CN106978207B - A kind of method of sulfur-bearing lighter hydrocarbons deep desulfuration - Google Patents
A kind of method of sulfur-bearing lighter hydrocarbons deep desulfuration Download PDFInfo
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- CN106978207B CN106978207B CN201610028953.8A CN201610028953A CN106978207B CN 106978207 B CN106978207 B CN 106978207B CN 201610028953 A CN201610028953 A CN 201610028953A CN 106978207 B CN106978207 B CN 106978207B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
- C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
- C10G2300/1092—C2-C4 olefins
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/06—Gasoil
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明涉及炼油领域，公开了一种含硫轻烃深度脱硫的方法，该方法包括：将碱液从空腔单元的入口引入至空腔单元中，并且经分布孔进入混合流道与该混合流道中的含硫轻烃进行接触；所述碱液在所述空腔单元中的流动方向与在所述混合流道中的流动方向相反，且所述含硫轻烃依次通过所述两相混合反应器的反应器入口和混合流道的入口引入至所述混合流道中，所述碱液与所述含硫轻烃接触后形成的混合物依次经过混合流道的出口和所述两相混合反应器的反应器出口引出至所述两相混合反应器之外。本发明特别适合于轻烃中酸性含硫物质浓度较低，因而传质推动力较低的情况下进行深度脱硫。
The invention relates to the field of oil refining, and discloses a method for deep desulfurization of sulfur-containing light hydrocarbons. The method comprises: introducing alkali liquor from an inlet of a cavity unit into a cavity unit, and entering a mixing flow channel through a distribution hole to mix with the The sulfur-containing light hydrocarbons in the flow channel are contacted; the flow direction of the alkali solution in the cavity unit is opposite to the flow direction in the mixing flow channel, and the sulfur-containing light hydrocarbons are sequentially mixed through the two phases The reactor inlet of the reactor and the inlet of the mixed flow channel are introduced into the mixed flow channel, and the mixture formed after the alkaline solution is contacted with the sulfur-containing light hydrocarbons passes through the outlet of the mixed flow channel and the two-phase mixed reaction in turn. The reactor outlet of the reactor is led out of the two-phase mixing reactor. The invention is particularly suitable for deep desulfurization under the condition that the concentration of acidic sulfur-containing substances in light hydrocarbons is low, and thus the driving force for mass transfer is low.
Description
Technical field
The present invention relates to refining arts, and in particular, to a kind of method of sulfur-bearing lighter hydrocarbons deep desulfuration.
Background technique
Contain in the lighter hydrocarbons such as thick liquefied gas (predominantly C4 hydro carbons) and light petrol (predominantly C5 hydro carbons) that oil plant generates
A large amount of acidity sulphur-containing substances (predominantly hydrogen sulfide and mercaptan), the industrial general method by alkali cleaning remove acid sulfur-bearing object
Matter.
Removal of mercaptans is step important in liquefied gas subtractive process.The common alkali washing method of industrial liquid gas sweetening
The lye containing excessive NaOH is usually used to contact with liquefied gas, so that mercaptan is reacted with NaOH generates sodium mercaptides, mercaptan
Sodium is dissolved in lye to remove the mercaptan in liquefied gas.
Lye containing sodium mercaptides needs to regenerate, and removes mercaptan sodium.The method of alkali liquid regeneration is usually lye and gas
Body (can be air or oxygen rich gas) mixes, dissolved with catalyst (such as sulfonated phthalocyanine cobalt) in lye, in the effect of catalyst
Under, the sodium mercaptides in lye can be oxidized by oxygen generation disulphide.Disulphide is not soluble in water, as long as therefore generation
Disulphide is separated from lye, can realize the regeneration of lye.
But in the actual process, the density of disulphide and lye is very close, and disulphide and lye have cream
The phenomenon that change, therefore a large amount of disulphide are difficult to be kept completely separate out from lye, but be reproduced lye entrainment and return to
In liquefied gas caustic wash desulfuration equipment.
Moreover, because disulphide is soluble in liquefied gas, therefore the disulphide carried secretly in lye can be dissolved in liquefaction
Gas causes desulfuration of liquefied gas ineffective.
Further, since partial oxidation can be dissolved in lye during alkali liquid regeneration.This is partly dissolved oxygen can be in regenerating alkali
Liquid generates disulphide, and be stranded in liquefied gas again and in liquefied gas contact process under the action of catalyst, so as to cause
Liquefied gas caustic wash desulfuration partial failure.
Therefore, during liquid gas sweetening, the removing of disulphide is extremely important.
Summary of the invention
The purpose of the present invention is overcoming the deficiencies of existing technologies, a kind of satisfaction containing under low mass transfer Impetus Condition is provided
The method of sulphur lighter hydrocarbons deep desulfuration.
To achieve the goals above, the present invention provides a kind of method of sulfur-bearing lighter hydrocarbons deep desulfuration, and this method is including alkali
It washes in the system of unit and implements, the caustic wash unit includes the two-phase mixtures reactor containing reactor tank body and reaction module,
The outer surface of the reaction module is provided at least two groove structures, the protrusion side wall and the reactor of the groove structure
The inner wall of tank body connects, and is formed between the groove structure and the inner wall of the reactor tank body and mixes runner, the reaction mould
Block is internally provided with cavity unit, and the cavity unit passes through point for the bottom that the groove structure of the reaction module is arranged in
Cloth hole is connected to the mixing runner, this method comprises: lye is introduced to the cavity list from the entrance of the cavity unit
In member, and enters mixing runner through the distribution hole and contacted with the sulfur-bearing lighter hydrocarbons in the mixing runner；The lye exists
Flow direction in the cavity unit in the flow direction mixed in runner on the contrary, and the sulfur-bearing lighter hydrocarbons successively lead to
The entrance of the reactor inlet and mixing runner of crossing the two-phase mixtures reactor is introduced in the mixing runner, the lye
The mixture formed after contacting with the sulfur-bearing lighter hydrocarbons successively passes through the outlet and the two-phase mixtures reactor for mixing runner
Reactor outlet is led to except the two-phase mixtures reactor.
In the method for sulfur-bearing lighter hydrocarbons deep desulfuration of the invention, by using two-phase mixtures reactor, enable to contain
Sulphur lighter hydrocarbons and lye are flowed and are vigorously mixed mixing runner high speed, and resistance to mass tranfer is low, so that contained acidity in sulfur-bearing lighter hydrocarbons
Sulphur-containing substance (such as mercaptan) is sufficiently reacted with lye, realizes that the deep desulfuration of sulfur-bearing lighter hydrocarbons, acid sulphur-containing substance removal efficiency are big
In 90%, it is preferable that the acid sulphur-containing substance concentration in lighter hydrocarbons can be down to 10ppm or less or lower.
The method of sulfur-bearing lighter hydrocarbons deep desulfuration of the invention is particularly suitable in lighter hydrocarbons (such as liquefied gas and/or light petrol)
Acid sulphur-containing substance concentration is lower (such as tens ppm), thus carries out deep desulfuration in the lower situation of mass transfer force.This
When, the two-phase mixed at high speed contact in the two-phase mixtures reactor in method of the invention, resistance to mass tranfer is very low, the acidity such as mercaptan
Sulphur-containing substance can separated fully with after lye haptoreaction with lighter hydrocarbons.
Two-phase mixtures reactor of the invention, before two-phase mixtures contact, flow direction of the two-phase in respective runner is excellent
It is selected as 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
The outflow of a distribution hole and with another mixing that is in contact, thus the effect that realization multistage cross flow is mixed in two-phase mixtures reactor
Fruit strengthens mass-transfer performance, and avoiding the part distribution hole as caused by Pressure difference distribution is uneven can not push fluid out, to reduce
The phenomenon that mass-transfer efficiency.
Moreover, the two-phase mixtures reactor for treatment amount that the present invention applies is big, structure is simple, and size is small, and voltage endurance capability is strong, and
Have the advantages that convenient for sealing, installation and maintenance.
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 cross-sectional structure schematic diagram of the two-phase mixtures reactor of a preferred embodiment of the invention.
Fig. 2 is the vertical section structure schematic diagram of the two-phase mixtures reactor of a preferred embodiment of the invention.
Fig. 3 is the flow chart of the method for the sulfur-bearing lighter hydrocarbons deep desulfuration of a preferred embodiment of the invention.
Description of symbols
1, reactor inlet 2, reactor outlet
3, reactor tank body 4, reaction module
5, cavity unit 6, mixing runner
7, alkali liquor inlet 8, distribution hole
9, protrusion side wall 10, distributing chamber
11, collecting chamber 12, caustic wash unit
13, sedimentation unit 14, oxidation regeneration unit
15, anti-extraction unit 16, fresh lye
17, sulfur-bearing lighter hydrocarbons 18, regeneration lye
19, sulfur-bearing lye 20, oxygen-containing gas
21, light-end products 22, sulfur-bearing light-end products
23, desulfurization lighter hydrocarbons
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.
The present invention provides a kind of method of sulfur-bearing lighter hydrocarbons deep desulfuration, this method is real in the system for including caustic wash unit
Apply, the caustic wash unit includes the two-phase mixtures reactor containing reactor tank body and reaction module, the reaction module it is outer
Surface is provided at least two groove structures, and the protrusion side wall of the groove structure is connect with the inner wall of the reactor tank body,
It is formed between the groove structure and the inner wall of the reactor tank body and mixes runner, the reaction module is internally provided with sky
Chamber unit, the cavity unit pass through the distribution hole and the mixed flow that the bottom of groove structure of the reaction module is arranged in
Road connection, this method comprises: lye is introduced in the cavity unit from the entrance of the cavity unit, and through described point
Cloth hole enters mixing runner and is contacted with the sulfur-bearing lighter hydrocarbons in the mixing runner；Stream of the lye in the cavity unit
Dynamic direction in the flow direction mixed in runner on the contrary, and the sulfur-bearing lighter hydrocarbons pass sequentially through the two-phase mixtures and react
The reactor inlet of device and the entrance of mixing runner are introduced in the mixing runner, and the lye is contacted with the sulfur-bearing lighter hydrocarbons
The mixture formed afterwards successively leads to institute by the outlet of mixing runner and the reactor outlet of the two-phase mixtures reactor
It states except two-phase mixtures reactor.
In the two-phase mixtures reactor of the invention, the protrusion side wall of the groove structure and the reactor tank body
Inner wall connection in lye and the contact of sulfur-bearing lighter hydrocarbons and reacted so that each mixing runner formed keeps mutually indepedent
Cheng Zhong, the fluid between each item mixing runner will not interfere with each other.
The fluid of the invention can be appointing in sulfur-bearing lighter hydrocarbons, lye, desulfurization lye, sulfur-bearing lye, desulfurization lighter hydrocarbons
It anticipates one or more, those skilled in the art according to the present invention can describe unambiguously to determine fluid difference herein
Which kind of substance is represented, those skilled in the art should not be construed as limiting the invention.
The outer shape of the two-phase mixtures reactor is not required particularly, can for cylindrical shape, rectangular-shape,
Elliptic Cylinder shape, cube-shaped, prism-shaped etc., under preferable case, the two-phase mixtures reactor is cylindrical shape.
Preferably, the two-phase mixtures reactor further comprises collecting chamber and distributing chamber, and the sulfur-bearing lighter hydrocarbons successively pass through
Cross the reactor inlet, the distributing chamber and it is described mixing runner entrance enter the mixing runner in, the lye and
The mixture formed after the sulfur-bearing lighter hydrocarbons contact is successively by outlet, the collecting chamber and the reaction of the mixing runner
Device outlet is led to except the two-phase mixtures reactor.Distributed component can be contained in the distributing chamber of the invention.
Preferably, the space that the inner wall of reactor tank body surrounds is cylindrical shape, Elliptic Cylinder shape, cube-shaped and rectangular
At least one of body shape；The space that the inner wall of the more preferable reactor tank body surrounds is cylindrical shape.
Preferably, the bottom of the cavity unit is provided with so that the fluid enters the dispersion coupling of the cavity unit
Enter pipe.
Preferably, in the two-phase mixtures reactor, the number phase of the distribution hole of the bottom of each groove structure
It is same or different, and the number of the distribution hole of the bottom of each groove structure is each independently 1-100.
Preferably, in the two-phase mixtures reactor, the aperture of each distribution hole is 0.1-2mm.
Preferably, described according to the flow direction of the lye in the cavity unit in the two-phase mixtures reactor
The aperture of distribution hole is sequentially increased.
Preferably, in the two-phase mixtures reactor, according to the flow direction of the lye in the cavity unit, upstream
Distribution hole the adjacent distribution hole in aperture ratio downstream the small 0.01-1mm in aperture.
Preferably, in the two-phase mixtures reactor, in the bottom of each groove structure, two neighboring distribution hole
Central point distance be 0.5-40mm；More preferably 1-30mm.
Preferably, in the two-phase mixtures reactor, the depth of the distribution hole is 0.1-3mm；More preferably 0.3-
2.5mm。
Preferably, in the two-phase mixtures reactor, the axial direction (center of the as described distribution hole of the distribution hole
Line) it with the angle of the flow direction of the fluid mixed in runner is any angle, the preferably described angle is 45-90 degree, more preferably
It is 90 degree.
Preferably, in the two-phase mixtures reactor, the distribution hole is flowed along the fluid in the mixing runner
Direction is point-blank set gradually.But the setting of the distribution hole is not limited thereto, when the number of the distribution hole
When being more than one, the distribution hole can not also be set along the straight line parallel with the fluid flow direction in mixing runner
It sets.
The distribution hole can be set in the entire bottom of each groove structure, it is preferable that the distribution hole setting
In proximal response device arrival end, to be conducive to lye from the cavity unit and light from the sulfur-bearing of the reactor inlet
Hydrocarbon can the mixing runner nearly entrance end in contact and react, and obtained fluid-mixing can be in reaction mould after mixing
Make contact and the reaction of fluid-mixing more abundant in the longer mixing runner that block provides.Preferably, it is provided with distribution hole
The internal diameter of the cavity unit of proximal response device arrival end is identical and center line having the same.
Preferably, according to the flow direction of the lye in the cavity unit, the entrance of the cavity unit is arranged in institute
The upstream of cavity unit is stated, also, the upstream of each distribution hole is arranged in the entrance of the cavity unit.
Preferably, at least one fiber filament can be set in the mixing runner.The filametntary material can be gold
The inorganic material such as category, glass are also possible to organic material, or the composite material of the above different materials.Filametntary selection root
Depending on property according to the fluid in cavity unit, if the fluid in cavity unit is aqueous solution, fiber filament is optional
With hydrophilic materials such as stainless steel or glass；If the fluid in cavity unit is oil product, oleophylic is can be selected in fiber filament
The organic material of property.It is preferred that the filametntary diameter is 1 μm to 5mm, more preferably 2-50 μm.Fiber is added in mixing runner
Silk, can be formed by the compatibility of drop with the lye in cavity unit by it, be formed in filament surface very thin
Liquid film, increase interphase mass transfer area, shorten mass transfer distance, improve mixing efficiency.
To the filametntary diameter and length, there is no particular limitation, and those skilled in the art can be according in the art
Conventional parameter selected.The filametntary length can be arranged, the fiber according to the length of the mixing runner
Silk can mix runner through entire, and preferably according to the fluid flow direction in mixing runner, the filametntary length is
From the central point of the distribution hole of most downstream to the distance of mixing runner exit.
Under preferable case, the fiber filament is linear or helical form.
Preferably, the open at one end of the cavity unit is alkali liquor inlet, and the other end is closed end.That is, lye
Cavity unit can be entered by alkali liquor inlet, and entered by the distribution hole of connection cavity unit and the mixing runner
It is contacted and/or is reacted with the sulfur-bearing lighter hydrocarbons from the reactor inlet in the mixing runner in mixing runner, and
And the reactor outlet is led to from the outlet of the mixing runner.
Preferably, the connection type between the protrusion side wall of the groove structure and the inner wall of the reactor tank body includes
Detachable connection method and non-detachable connection method.
Preferably, the connection type between the protrusion side wall of the groove structure and the inner wall of the reactor tank body is selected from
Welded connecting threaded connection, expanded joint, stings seam connection, is glued and at least one of connects with blind rivet.
Preferably, the reaction module includes that multiple groove structures are conducive to make to form multiple mixing runners
The two-phase mixtures reactor has biggish processing capacity, it is preferable that the distance between adjacent mixing runner is
0.5mm-10mm, the distance between adjacent mixing runner at this are the thickness of the protrusion side wall between adjacent mixing runner.
Preferably, the cross-sectional area in each mixing runner perpendicular to fluid flow direction is 0.5-20mm2, preferably
For 1-10mm2。
According to a kind of preferred embodiment, the cross-sectional structure of the two-phase mixtures reactor of the invention is illustrated
For figure as shown in Figure 1, specifically, the two-phase mixtures reactor includes that reactor inlet (not shown), reactor outlet (do not show
Out), reactor tank body 3 and reaction module 4, the outer surface of the reaction module 4 is provided at least two, and (example is arranged as shown in figure 1
Have 11) groove structure, the protrusion side wall 9 of the groove structure connect with the inner wall of the reactor tank body 3, the groove knot
It being formed between structure and the inner wall of the reactor tank body and mixes runner 6, the reaction module is internally provided with cavity unit 5,
The cavity unit 5 is connected by the way that the distribution hole 8 of the bottom of the groove structure of the reaction module is arranged in the runner 6 that mixes
It is logical, the setting of the entrance of the cavity unit 5 so that flow direction of the lye in the cavity unit 5 in the mixed flow
Flow direction in road 6 is opposite；It is described mixing runner 6 entrance and it is described mixing runner 6 outlet respectively with the reactor
Entrance is connected to reactor outlet holding.In the preferred embodiment of the invention, the reactor tank body and reaction
Module is disposed as cylindrical, however, the two-phase mixtures reactor of the invention may be set to be triangular prism, quadrangular
Etc. shapes, those skilled in the art above-mentioned preferred cylindrical shape should not be interpreted as limitation of the present invention.
According to another preferred embodiment, the vertical section structure of the two-phase mixtures reactor of the invention shows
It is intended to as shown in Fig. 2, specifically, the two-phase mixtures reactor includes reactor inlet 1, reactor outlet 2, reactor tank body
3 and reaction module 4, the outer surface of the reaction module be provided at least two groove structures, the raised sides of the groove structure
Wall 9 is connect with the inner wall of the reactor tank body, is formed and is mixed between the groove structure and the inner wall of the reactor tank body
Runner 6, the reaction module 4 are internally provided with cavity unit 5, and the cavity unit 5 is by being arranged in the reaction module 4
The distribution hole 8 of bottom of groove structure be connected to the mixing runner 6, the setting of the entrance of the cavity unit 5 is so that alkali
Liquid is opposite with the flow direction in the mixing runner 6 in the flow direction in the cavity unit 5；The mixing runner 6
Entrance and it is described mixing runner 6 outlet respectively with the reactor inlet 1 and the reactor outlet 2 holding be connected to；Gently
Hydrocarbon enters in the two-phase mixtures reactor from reactor inlet 1, successively enters by the entrance of distributing chamber 10 and mixing runner 6
In the mixing runner 6, and in the mixing runner 6 and successively through alkali liquor inlet 7, cavity unit 5 and the distribution hole 8
The lye is mixed, and gained mixture enters in collecting chamber 11 through the outlet of the mixing runner 6 and reacted device goes out
Mouth 2 is led to except the two-phase mixtures reactor.
Preferably, method of the invention further include: the mixture obtained from the outlet of the mixing runner is introduced into alkali cleaning
Initial gross separation is carried out in the precipitation apparatus of unit, obtains the first sulfur-bearing lye and the first lighter hydrocarbons；Then first lighter hydrocarbons are drawn
Enter to be located in the sedimentation unit in the caustic wash unit downstream and carry out the second separation, obtains the second sulfur-bearing lye and desulfurization lighter hydrocarbons；And
And the first sulfur-bearing lye and the second sulfur-bearing lye are introduced into oxidation regeneration unit anti-with oxygen-containing gas progress oxidation regeneration
It answers；And the desulfurization lye obtained in the oxidation regeneration unit is introduced into anti-extraction unit and is separated, obtain regenerating alkali
Liquid；And the regeneration lye is recycled back in the caustic wash unit.
That is, the method for the sulfur-bearing lighter hydrocarbons deep desulfuration of the invention is successively including caustic wash unit, sedimentation list
Implement in the system of member, oxidation regeneration unit and anti-extraction unit, sulfur-bearing lighter hydrocarbons remove institute by caustic wash unit and sedimentation unit
Containing acid sulphur-containing substance, and lye realizes regeneration by oxidation regeneration unit and anti-extraction unit.
In the liquid liquid two phase flow that lye and sulfur-bearing lighter hydrocarbons are formed, a phase is as continuous phase, and another phase is as dispersed phase.
NaOH can be contained in the lye, the preferably concentration of NaOH is 10-20 weight %.In the caustic wash unit,
Acid sulphur-containing substance in sulfur-bearing lighter hydrocarbons is reacted with NaOH generates sulfur-bearing sodium salt, and sulfur-bearing sodium salt is dissolved in lye.By
The mixture that the lighter hydrocarbons and lye of desulphurization reaction are formed, which enters, carries out initial gross separation in the precipitation apparatus of caustic wash unit, obtain first
Sulfur-bearing lye and the first lighter hydrocarbons；Then first lighter hydrocarbons are introduced into the sedimentation unit in the caustic wash unit downstream and are carried out
(the described second isolated first purpose is that the lye by the sulfur-bearing carried secretly in first lighter hydrocarbons is sufficiently divided for second separation
From), obtain the second sulfur-bearing lye and desulfurization lighter hydrocarbons；The desulfurization lighter hydrocarbons can enter subsequent washing purification etc. processes progress after
Continuous processing.
The first sulfur-bearing lye and the second sulfur-bearing lye are introduced into oxidation regeneration unit (usually can be with oxygen-containing gas
For air, oxygen rich gas or oxygen) carry out oxidation regeneration reaction.The reactor of oxidation regeneration unit typically bubbling bed
Reactor and/or filler bubbling bed reactor.In the reactor of oxidation regeneration unit, the first sulfur-bearing lye and described
Sulfur-bearing sodium salt and oxygen-containing gas in two sulfur-bearing lye catalyst (the ARI 100EXL catalyst containing sulfonated phthalocyanine cobalt or its
It has catalytic action substance) under the action of reacted, will be in the first sulfur-bearing lye and the second sulfur-bearing lye
Sulfur-bearing sodium salt be converted into disulphide not soluble in water, obtain desulfurization lye.
The disulphide does not dissolve in lye, therefore separates disulphide by the precipitation apparatus in oxidation regeneration unit
With desulfurization lye.But since the density of lye and disulphide is very close, the desulfurization lye that is discharged by oxidation regeneration unit
In still contain a large amount of disulphide, need to introduce anti-extraction unit and continue to separate.
It include at least one present invention two-phase mixtures reactor above-mentioned under preferable case, in the anti-extraction unit.
For the two-phase mixtures reactor in the caustic wash unit, the preferably described sulfur-bearing lighter hydrocarbons are made as continuous phase, lye
For dispersed phase；And for the two-phase mixtures reactor in the anti-extraction unit, the preferably described lye is as continuous phase, lightweight vapour
Oil is used as dispersed phase.In the anti-extraction unit of the invention, the petroleum benzin as dispersed phase can be routine in the art
The various gasoline used.
In caustic wash unit and anti-extraction unit, in the two-phase mixtures reactor, preferably continuous phase is from the reaction
Device entrance enters in the mixing runner, and the dispersed phase from the entrance of the cavity unit successively through the cavity unit with
The distribution hole enters in the mixing runner.
In the anti-extraction unit, the desulfurization lye and disulphide are soluble in light-end products therein such as gasoline
It is contacted Deng in the two-phase mixtures reactor, realizes the separation of desulfurization lye with the disulphide wherein carried secretly, regenerated
Lye.Precipitation apparatus through anti-extraction unit, regeneration lye is separated with the light-end products containing disulphide, by the regeneration lye
It is recycled back to the desulfurization that the caustic wash unit carries out sulfur-bearing lighter hydrocarbons.It is mixed using two-phase of the present invention in the anti-extraction unit
The operating method for closing reactor is similar to the operating method of caustic wash unit, and details are not described herein by the present invention.
Preferably, in the caustic wash unit, the contact conditions of the lye and the sulfur-bearing lighter hydrocarbons include: reaction temperature
It is 25-80 DEG C, reaction pressure 0.2-2MPa.
It is preferred that apparent velocity of the dispersed phase at the alkali liquor inlet of cavity unit is 0.2-5m/s, more preferably 0.3-
3m/s。
Preferably, in the caustic wash unit, apparent velocity of the lye at the alkali liquor inlet of the cavity unit
For 0.2-5m/s；Apparent velocity of the sulfur-bearing lighter hydrocarbons in the inlet of the mixing runner is 0.5-20m/s.
It is preferred that it is 25-80 DEG C that the reaction condition of the anti-extraction unit, which includes: reaction temperature, reaction pressure 0.2-
2MPa。
Preferably, apparent velocity of the continuous phase in the inlet of the mixing runner is 0.5-20m/s, more preferably
4-10m/s。
In the present invention, swiftly flowing liquid liquid two-phase is vigorously mixed in two-phase mixtures reactor, the liquid that dispersed phase is formed
Drop mixes acutely with continuous, and resistance to mass tranfer is low, enables to the mass transport process between two-phase sufficiently to carry out, desulfuration efficiency can
Reach 90% or more, that is to say, that contained acidity sulphur-containing substance (such as mercaptan) and alkali in lighter hydrocarbons can be made in caustic wash unit
Liquid sufficiently reacts, and realizes that the deep desulfuration of lighter hydrocarbons, acid sulphur-containing substance removal efficiency are greater than 90 weight %, acid sulfur-bearing object in lighter hydrocarbons
The mass concentration of matter can be down to 10ppm or less；And being sufficiently mixed for lye and light-end products may be implemented in anti-extraction unit, it will
The disulphide of entrained with is extracted in oily phase (light-end products) in lye after desulfurization, and the extraction yield of disulphide is greater than 90 weights
Measure %.
It is preferred that the pressure drop in two-phase mixtures reactor is 10-800kPa；More preferably 100-600kPa.Dispersed phase is through dividing
Drop is formed after cloth hole to be mixed with continuous phase.Since the diameter of distribution hole is smaller, the size of drop is also smaller, can be with
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.
Under preferable case, the petroleum hydrocarbon-fraction that the sulfur-bearing lighter hydrocarbons are the C4-C5 containing acid sulphur-containing substance is wherein described
Acid sulphur-containing substance be mercaptan, the sulfur content in terms of element sulphur in the lighter hydrocarbons is 50-2000ppm.It is preferred that the sulfur-bearing
Lighter hydrocarbons are sulfur-bearing liquefied gas and/or sulfur-bearing light petrol.
By anti-extraction unit be discharged regeneration lye in sulfur content it is lower, can hardly using other extraction steps into
One step reduces sulfur content, therefore returning to sulphur contained in the regeneration lye of caustic wash unit substantially will not be by lighter hydrocarbons in alkaline cleaning procedure
It extracts and the desulfuration efficiency in lighter hydrocarbons is impacted.
It, can be anti-by two-phase mixtures of the invention according to the treating capacity of the concentration of the acid sulphur-containing substance in lighter hydrocarbons and lighter hydrocarbons
Device is answered to carry out separate unit or multi-platform combined use.
Preferred embodiment according to the present invention, two-phase mixtures reactor provided by the invention is using more series connection
Form uses, and the reaction condition in each two-phase mixtures reactor can be identical or different, each independently includes: reaction
Temperature is 25-80 DEG C, reaction pressure 0.2-2MPa.
A kind of preferred embodiment according to the present invention, the method for sulfur-bearing lighter hydrocarbons deep desulfuration of the present invention
It is carried out using the technique in flow chart shown in Fig. 3, specifically:
In the present invention, fresh lye 16 and/or regeneration lye 18 and sulfur-bearing lighter hydrocarbons 17 are introduced into caustic wash unit 12,
In the caustic wash unit 12, the acid sulphur-containing substance in sulfur-bearing lighter hydrocarbons is reacted with the NaOH in lye generates sulfur-bearing sodium salt, and
Sulfur-bearing sodium salt is dissolved in lye.The mixture obtained from the outlet of the mixing runner is introduced to the precipitation apparatus of caustic wash unit
Middle carry out initial gross separation, obtains the first sulfur-bearing lye and the first lighter hydrocarbons；Then first lighter hydrocarbons are introduced and is located at the alkali cleaning
The second separation is carried out in the sedimentation unit 13 in 12 downstream of unit, obtains the second sulfur-bearing lye and desulfurization lighter hydrocarbons 23；Desulfurization lighter hydrocarbons 23
It is continued with into processes such as subsequent washing purifications.And by the first sulfur-bearing lye and the second sulfur-bearing lye
The sulfur-bearing lye 19 of formation is introduced into oxidation regeneration unit 14 to react with the progress oxidation regeneration of oxygen-containing gas 20, in oxidation regeneration list
In the reactor of member, the sulfur-bearing sodium salt in sulfur-bearing lye 19 is reacted with oxygen-containing gas 20, the sulfur-bearing sodium salt turn by sulfur-bearing alkali, in 19
Disulphide is turned to, desulfurization lye is obtained.The desulfurization lye being discharged by oxidation regeneration unit, which is introduced into anti-extraction unit 15, to be continued
Carry out the separation of desulfurization lye and disulphide.In the anti-extraction unit 15, desulfurization lye is contacted with light-end products 21, real
The separation of existing desulfurization lye and the disulphide wherein carried secretly, obtains regeneration lye 18 and sulfur-bearing light-end products 22.By described in again
Raw lye 18 is recycled back to progress lighter hydrocarbons desulfurization in the caustic wash unit 12.
Two-phase mixtures reactor provided by the invention and its application also have the advantages that following specific:
Two-phase mixtures reactor is coupled in lighter hydrocarbons sulfur removal technology, the special construction design of two-phase mixtures reactor both may be used
To strengthen above-mentioned reaction process, 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 weight % or more.Two-phase mixtures are anti-
The problem of answering two-phase apparent velocity height in device, being not susceptible to runner blocking.Utilize the high feature of interface tension, it is not necessary to use
Surface reactive material avoids emulsification problem in two-phase mixtures reactor, after two-phase mixtures contact, convenient for split-phase and carries out subsequent
Processing.The treating capacity of two-phase mixtures reactor is big, and structure is simple, and size is small, and voltage endurance capability is strong, and convenient for sealing, installation and dimension
Shield.
The present invention will be described in detail by way of examples below.
Below in case of no particular description, used a variety of materials are all from commercially available.
Embodiment 1
The present embodiment carries out the deep desulfuration of sulfur-bearing lighter hydrocarbons using two-phase mixtures reactor of the present invention, specifically such as
Under:
Liquefied gas and lye containing mercaptan contact in caustic wash unit, and mercaptan is reacted with the NaOH in lye generates mercaptan
Sodium is simultaneously dissolved in lye.It is completed 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
The purpose of removal of mercaptans.By sedimentation unit be discharged lye enter oxidation regeneration unit, in filler bubbling bed reactor, lye with
Sodium mercaptides are converted disulphide by air haptoreaction.Lye after the desulfurization being discharged by oxidation regeneration unit enters back suction
Bill of lading member, contacts with gasoline, removes the disulphide of entrained with, obtains regeneration lye.The regenerating alkali being discharged by anti-extraction unit
Liquid is recycled back to caustic wash 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 above-mentioned liquefied gas is provided using SH/T 0222-92, the group of acid mercaptan
It is measured at using 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 depicted in figs. 1 and 2.Two-phase mixtures reaction
It include 11 groove structures in device, for caustic wash unit, the liquefied gas containing mercaptan enters two-phase mixtures via reactor inlet
In the distributing chamber of reactor, and mixing runner is entered by the entrance of mixing runner.Concentration is the NaOH aqueous solution of 15 weight %
Drop, which is formed, through distribution hole by cavity unit enters mixing runner, and the cross section of the cavity unit perpendicular to lye flow direction
Product is 280mm2, the cross-sectional area perpendicular to the mixing runner of sulfur-bearing lighter hydrocarbons flow direction is 3mm2, the length for mixing runner is
1000mm.The quantity of the distribution hole of the bottom of each groove structure is 4, and distribution hole depth is 1.0mm, according to lye in cavity
Flow direction in unit, the aperture of each distribution hole are respectively 0.9mm, 1.0mm, 1.1mm and 1.2mm, two neighboring distribution
The centre distance in hole is 23mm.Before entering mixing runner, the flow direction of liquefied gas and lye is adverse current, cavity unit
One end be closed 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.
Apparent velocity of the liquefied gas in the inlet of mixing runner is 6m/s, and lye is at the alkali liquor inlet of cavity unit
Apparent velocity is 0.8m/s, and the content of mercaptan sulfur is 1000ppm in liquefied gas.Liquefied gas fills in mixing runner with lye two-phase
Enter collecting chamber after dividing mixing mass transfer, and draw reactor from reactor outlet, is separated into subsequent separation equipment.
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 (second level two-phase mixtures reactor is identical as the size of the first order two-phase mixtures reactor) is answered to continue to take off
Sulphur, by liquid of the fluid of second level two-phase mixtures reactor discharge after just dividing the desulfurization obtained after separation with sedimentation unit
Change air-flow and goes out reaction system.In liquefied gas after resulting desulfurization, the content of mercaptan sulfur is 3ppm, and desulfurization degree is 99.7 weights
Measure %.
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 structure snd size of the two-phase mixtures reactor of caustic wash unit are all the same.The temperature of first order two-phase mixtures reactor is 50 DEG C,
Pressure is 1.0MPa, and the temperature of second level two-phase mixtures reactor is 50 DEG C, pressure 0.6MPa.Lye is in mixing flow channel entry point
The apparent velocity at place is 6m/s, and apparent velocity of the gasoline at alkali liquor inlet is 0.6m/s.Two are entrained in lye after desulfurization
Sulfide, sulfur content 325ppm.The sulfur content in regeneration lye obtained after anti-extraction unit is 12ppm.
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 the deep desulfuration of sulfur-bearing lighter hydrocarbons using two-phase mixtures reactor of the present invention, specifically such as
Under:
The method of lighter hydrocarbons desulfurization in the present embodiment is similar to embodiment 1, also includes 11 in two-phase mixtures reactor
Groove structure, 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: 3 distribution holes are provided in the bottom of each groove structure, distribution hole depth is 1.1mm, and
According to flow direction of the lye in cavity unit, 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 cavity unit of lye flow direction is 280mm2,
Cross-sectional area perpendicular to the mixing runner of sulfur-bearing lighter hydrocarbons flow direction is 3mm2, the length for mixing runner is 500mm.Two-phase is mixed
Closing the temperature in reactor is 45 DEG C, pressure 1.2MPa.Light petrol is 8m/s, alkali in the apparent velocity of mixing flow passage entry
Apparent velocity of the liquid at alkali liquor inlet is 0.48m/s, and the content of mercaptan sulfur is 78ppm in light petrol.
By in the light petrol of caustic wash unit, the content of mercaptan sulfur is 3.5ppm, desulfurization degree is 95.5 weight %.
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 snd size all the same.The temperature of two-phase mixtures reactor is 52 DEG C, pressure 1.0MPa.Lye is in mixing runner
The apparent velocity of inlet is 7m/s, and apparent velocity of the gasoline at the alkali liquor inlet of cavity unit is 2m/s.Alkali after desulfurization
Disulphide, sulfur content 48ppm are entrained in liquid.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 the deep desulfuration of sulfur-bearing lighter hydrocarbons using two-phase mixtures reactor of the present invention, specifically such as
Under:
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 cavity unit, 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 cavity unit of flow direction is 280mm2, perpendicular to the cross section of the mixing runner of sulfur-bearing lighter hydrocarbons flow direction
Product is 6mm2, the length for mixing runner is 1000mm.Temperature in two-phase mixtures reactor is 50 DEG C, pressure 1.2MPa.Gently
Gasoline is 8m/s in the apparent velocity of mixing flow passage entry, and apparent velocity of the lye at alkali liquor inlet is 1.25m/s.This reality
Applying example uses light petrol same as Example 2 as sulfur-bearing lighter hydrocarbons, and ethyl mercaptan is added thereto and makes the present embodiment
The content of mercaptan sulfur is 1000ppm in light petrol.
By in the light petrol of caustic wash unit, the content of mercaptan sulfur is 14ppm, desulfurization degree is 98.6 weight %.
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 and size of member are all the same.The temperature of two-phase mixtures reactor is 52 DEG C, pressure 1.1MPa.Alkali
Apparent velocity of the liquid in the inlet of mixing runner is 6m/s, and apparent velocity of the gasoline at the alkali liquor inlet of cavity unit is
3m/s.Disulphide, sulfur content 560ppm are entrained in lye after desulfurization.The regenerating alkali obtained after anti-extraction unit
Sulfur content in liquid is 45ppm.
Remaining is in the same manner as in Example 2.
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 be concatenated two identical micro- blenders of T-type (runner i.e. where lye with mix runner directly intersect vertically without
The structure of reflux type), the mixing runner cross-sectional area of each mixer is 4mm2, dispersed phase flow diameter is 2mm.Each T
The processing capacity of the micro- blender of type mixes runner using one of two-phase mixtures reactor of the present invention with embodiment 2
Processing capacity is identical.
Remaining is in the same manner as in Example 2.
As a result: the desulfurization degree of light petrol is 72 weight %, has fully demonstrated two-phase mixtures provided by the invention in contrast
The high feature of reactor mass-transfer efficiency.
It is can be seen that from the result of the embodiment of the present invention 1-3 and comparative example 1-2 by the present invention in that anti-with two-phase mixtures
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 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 (16)
1. a kind of method of sulfur-bearing lighter hydrocarbons deep desulfuration, this method is implemented in the system for including caustic wash unit, the alkali cleaning list
Member includes the two-phase mixtures reactor containing reactor tank body and reaction module, and the outer surface of the reaction module is provided at least
Two groove structures, the protrusion side wall of the groove structure are connect with the inner wall of the reactor tank body, the groove structure with
Mixing runner is formed between the inner wall of the reactor tank body, the reaction module is internally provided with cavity unit, the sky
Chamber unit is connected to by the way that the distribution hole of the bottom of the groove structure of the reaction module is arranged in the mixing runner, this method
It include: to be introduced to lye in the cavity unit from the entrance of the cavity unit, and enter mixing through the distribution hole
Runner is contacted with the sulfur-bearing lighter hydrocarbons in the mixing runner；Flow direction of the lye in the cavity unit in institute
State the flow direction in mixing runner on the contrary, and the sulfur-bearing lighter hydrocarbons pass sequentially through the reactor of the two-phase mixtures reactor and enter
The entrance of mouth and mixing runner is introduced in the mixing runner, the mixing that the lye is formed after contacting with the sulfur-bearing lighter hydrocarbons
It is anti-that object successively leads to the two-phase mixtures by the outlet of mixing runner and the reactor outlet of the two-phase mixtures reactor
It answers except device；The mixture obtained from the outlet of the mixing runner is introduced into the precipitation apparatus of caustic wash unit and is tentatively divided
From obtaining the first sulfur-bearing lye and the first lighter hydrocarbons；Then first lighter hydrocarbons are introduced and is located at the heavy of the caustic wash unit downstream
It drops and carries out the second separation in unit, obtain the second sulfur-bearing lye and desulfurization lighter hydrocarbons；And by the first sulfur-bearing lye and second
Sulfur-bearing lye is introduced into oxidation regeneration unit to react with oxygen-containing gas progress oxidation regeneration；And it will be in the oxidation regeneration unit
The desulfurization lye of acquisition, which is introduced into anti-extraction unit, to be separated, and regeneration lye is obtained；And the regeneration lye is recycled back to
In the caustic wash unit.
2. according to the method described in claim 1, wherein, the two-phase mixtures reactor further comprises collecting chamber and distribution
Room, the sulfur-bearing lighter hydrocarbons are successively described in the entrance entrance by the reactor inlet, the distributing chamber and the mixing runner
It mixes in runner, the mixture that the lye is formed after contacting with the sulfur-bearing lighter hydrocarbons successively mixes going out for runner by described
Mouth, the collecting chamber and the reactor outlet are led to except the two-phase mixtures reactor.
3. method according to claim 1 or 2, wherein in the two-phase mixtures reactor, each groove structure
Bottom distribution hole number it is identical or different, and the number of the distribution hole of the bottom of each groove structure is respectively independent
Ground is 1-100.
4. method according to claim 1 or 2, wherein in the two-phase mixtures reactor, each distribution hole
Aperture is 0.1-2mm.
5. according to the method described in claim 4, wherein, in the two-phase mixtures reactor, according in the cavity unit
Lye flow direction, the aperture of the distribution hole is sequentially increased.
6. according to the method described in claim 4, wherein, in the two-phase mixtures reactor, according in the cavity unit
Lye flow direction, the small 0.01-1mm in aperture of the adjacent distribution hole in the aperture ratio downstream of the distribution hole of upstream.
7. method according to claim 1 or 2, wherein in the two-phase mixtures reactor, in each groove knot
The bottom of structure, the distance of the central point of two neighboring distribution hole are 0.5-40mm.
8. according to the method described in claim 7, wherein, in the two-phase mixtures reactor, in each groove structure
Bottom, the distance of the central point of two neighboring distribution hole is 1-30mm.
9. method according to claim 1 or 2, wherein in the two-phase mixtures reactor, the depth of the distribution hole
For 0.1-3mm.
10. according to the method described in claim 9, wherein, in the two-phase mixtures reactor, the depth of the distribution hole is
0.3-2.5mm。
11. method according to claim 1 or 2, wherein in the two-phase mixtures reactor, the cavity unit
Open at one end is alkali liquor inlet, and the other end is closed end.
12. method according to claim 1 or 2, wherein in the two-phase mixtures reactor, the groove structure
Connection type between protrusion side wall and the inner wall of the reactor tank body, which is selected from, to be welded to connect, is threadedly coupled, expanded joint, stinging seam company
It connects, be glued and at least one of connected with blind rivet.
13. according to the method described in claim 1, including at least one described two-phase mixtures in the anti-extraction unit wherein
Reactor.
14. method according to claim 1 or 2, wherein table of the lye at the alkali liquor inlet of the cavity unit
Sight flow velocity is 0.2-5m/s；Apparent velocity of the sulfur-bearing lighter hydrocarbons in the inlet of the mixing runner is 0.5-20m/s.
15. method according to claim 1 or 2, wherein in the caustic wash unit, the lye and the sulfur-bearing are light
The contact conditions of hydrocarbon include: that temperature is 25-80 DEG C, reaction pressure 0.2-2MPa.
16. according to the method described in claim 1, wherein, the sulfur-bearing lighter hydrocarbons include sulfur-bearing liquefied gas and/or the light vapour of sulfur-bearing
Oil.
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| CN1632072A (en) * | 2004-12-01 | 2005-06-29 | 中国石油天然气股份有限公司 | Alkaline extraction for light oil agent - combined device for fixed bed catalytic oxidation sweetening |
| CN1693423A (en) * | 2005-04-29 | 2005-11-09 | 清华大学 | A method for alkaline cleaning of oil products |
| EP2431091A1 (en) * | 2009-04-17 | 2012-03-21 | Nisso Engineering Co., Ltd. | Tubular flow type reactor |
| CN102757809A (en) * | 2012-08-03 | 2012-10-31 | 宁波中一石化科技有限公司 | Mercaptan removal and lye regeneration device and method for gasoline light fractions |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5030520B2 (en) * | 2006-09-29 | 2012-09-19 | 富士フイルム株式会社 | Fluid mixing method and microdevice |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1632072A (en) * | 2004-12-01 | 2005-06-29 | 中国石油天然气股份有限公司 | Alkaline extraction for light oil agent - combined device for fixed bed catalytic oxidation sweetening |
| CN1693423A (en) * | 2005-04-29 | 2005-11-09 | 清华大学 | A method for alkaline cleaning of oil products |
| EP2431091A1 (en) * | 2009-04-17 | 2012-03-21 | Nisso Engineering Co., Ltd. | Tubular flow type reactor |
| CN102438742A (en) * | 2009-04-17 | 2012-05-02 | 日曹工程股份有限公司 | Tubular flow type reactor |
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