarbons doctor process, the special construction design of two-phase mixtures reactor was both
Above-mentioned reaction process can be strengthened, and can be with idetified separation process.Two-phase mixtures reactor uses special mixing runner design,
Liquid liquid two-phase mixed at high speed in two-phase mixtures reactor, enhances mass transport process, realizes lighter hydrocarbons deep desulfuration, can will be light
Acid sulphur-containing substance concentration in hydrocarbon is down to the even lower level of 10ppm, and desulfurization degree is up to 90% (w/w) or more.Two-phase mixtures
The problem of two-phase apparent velocity is high in reactor, is not susceptible to runner blocking.Utilize the high feature of interface tension, it is not necessary to make
With surface reactive material, emulsification problem is avoided in two-phase mixtures reactor, after two-phase mixtures contact, convenient for split-phase and after carrying out
Continuous processing.The treating capacity of two-phase mixtures reactor is big, and structure is simple, and size is small, is easily installed and safeguards.
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
The present embodiment carries out lighter hydrocarbons desulfurization using two-phase mixtures reactor of the present invention, specifically as follows:
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 being entered sedimentation unit by the liquefied gas that caustic wash unit is discharged and separated with the part lye that it is carried secretly
Purpose.Oxidation regeneration unit is entered by the lye that sedimentation unit is discharged, in filler bubbling bed reactor, lye is contacted with air
Reaction, converts disulphide for sodium mercaptides.Lye after the desulfurization be discharged by oxidation regeneration unit enters anti-extraction unit, with
Gasoline contact, 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 petrochemical industry, and volume basis composition is as shown in table 1.
Table 1: liquefied gas hydro carbons volume basis composition
| 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 acid mercaptan total amount in liquefied gas is provided using SH/T 0222-92, the composition of acid mercaptan are adopted
It is measured with GC-SCD chromatography (PONA column).The quality group of surveyed mercaptan total amount becomes methyl mercaptan and accounts for 70.3%, 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 2.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 11
In the distributing chamber 7 containing distributed component 8 of reactor, and mixing runner 5 is entered by mixing flow channel entry point 1.Concentration is 15 weights
The NaOH aqueous solution for measuring % forms drop through distribution hole 3 by dispersed phase runner and enters mixing runner 5, perpendicular to lye flow direction
Dispersed phase runner cross-sectional area be 15mm2, the cross-sectional area perpendicular to the mixing runner of lighter hydrocarbons flow direction is 3mm2, mix
The length for collaborating road is 1000mm.The quantity of distribution hole 3 is 4, and distribution hole depth is 1.0mm, according to lye in dispersed phase stream
Flow direction in road, the aperture of each distribution hole are respectively 0.9mm, 1.0mm, 1.1mm and 1.2mm, two neighboring distribution hole
Centre distance be 23mm.Before entering mixing runner 5, the flow direction of liquefied gas and lye is adverse current, dispersed phase stream
The one end in road is dead end.Caustic wash unit is in such a way that two two-phase mixtures reactors are used in series, according to logistics direction, first
Temperature in grade two-phase mixtures reactor is 50 DEG C, pressure 1.2MPa；Temperature in the two-phase mixtures reactor of the second level is 50
DEG C, pressure 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
Enter collecting chamber 9 after matter, and draw reactor from product exit 12, is separated into subsequent separation equipment, wherein mixed
Collaborate in road 5 equipped with a branch of linear stainless steel fiber filament 6.
After being separated by the fluid that first order two-phase mixtures reactor flows out, it is anti-that liquefied gas enters second level two-phase mixtures
Device is answered to continue desulfurization, by the fluid of second level two-phase mixtures reactor discharge after separation, liquefied gas flows out alkali cleaning list
Member.By in the liquefied gas of caustic wash unit, the content of mercaptan is 8ppm, desulfurization degree is 99.2% (w/w).
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
1.0MPa, the temperature of 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 0.6m/s in the apparent velocity of dispersed phase flow passage entry.Two are entrained in lye after desulfurization
Sulfide, sulfur content 300ppm.The sulfur content in regeneration lye obtained after anti-extraction unit is 17ppm.
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 and lye split-phase can be clarified rapidly in precipitation apparatus, and occur without emulsion layer.
Embodiment 2
The present embodiment carries out lighter hydrocarbons desulfurization using two-phase mixtures reactor of the present invention, specifically as follows:
The method of lighter hydrocarbons desulfurization in the present embodiment is similar to embodiment 1, also includes 5 two in two-phase mixtures reactor
Unit is mixed, except that:
Lighter hydrocarbons in the present embodiment are light petrol, and it is anti-to only have a two-phase mixtures in caustic wash unit and anti-extraction unit
Answer device.
Selected light petrol is derived from Jiujiang petrochemical industry, and hydro carbons volume basis composition is as shown in table 2.
Table 2: light petrol hydro carbons volume basis composition
| N-alkane/% | Isoparaffin/% | Alkene/% | Diene/% | |
| C4 | 2.141 | 0.978 | 5.237 | 0 |
| C5 | 13.368 | 41.388 | 29.821 | 0.039 |
| C6 | 0 | 5.889 | 1.140 | 0 |
The method measurement that acid mercaptan total amount in light petrol is provided using GB/T 1792-1988, the composition of acid mercaptan
It is measured using GC-SCD chromatography (PONA column).The quality group of surveyed mercaptan total amount becomes methyl mercaptan and accounts for 8.89%, and ethyl mercaptan accounts for
66.7%, propanethiol accounts for 24.4%.
In caustic wash unit: being provided with 3 distribution holes 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 respectively 1.05mm, 0.8mm and 0.6mm, adjacent
The centre distance of two distribution holes is 25mm.Cross-sectional area perpendicular to the dispersed phase runner of lye flow direction is 20mm2,
Cross-sectional area perpendicular to the mixing runner of lighter hydrocarbons flow direction is 6mm2, the length for mixing runner is 500mm.Two-phase mixtures are anti-
Answering the temperature in device is 45 DEG C, pressure 1.2MPa.Light petrol is 8m/s in the apparent velocity of mixing flow passage entry, and lye exists
The apparent velocity of dispersed phase flow passage entry is 0.48m/s, and the content of mercaptan is 78ppm in light petrol.
By in the light petrol of caustic wash unit, the content of mercaptan is 2ppm, desulfurization degree is 97.4% (w/w).
In anti-extraction unit: the two-phase mixtures of the 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 46ppm.The sulfur content in regeneration lye obtained after anti-extraction unit is 3ppm.
Remaining is in the same manner as in Example 1.
Embodiment 3
The present embodiment carries out lighter hydrocarbons desulfurization using two-phase mixtures reactor of the present invention, specifically as follows:
The method of lighter hydrocarbons desulfurization in the present embodiment is similar to embodiment 2, except that:
In caustic wash unit: according to flow direction of the lye in dispersed phase runner, the aperture of each distribution hole is respectively
1mm, 0.7mm and 0.4mm, distribution hole depth are 1mm, and the centre distance of two neighboring distribution hole is 27mm.Perpendicular to lye
The cross-sectional area of the dispersed phase runner of flow direction is 8mm2, the cross-sectional area perpendicular to the mixing runner of lighter hydrocarbons flow direction is
5mm2, the length for mixing runner is 1000mm.Temperature in two-phase mixtures reactor is 50 DEG C, pressure 1.2MPa.Light petrol
It is 8m/s in the apparent velocity of mixing flow passage entry, lye is 1.25m/s in the apparent velocity of dispersed phase flow passage entry.This
Embodiment uses light petrol same as Example 2, and ethyl mercaptan is added thereto and makes sulphur in the light petrol of the present embodiment
The content of alcohol is 1000ppm.
By in the light petrol of caustic wash unit, the content of mercaptan is 27ppm, desulfurization degree is 97.3% (w/w).
In anti-extraction unit: the alkali cleaning list in the structure and the present embodiment of the two-phase mixtures reactor in anti-extraction unit
The two-phase mixtures structure of reactor of member is identical.The temperature of two-phase mixtures reactor is 52 DEG C, pressure 1.1MPa.Lye is mixing
The apparent velocity of flow passage entry is 6m/s, and gasoline is 3m/s in the apparent velocity of dispersed phase flow passage entry.Alkali after desulfurization
Disulphide, sulfur content 880ppm are entrained in liquid.The sulfur content in regeneration lye obtained after anti-extraction unit is
75ppm。
Remaining is in the same manner as in Example 2.
Embodiment 4
The method of lighter hydrocarbons desulfurization in the present embodiment is similar to embodiment 2, except that:
In the two-phase mixtures unit of the present embodiment, the aperture of distribution hole is 0.8mm.
Remaining is in the same manner as in Example 2.
As a result: by the light petrol of caustic wash unit, the content of mercaptan is 7.57ppm, desulfurization degree is 90.3% (w/w).
Disulphide, sulfur content 51ppm are entrained in lye after desulfurization.In the regeneration lye obtained after anti-extraction unit
Sulfur content is 5ppm.
Embodiment 5
The method of lighter hydrocarbons desulfurization in the present embodiment is similar to embodiment 3, except that:
In the two-phase mixtures unit of the present embodiment, the centre distance of two neighboring distribution hole is 32mm.
Remaining is in the same manner as in Example 3.
As a result: by the light petrol of caustic wash unit, the content of mercaptan is 96ppm, desulfurization degree is 90.4% (w/w).It is de-
Disulphide, sulfur content 345ppm are entrained in lye after sulphur.In the regeneration lye obtained after anti-extraction unit
Sulfur content is 41ppm.
Embodiment 6
The method of lighter hydrocarbons desulfurization in the present embodiment is similar to embodiment 1, except that:
In the two-phase mixtures unit of the present embodiment, the depth of distribution hole is 2.5mm.
Remaining is in the same manner as in Example 1.
As a result: by the liquefied gas of caustic wash unit, the content of mercaptan is 56ppm, desulfurization degree is 94.4% (w/w).It is de-
Disulphide, sulfur content 364ppm are entrained in lye after sulphur.In the regeneration lye obtained after anti-extraction unit
Sulfur content is 30ppm.
Comparative example 1
This comparative example is carried out using method similar to Example 2, the difference is that the two-phase mixtures of this comparative example react
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
Diameter is 16mm.The processing capacity of packed tower is identical as the ability of two-phase mixtures reactor used in 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 and 2 phases of implementation
Seemingly, 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 demonstrate that two-phase mixtures reactor volume provided by the invention is small, processing capacity is big, mass transfer in contrast
High-efficient feature.
Comparative example 2
This comparative example is carried out using method similar to Example 2, the difference is that the two-phase mixtures of this comparative example react
Device is concatenated two identical micro- blenders of T-type (i.e. dispersed phase runner with 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 each micro- blender of T-type
Power uses the processing capacity of a two-phase mixtures unit of two-phase mixtures reactor of the present invention identical with embodiment 2.
Remaining is in the same manner as in Example 2.
As a result: the desulfurization degree of light petrol is 72% (w/w), has fully demonstrated two-phase mixtures provided by the invention in contrast
The high feature of reactor mass-transfer efficiency.
It can be seen that from the result of the embodiment of the present invention 1-6 and comparative example 1-2 and reacted using two-phase mixtures of the invention
When device carries 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 within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, 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 where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
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 (18)
1. a kind of two-phase mixtures unit, which is characterized in that the two-phase mixtures unit is including mixing runner (5) and is set to the mixing
The dispersed phase runner (2) of runner (5) side, mixing runner (5), which passes through, to be set on the flow path wall (4) of mixing runner (5)
Distribution hole (3) be connected to the dispersed phase runner (2), wherein the setting of the entrance of the dispersed phase runner (2) is so that fluid
In dispersed phase runner (2) flow direction with mix flow direction in runner (5) on the contrary, the distribution hole (3)
Number is 3-10, and the aperture of the distribution hole (3) is each independently 0.1-2mm, and according to the stream in dispersed phase runner (2)
The flow direction of body, by upstream to downstream, the aperture of the distribution hole (3) is sequentially increased.
2. two-phase mixtures unit according to claim 1, which is characterized in that perpendicular to stream in the dispersed phase runner (2)
The cross-sectional area of body flow direction is 1-40mm2；One end of the dispersed phase runner (2) is entrance, is provided with point
The other end of cloth hole is closed end.
3. two-phase mixtures unit according to claim 1, which is characterized in that perpendicular to stream in the dispersed phase runner (2)
The cross-sectional area of body flow direction is 2-30mm2。
4. two-phase mixtures unit according to claim 1, which is characterized in that the dispersed phase runner (2) be cylindrical shape,
Elliptic Cylinder shape or rectangular-shape.
5. two-phase mixtures unit according to claim 1, which is characterized in that the dispersed phase runner (2) is rectangular-shape.
6. two-phase mixtures unit described in any one of -5 according to claim 1, which is characterized in that the mixing runner (5)
In perpendicular to fluid flow direction cross-sectional area be 0.5-10mm2。
7. two-phase mixtures unit described in any one of -5 according to claim 1, which is characterized in that the mixing runner (5)
In perpendicular to fluid flow direction cross-sectional area be 1-6mm2。
8. two-phase mixtures unit described in any one of -5 according to claim 1, which is characterized in that the mixing runner (5)
For cylindrical shape, Elliptic Cylinder shape or rectangular-shape.
9. two-phase mixtures unit described in any one of -5 according to claim 1, which is characterized in that the mixing runner (5)
For rectangular-shape.
10. two-phase mixtures unit according to claim 1, which is characterized in that according to the fluid in dispersed phase runner (2)
Flow direction, the small 0.01-1mm in aperture of the adjacent distribution hole (3) in the aperture ratio downstream of the distribution hole (3) of upstream.
11. two-phase mixtures unit according to claim 1, which is characterized in that the distribution hole (3) is along the dispersed phase
Runner (2), the centre distance of two neighboring distribution hole (3) are 0.5-40mm along fluid flow direction.
12. two-phase mixtures unit according to claim 1, which is characterized in that the depth of the distribution hole (3) is 0.1-
3mm。
13. two-phase mixtures unit according to claim 1, which is characterized in that the depth of the distribution hole (3) is 0.3-
2.5mm。
14. two-phase mixtures unit described in any one of -5 according to claim 1, which is characterized in that the mixing runner (5)
In be provided with fiber filament (6).
15. two-phase mixtures unit according to claim 14, which is characterized in that the fiber filament is linear or spiral
Shape.
16. a kind of two-phase mixtures reactor, which is characterized in that include continuous phase entrance, dispersed phase in the two-phase mixtures reactor
Entrance, at least one two-phase mixtures unit and product exit, the two-phase mixtures unit are any one of claim 1-15
The two-phase mixtures unit, the entrance of the continuous phase entrance connection mixing runner, the dispersed phase entrance
The entrance of the connection dispersed phase runner, the outlet of the product exit connection mixing runner.
17. two-phase mixtures reactor according to claim 16, which is characterized in that further include in the two-phase mixtures reactor
Collecting chamber (9) and the distributing chamber (7) for containing distributed component (8)；The continuous phase entrance is mixed through distributing chamber (7) connection is described
Collaborate the entrance in road, the outlet of the mixing runner product exit described through collecting chamber (9) connection.
18. two-phase mixtures reactor described in claim 16 or 17, in liquid-liquid diphase or gas-liquid two-phase mixing and reaction
Using.
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| JP2010172800A (en) * | 2009-01-28 | 2010-08-12 | Nakamura Bussan Kk | Apparatus and method for generating fine air bubbles |
| CN102258968A (en) * | 2004-11-16 | 2011-11-30 | 万罗赛斯公司 | Multiphase reaction process using microchannel technology |
| CN203874685U (en) * | 2014-05-22 | 2014-10-15 | 西安交通大学 | Novel Venturi mixer containing special guiding pipes at throat part |
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| CN102258968A (en) * | 2004-11-16 | 2011-11-30 | 万罗赛斯公司 | Multiphase reaction process using microchannel technology |
| JP2010172800A (en) * | 2009-01-28 | 2010-08-12 | Nakamura Bussan Kk | Apparatus and method for generating fine air bubbles |
| CN203874685U (en) * | 2014-05-22 | 2014-10-15 | 西安交通大学 | Novel Venturi mixer containing special guiding pipes at throat part |
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