CN107557060B - A kind of method that diesel oil extracted-aoxidized ultra-deep desulfurization in microreactor system - Google Patents
A kind of method that diesel oil extracted-aoxidized ultra-deep desulfurization in microreactor system Download PDFInfo
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Abstract
The present invention provides the methods that diesel oil in a kind of microreactor system extracted-aoxidized ultra-deep desulfurization.It is to extract-aoxidize the method after ultra-deep desulfurization technique improves to the existing diesel oil based on ionic liquid using microreactor system.Diesel oil and extractant ionic liquid are first contacted mixing by this method in first micro-mixer, most of sulfide is extracted to ionic liquid from diesel oil in microring array channel, diesel oil-non-aqueous ionic liquid mixed material contacts mixing in second micro-mixer with oxidant later, and in the oxidation and removing with completion sulfide in the micro passage reaction of second micro-mixer outlet connection, Ultra-deep Desulfurization of Diesel Fuels is realized.Residence time of the reaction mass in micro passage reaction is 10~90min.Compared with prior art, high-efficiency desulfurization and device miniaturization are realized by reinforcing to sweetening process, and simple process and can continuous production, with wide practical application in industry prospect.
Description
■ technical field
The present invention relates to the methods that diesel oil in a kind of microreactor system extracted-aoxidized ultra-deep desulfurization, belong to petroleum-type
Product desulfuration field.
■ background technique
Diesel oil proportion in vehicle fuel is increasing, the SO that when institute's sulfur compound high-temp combustion generatesXIt can make
Increase at the sulphates content on solid particulate matter in the irreversible poisoning of the three-way catalyst in automobile exhaust purifier, atmosphere,
The harm such as the components corrosion of engine, eventually lead to NOX, CO and volatile CHXDischarge amount increases, and adds acid rain, haze
It is acute.For this purpose, countries in the world implement stringent limitation to diesel oil sulfur content.The U.S. begins to supply sulfur content and is less than from 2006
The diesel oil of 15 μ g/g, and Japan and European Union also successively started to execute the bavin that sulfur content is not more than 10 μ g/g in 2008 and 2009
Oil standard；China starts to execute state IV standards in January, 2015, it is desirable that diesel oil sulfur content is not more than 50 μ g/g, and in January, 2017
State of enforcement's V standard, it is desirable that diesel oil sulfur content is not more than 10 μ g/g.Become as it can be seen that lower sulfur diesel even has become development without vulcanization
Gesture, ultra-deep desulfurization become inevitable.Researching and developing a kind of effective ultra-deep desulfurization technique is to control the most important way of diesel oil sulfur content
Diameter.
Sulfide is divided into fats and thiophene-based in diesel oil, and sulfur removal technology includes adding two class of hydrogen and Fei Jia hydrogen, the former is to work as
Preceding prevailing technology generates H by the catalytic action of hydrogen and sulfide2S, realizes desulfurization, this method easily removes fats and low
The thiophene-type sulfide of molecular weight, but it is difficult to be removed in depth the dibenzothiophenes in diesel oil and its derivative (especially 4,6- bis-
Methyldibenzothiophene).Using existing desulphurization catalyst, hydrodesulfurization generally can drop diesel oil sulfur content from thousands of μ g/g
Extremely hundreds of μ g/g, if but sulfur content is dropped into 15 μ g/g, catalyst bed volume need to be improved 3 times or more；If sulfur content is dropped
To 0.1 μ g/g, catalyst bed volume need to increase by 7 times or so, and investment and production cost is undoubtedly greatly improved in this, limit the work
Further development of the skill in terms of Ultra-deep Desulfurization of Diesel Fuels.At the same time, some non-hydrodesulfurizations (such as: oxidation, extraction,
Absorption, biological desulphurization etc.) there is higher removal efficiency to dibenzothiophenes and its derivative, wherein the diesel oil based on ionic liquid
Extraction-oxidation desulfuration process by the advantages that reaction condition is mild, equipment investment is few, become the biggish diesel oil of application prospect it is non-plus
One of hydrogen ultra-deep desulfurization method.
Diesel oil extraction-oxidation desulfuration process technology based on ionic liquid will be aoxidized and be combined with ion liquid abstraction
A kind of sulfur removal technology, its basic principle are that the sulfide in diesel oil is first extracted into extractant ionic liquid, are being urged later
Under the action of agent, sulfide is oxidized agent and is oxidized to the highly polar oxysulfide such as sulfone class, since the electronegativity of oxygen is higher than sulphur, because
The polarity of this oxysulfide is more much bigger than sulfide, it is made to be easier to stay in ionic liquid；On the other hand, due to sulfide from
Reduced in sub- liquid, its extraction equilibrium in diesel oil and ionic liquid caused to be broken, can promote sulfide in diesel oil after
It is continuous to be extracted in ionic liquid, repeatedly, finally by liquid-liquid two-phase laminated flow, it can be obtained low-sulfur diesel-oil and rich in sulphur oxygen
The ionic liquid of compound.Ionic liquid can be removed oxysulfide therein by modes such as distillations, realize recycling.
It is mostly at present opening for ionic liquid for the open report of diesel oil extraction-oxidation desulfuration process based on ionic liquid
Hair, and for then shorter mention in terms of novel process process.It is published positive for diesel oil extraction-oxidation sweetening ionic liquid
Ion has imidazoles (CN105176570A, CN103834432A), pyridines (CN102465002A), thiazoles
(CN104673370A), quaternary amines (CN104593056A) etc.；Anion hasAcids (CN102465002A),
Lewis acids (CN103509590A, CN101508907A) etc..It is low, anti-more or less to there is one way desulfurization degree in these systems
Long, ionic liquid and the problems such as oxidizer is big, higher cost between seasonable.
All of above reaction system is all made of batch stirred tank reactor technique, that there are multi-phase material mixed effects is poor,
The disadvantages such as mass-transfer performance is poor, process is discontinuous, safety is low.Extraction based on ionic liquid-oxidation sweetening process is related to bavin
Oil-ionic liquid mutually disperses, sulfide is from oily phase transfer to ionic liquid phase, ionic liquid-oxidant mixing, sulfide and oxygen
The complicated complex process such as agent reaction and corresponding heat transfer, is controlled, existing stirred-tank reactor technique energy by liquid-liquid mass transfer
Diesel oil sulfur content is down to tens of μ g/g from hundreds of μ g/g, if but sulfur content is dropped to 10 μ g/g hereinafter, (3 need to be reacted a few hours
Hour or more, CN104593056A) or increase Multistage desulfuration technique (CN104673370A), this also leads to ionic liquid dosage
Increase (molar ratio of ionic liquid and sulphur is higher than 500).
In addition, oxidant is more at present in the open report of diesel oil extraction-oxidation desulfuration process based on ionic liquid
Peroxide such as hydrogen peroxide (CN102408915A, CN101220293B, CN105176570A, CN103509590A) are selected, and
These peroxide properties are unstable, easily decompose in range of reaction temperature, cause its oxidation to weaken, therefore existing
Excessive oxidant (molar ratio of oxidant and sulphur is higher than 50) would generally be added in batch stirred tank reactor technique, to guarantee
Sulfide is fully oxidized.
In addition, batch stirred tank reactor complex operation, energy consumption is high, and a large amount of oxidants are in operation and storage side
There is security risk in face, be unfavorable for industrialized production.
Process efficiency is improved, the industrialized production route that development process is continuous, safety is good, at low cost is to realize that diesel oil is super
The developing direction of deep desulfuration.
■ summary of the invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide diesel oil extraction-is carried out in a kind of microreactor system
The new method and new process for aoxidizing ultra-deep desulfurization realize the residence time by the mass transfer mixed characteristic of microreactor system high efficiency
Short, ionic liquid and oxidizer are few and can continuous, safe production high-efficiency desulfurization.
The present invention is to provide the method that diesel oil extracted-aoxidized ultra-deep desulfurization in microreactor system, this method will
Diesel oil and the extractant ionic liquid of catalyst is dispersed with after temperature regulating device is preheated to reaction temperature, in first micro-mixer
Interior mixing, most of sulfide is extracted to ionic liquid, mixed diesel oil-ionic liquid two from diesel oil in microring array channel
Phase materials mix in second micro-mixer again with oxidant after temperature regulating device is preheated to reaction temperature, mixed
Diesel oil-three phase materials of ionic liquid-oxidant enter micro passage reaction, and the oxygen of sulfide is completed under default reaction condition
Change and removes；Material after reaction enters in the product receiver being located in cooling device through counterbalance valve, then receives product
Device, which is placed in a centrifuge, to be centrifuged, and upper phase is desulfurized diesel oil, and middle layer liquid phase is oxidant and its reaction product,
Lower layer's liquid phase is the ionic liquid for being dispersed with catalyst, which is recycled.
In method provided by the invention, the microreactor system includes stock bottle, feed pump, micro-mixer, microchannel
Reactor, temperature regulating device, counterbalance valve, product receiver and cooling device.The stock bottle, feed pump, micro-mixer, microchannel
Reactor, counterbalance valve and product receiver are connected in series；The micro-mixer and micro passage reaction are placed in temperature control dress
In setting；The product receiver is placed in cooling device.
In method provided by the invention, reaction temperature is 30~100 DEG C, specially 50~80 DEG C；Micro passage reaction goes out
Mouthful pressure is controlled by being connected to the counterbalance valve among micro passage reaction and product receiver, in order to inhibit oxidant decomposition and
Too many energy consumption is not increased, reaction pressure is 200~500kPa, specially 250~400kPa；Reaction mass matches and its micro- logical
Residence time in road reactor is determined by material feed rate and micro passage reaction size, wherein ionic liquid and sulphur
Molar ratio is 20:1~400:1, specially 100:1~250:1, and the molar ratio of oxidant and sulphur is 1:1~100:1, specially
10:1~50:1；Diesel oil (such as sulfur content is lower than 100 μ g/g) lower for sulfur content, in order to guarantee ionic liquid and oxidant
It can be uniformly mixed with diesel oil, should ensure that the volume ratio of ionic liquid and diesel oil is not less than 0.05, the volume ratio of oxidant and diesel oil
Not less than 0.01；Diesel oil-residence time of three phase materials of ionic liquid-oxidant in micro- reaction channel is 10~90min, tool
Body is 30~60min.
In method provided by the invention, the diesel oil sulfur content is 10~5000 μ g/g；The catalyst is a kind of molybdic acid
Ammonium salt in catalysis agent, be specifically positive ammonium molybdate ((NH4)2MoO4), ammonium dimolybdate ((NH4)2Mo2O7), ammonium tetramolybdate ((NH4)2Mo4O13), ammonium heptamolybdate ((NH4)6Mo7O24) one of or two kinds or more, mass concentration of the catalyst in ionic liquid be
2~10g/L；The ionic liquid includes 1- butyl -3- methylimidazole hexafluorophosphate (BmimPF6) and 1- octyl -3- methyl
Limidazolium hexafluorophosphate (OmimPF6) one of or two kinds；The oxidant include mass concentration 35wt% Peracetic acid,
One of the tertbutanol peroxide of mass concentration 70wt%, mass concentration 30wt% hydrogen peroxide or two kinds or more.
In microreactor system of the present invention, microring array channel equivalent diameter in the micro-mixer is 0.1~
1mm, specially 0.5~0.8mm, length are 50~300mm, specially 100~200mm；It is micro- in the micro passage reaction
Reaction channel equivalent diameter be 0.1~1mm, specially 0.5~0.8mm, length be 1000~50000mm, specially 5000~
20000mm。
In method provided by the invention, micro-mixer has the characteristics that Liquid-liquid mixing is uniform, can be by diesel oil and ionic liquid
Body, disperse oxidant drop small at size, uniform and controllable shorten material incorporation time；Micro passage reaction has mass transfer
The advantages of performance is good, the residence time can easily be accommodated is, it can be achieved that residence time of material, effective of reaction time and mass transfer time
Match, improves one way desulfuration efficiency；Counterbalance valve can be precisely controlled reaction and carry out under slightly above normal pressure, hardly increase energy consumption
Under the premise of inhibit oxidant decompose, reduce oxidizer, improve production security.Importantly, this method can pass through letter
Single increase and decrease microreactor system quantity carrys out regulating device processing capacity, has on the one hand prevented " amplification when traditional handicraft amplification
Effect ", on the other hand in different microreactor systems, security risk substantially reduces a large amount of disperse oxidants.
The present invention is applied to the liquid-liquid-liquid reaction process that diesel oil extracted-aoxidized ultra-deep desulfurization using macro work technology,
Have the effect that mass transfer compared with prior art and reaction rate is fast, the reaction time is short, one way desulfurization degree is high, oxidant and
Ionic liquid dosage is few, system bulk is small, simple process, process is continuous, operating flexibility is big, highly-safe.
Below according to the drawings and specific embodiments, technical solution of the present invention is described in detail.
Detailed description of the invention
Fig. 1 is the flow diagram of method provided by the invention.In figure:
1 is fresh ionic liquid stock bottle；2 be diesel raw material bottle；3 be oxidant feed bottle；4 pump for ionic liquid；5 are
Diesel pump；6 be oxidant pump；7 be first micro-mixer；8 be microring array channel；9 be second micro-mixer；10 be micro- logical
Road reactor；11 be temperature regulating device；12 be counterbalance valve；13 be product receiver；14 be cooling device；15 be desulfurized diesel oil；16
For oxidant and its reaction product；17 be recycling ionic liquid.
Specific embodiment
As shown in Figure 1, being flow chart of the invention.As can be known from Fig. 1, the fresh ionic liquid stock bottle 1 containing catalyst
It is connected through ionic liquid pump 4 with an entrance of first micro-mixer 7 by pipeline, diesel raw material bottle 2 is by pipeline through bavin
Oil pump 5 is connected with another entrance of first micro-mixer 7, the outlet of first micro-mixer 7 and entering for microring array channel 8
Mouth is connected, and the outlet in microring array channel 8 is connected with an entrance of second micro-mixer 9, and oxidant feed bottle 3 passes through pipeline
It is connected through oxidant pump 6 with another entrance of second micro-mixer 9, the outlet of second micro-mixer 9 and microchannel plate
The entrance of device 10 is answered to be connected, the outlet of micro passage reaction 10 is connected with the entrance of counterbalance valve 12, the outlet and production of counterbalance valve 12
Product receiver 13 is connected；Wherein, first micro-mixer 7 and second micro-mixer 9, microring array channel 8 and microchannel plate are answered
Device 10 is placed in temperature regulating device 11；Product receiver 13 is placed in cooling device 14.
After fresh ionic liquid containing catalyst and recycling ionic liquid 17 mix, with diesel oil respectively through ionic liquid pump 4,
Diesel pump 5 mixes in first micro-mixer 7 according to a certain percentage, and then diesel oil-ionic liquid mixture material is again and through oxygen
Agent pump 6 injection oxidant mixed in second micro-mixer 9, subsequent diesel oil-ionic liquid-oxidant mixture material into
Enter micro passage reaction 10, and completes the oxidation and removing of sulfide, the mixed material warp after reaction under default reaction condition
Enter in the product receiver 13 being located in cooling device 14 after crossing counterbalance valve 12, product receiver 13 is then placed in centrifuge
In be centrifuged, upper phase be desulfurized diesel oil 15, middle layer liquid phase be oxidant and its reaction product 16, lower layer's liquid phase
For the ionic liquid 17 for being dispersed with catalyst, which is recycled.
Embodiment 1
To verify effect of the invention, with sulfur content for 500ppm model diesel oil (dibenzothiophenes and normal octane it is mixed
Close object) it is research object, using ionic liquid BmimPF6For the extractant, (H of hydrogen peroxide containing 30wt%2O2) hydrogen peroxide be oxygen
Agent, ammonium heptamolybdate [(NH4)6Mo7O24·4H2O] it is catalyst, using process flow shown in FIG. 1, model diesel oil is carried out
Desulfurization.Wherein, two micro-mixers are all made of T-type hybrid mode, and microring array channel diameter is 0.5mm, a length of 100mm；
Micro- reaction channel diameter is 0.5mm, a length of 5000mm.
Before carrying out desulfurization, preparation [(NH first4)6Mo7O24·4H2O] concentration be 4g/L BmimPF6-[(NH4)6Mo7O24·4H2O] mixture, and with ultrasonic oscillation, it is dispersed with [(NH4)6Mo7O24·4H2O] BmimPF6It suspends
Liquid.
Carry out desulfurization when, setting reaction temperature be 80 DEG C, micro passage reaction outlet pressure be 275kPa,
BmimPF6Molar ratio with sulphur is 100, H2O2Be 18 with the molar ratio of sulphur, adjustings diesel oil flow velocity be 27.67 μ L/min,
BmimPF6Suspension flow velocity is 5.53 μ L/min, dioxygen water flow velocity is 0.55 μ L/min, makes diesel oil-BmimPF6Hydrogen peroxide three-phase
Residence time of the material in micro- reaction channel is 30min.Gas chromatographic analysis is carried out to desulfurized diesel oil, learns desulfurized diesel oil sulphur
Content is 9.5ppm, and desulfurization degree 98.10% reaches Ultra-deep Desulfurization of Diesel Fuels requirement；Micro passage reaction pressure is reduced to
1.0kPa meets production engineering specifications.
Comparative example 1
Change micro passage reaction outlet pressure is 100kPa, remaining condition is the same as embodiment 1.Desulfurized diesel oil sulfur content is
58.7ppm, the requirement of desulfurization degree 88.26%, not up to Ultra-deep Desulfurization of Diesel Fuels.
Comparative example 2
Change micro passage reaction outlet pressure is 600kPa, remaining condition is the same as embodiment 1.Desulfurized diesel oil sulfur content is
8.2ppm, desulfurization degree 98.36% reach Ultra-deep Desulfurization of Diesel Fuels requirement；Micro passage reaction pressure is reduced to 1.0kPa, meets
Production engineering specifications.
Comparative example 3
Changing reaction temperature is 30 DEG C, remaining condition is the same as embodiment 1.Desulfurized diesel oil sulfur content is 357.2ppm, desulfurization degree
It is 28.56%, not up to Ultra-deep Desulfurization of Diesel Fuels requirement.
Comparative example 4
Changing reaction temperature is 90 DEG C, remaining condition is the same as embodiment 1.Desulfurized diesel oil sulfur content is 7.4ppm, and desulfurization degree is
98.52%, reach Ultra-deep Desulfurization of Diesel Fuels requirement；Micro passage reaction pressure is reduced to 1.0kPa, meets production engineering specifications.
Comparative example 5
Changing microring array channel and micro- reaction channel diameter is 0.10mm, adjustings diesel oil flow velocity be 1.07 μ L/min,
BmimPF6Suspension flow velocity is 0.21 μ L/min, dioxygen water flow velocity is 0.02 μ L/min, makes diesel oil-BmimPF6Hydrogen peroxide three-phase
Residence time of the material in micro- reaction channel is 30min, remaining condition is the same as embodiment 1.Desulfurized diesel oil sulfur content is 7.5ppm,
Desulfurization degree is 98.50%, reaches Ultra-deep Desulfurization of Diesel Fuels requirement；Micro passage reaction pressure is reduced to 26.1kPa, does not meet technique
Design requirement.
Comparative example 6
Changing microring array channel and micro- reaction channel diameter is 1mm, adjustings diesel oil flow velocity be 110.70 μ L/min,
BmimPF6Suspension flow velocity is 22.14 μ L/min, dioxygen water flow velocity is 2.21 μ L/min, makes diesel oil-BmimPF6Hydrogen peroxide three
Residence time of the phase materials in micro- reaction channel is 30min, remaining condition is the same as embodiment 1.Desulfurized diesel oil sulfur content is
83.2ppm, the requirement of desulfurization degree 83.36%, not up to Ultra-deep Desulfurization of Diesel Fuels.
Comparative example 7
Change a length of 1000mm of micro- reaction channel, diesel oil flow velocity is 5.53 μ L/min, BmimPF6Suspension flow velocity is 1.11
μ L/min, dioxygen water flow velocity are 0.11 μ L/min, the same embodiment of remaining condition.Desulfurized diesel oil sulfur content is 9.8ppm, desulfurization degree
It is 98.04%, reaches Ultra-deep Desulfurization of Diesel Fuels requirement；Micro passage reaction pressure is reduced to 0.4kPa, meets production engineering specifications.
Comparative example 8
Change a length of 25000mm of micro- reaction channel, diesel oil flow velocity is 138.37 μ L/min, BmimPF6Suspension flow velocity is
27.67 μ L/min, dioxygen water flow velocity are 2.77 μ L/min, the same embodiment of remaining condition.Desulfurized diesel oil sulfur content is 9.2ppm, is taken off
Sulphur rate is 98.16%, reaches Ultra-deep Desulfurization of Diesel Fuels requirement；Micro passage reaction pressure is reduced to 26.1kPa, does not meet technique and sets
Meter requires.
Comparative example 9
Change a length of 30mm in microring array channel, remaining condition is the same as embodiment 1.Desulfurized diesel oil sulfur content is 67.7ppm, desulfurization
Rate is 86.46%, not up to Ultra-deep Desulfurization of Diesel Fuels requirement.
Comparative example 10
Change a length of 300mm in microring array channel, remaining condition is the same as embodiment 1.Desulfurized diesel oil sulfur content is 9.6ppm, desulfurization
Rate is 98.08%, reaches Ultra-deep Desulfurization of Diesel Fuels requirement；Micro passage reaction pressure is reduced to 1.0kPa, meets technological design and wants
It asks.
Comparative example 11
Change BmimPF6Molar ratio with sulphur is 50, H2O2Molar ratio with sulphur is 9, and adjusting diesel oil flow velocity is 30.42 μ L/
min、BmimPF6Suspension flow velocity is 3.04 μ L/min, dioxygen water flow velocity is 0.30 μ L/min, makes diesel oil-BmimPF6Hydrogen peroxide
Residence time of three phase materials in micro- reaction channel is 30min, remaining condition is the same as embodiment 1.Desulfurized diesel oil sulfur content is
56.9ppm, the requirement of desulfurization degree 88.62%, not up to Ultra-deep Desulfurization of Diesel Fuels.
Comparative example 12
Change BmimPF6Molar ratio with sulphur is 250, H2O2Molar ratio with sulphur is 45, and adjusting diesel oil flow velocity is 21.78 μ
L/min、BmimPF6Suspension flow velocity is 10.89 μ L/min, dioxygen water flow velocity is 1.09 μ L/min, makes diesel oil-BmimPF6It is double
Residence time of three phase materials of oxygen water in micro- reaction channel is 30min, remaining condition is the same as embodiment 1.Desulfurized diesel oil sulfur content
For 2.7ppm, desulfurization degree 99.46% reaches Ultra-deep Desulfurization of Diesel Fuels requirement；Micro passage reaction pressure is reduced to 1.0kPa, symbol
Close production engineering specifications.
Embodiment 2
Reaction process is referring to described in embodiment 1.Setting reaction temperature is 60 DEG C, micro passage reaction outlet pressure is
275kPa、BmimPF6Molar ratio with sulphur is 100, H2O2Molar ratio with sulphur is 18, and adjusting diesel oil flow velocity is 13.83 μ L/
min、BmimPF6Suspension flow velocity is 2.77 μ L/min, dioxygen water flow velocity is 0.28 μ L/min, makes diesel oil-BmimPF6Hydrogen peroxide
Residence time of three phase materials in micro- reaction channel is 60min, to model in microreactor system same as Example 1
Diesel oil carries out desulfurization.The results show that desulfurized diesel oil sulfur content is 3.8ppm, desulfurization degree 99.24% reaches diesel oil ultra-deep
Spend desulfurization requirement；Micro passage reaction pressure is reduced to 0.7kPa, meets production engineering specifications.
Comparative example 13
Change micro passage reaction outlet pressure is 100kPa, remaining condition is the same as embodiment 2.Desulfurized diesel oil sulfur content is
15.7ppm, the requirement of desulfurization degree 96.86%, not up to Ultra-deep Desulfurization of Diesel Fuels.
Comparative example 14
Changing reaction temperature is 30 DEG C, remaining condition is the same as embodiment 2.Desulfurized diesel oil sulfur content is 285.7ppm, desulfurization degree
It is 42.86%, not up to Ultra-deep Desulfurization of Diesel Fuels requirement.
Comparative example 15
Adjusting diesel oil flow velocity is 27.67 μ L/min, BmimPF6Suspension flow velocity is 5.53 μ L/min, dioxygen water flow velocity is
0.55 μ L/min, makes diesel oil-BmimPF6Residence time of three phase materials of hydrogen peroxide in micro- reaction channel is 30min, remaining
Condition is the same as embodiment 2.Desulfurized diesel oil sulfur content is 150.6ppm, and desulfurization degree 69.88%, not up to Ultra-deep Desulfurization of Diesel Fuels are wanted
It asks.
Embodiment 3
Reaction process is referring to described in embodiment 1.Setting reaction temperature is 60 DEG C, micro passage reaction outlet pressure is
275kPa、BmimPF6Molar ratio with sulphur is 250, H2O2Molar ratio with sulphur is 45, and adjusting diesel oil flow velocity is 21.78 μ L/
min、BmimPF6Suspension flow velocity is 10.89 μ L/min, dioxygen water flow velocity is 1.09 μ L/min, makes diesel oil-BmimPF6Dioxygen
Residence time of three phase materials of water in micro- reaction channel is 30min, to mould in microreactor system same as Example 1
Type diesel oil carries out desulfurization.The results show that desulfurized diesel oil sulfur content is 6.2ppm, it is super to reach diesel oil for desulfurization degree 98.76%
Deep desulfuration requirement；Micro passage reaction pressure is reduced to 0.7kPa, meets production engineering specifications.
Comparative example 16
Change micro passage reaction outlet pressure is 100kPa, remaining condition is the same as embodiment 3.Desulfurized diesel oil sulfur content is
11.2ppm, the requirement of desulfurization degree 97.76%, not up to Ultra-deep Desulfurization of Diesel Fuels.
Comparative example 17
Changing reaction temperature is 30 DEG C, remaining condition is the same as embodiment 3.Desulfurized diesel oil sulfur content is 234.9ppm, desulfurization degree
It is 53.02%, not up to Ultra-deep Desulfurization of Diesel Fuels requirement.
Embodiment 4
Reaction process is referring to described in embodiment 1.In order to increase treating capacity, by microreactor system microring array channel and
Micro- reaction channel diameter be changed to 0.75mm, microring array channel it is long be changed to 200mm, micro- reaction channel length is changed to 20000mm, using with
The identical reaction condition of embodiment 1 carries out desulfurization to model diesel oil.Wherein, adjust diesel oil flow velocity be 189.92 μ L/min,
BmimPF6Suspension flow velocity is 94.96 μ L/min, dioxygen water flow velocity is 9.50 μ L/min, makes diesel oil-BmimPF6Hydrogen peroxide three
Residence time of the phase materials in micro- reaction channel is 30min.The results show that desulfurized diesel oil sulfur content is 9.7ppm, desulfurization degree
It is 98.06%, reaches Ultra-deep Desulfurization of Diesel Fuels requirement；Micro passage reaction pressure is reduced to 0.7kPa, meets production engineering specifications.
Comparative example 18
Change microring array channel is 50mm, remaining condition is the same as embodiment 4.Desulfurized diesel oil sulfur content is 37.8ppm, desulfurization degree
It is 92.44%, not up to Ultra-deep Desulfurization of Diesel Fuels requirement.
Claims (12)
1. a kind of method that diesel oil extracted-aoxidized ultra-deep desulfurization in microreactor system, it is characterised in that: by diesel oil and dispersion
Have in prior to first micro-mixer of the extractant ionic liquid of catalyst and mix, in microring array channel most of sulfide from
Diesel oil is extracted to ionic liquid, and mixed diesel oil-non-aqueous ionic liquid material is again with oxidant in second micro-mixer
Mix and complete under default reaction condition the oxidation and removing of sulfide；Material after reaction enters through counterbalance valve is located at cooling
In product receiver in device, then product receiver is placed in a centrifuge and is centrifuged, upper phase is desulfurization
Diesel oil, middle layer liquid phase are oxidant and its reaction product, and lower layer's liquid phase is the ionic liquid for being dispersed with catalyst, the ionic liquid
Body circulation uses；
This method be 30 ~ 100 DEG C of reaction temperature, micro passage reaction outlet pressure be 200 ~ 500 kPa, ionic liquid with
It is carried out in microreactor system under conditions of molar ratio 1:1 ~ 100:1 of molar ratio 20:1 ~ 400:1 of sulphur, oxidant and sulphur,
Diesel oil-residence time of three phase materials of ionic liquid-oxidant in micro passage reaction is 10 ~ 90 min.
2. according to the method described in claim 1, it is characterized by: diesel oil, ionic liquid, oxidant three strands of materials are respectively through controlling
Warm device is preheated to reaction temperature, then through described first, second micro-mixer mixing, mixed diesel oil-ionic liquid-
Three phase materials of oxidant enter micro passage reaction.
3. method according to claim 1 or 2, it is characterised in that: the micro-mixer and micro passage reaction are placed in
In temperature regulating device；The product receiver is placed in cooling device.
4. method according to claim 1 or 2, it is characterised in that: the method is suitable for Ultra-deep Desulfurization of Diesel Fuels, and diesel oil sulphur contains
Amount is 10 ~ 5000 μ g/g, and the desulfurized diesel oil sulfur content is not higher than 10 μ g/g.
5. method according to claim 1 or 2, it is characterised in that: the catalyst is a kind of dimolybdate salt catalyst, tool
Body is positive ammonium molybdate ((NH4)2MoO4), ammonium dimolybdate ((NH4)2Mo2O7), ammonium tetramolybdate ((NH4)2Mo4O13), ammonium heptamolybdate
((NH4)6Mo7O24) one of or two kinds or more, mass concentration of the catalyst in ionic liquid be 2 ~ 10 g/L.
6. method according to claim 1 or 2, it is characterised in that: the ion liquid abstraction agent includes 1- butyl -3- first
Base limidazolium hexafluorophosphate (BmimPF6) and 1- octyl -3- methylimidazole hexafluorophosphate (OmimPF6) one of or two kinds.
7. method according to claim 1 or 2, it is characterised in that: the oxidant includes the mistake of 35 wt% of mass concentration
One of fluoroacetic acid, the tertbutanol peroxide of 70 wt% of mass concentration, 30 wt% hydrogen peroxide of mass concentration or two kinds or more.
8. according to the method described in claim 3, it is characterized by: the microring array channel equivalent diameter in the micro-mixer is
0.1 ~ 1 mm, length are 50 ~ 300 mm.
9. according to the method described in claim 3, it is characterized by: micro- reaction channel equivalent in the micro passage reaction is straight
Diameter is 0.1 ~ 1 mm, and length is 1000 ~ 50000 mm.
10. according to the method described in claim 1, micro passage reaction exports it is characterized by: reaction temperature is 50 ~ 80 DEG C
Pressure is 250 ~ 400 kPa, and the molar ratio of ionic liquid and sulphur is 100:1 ~ 250:1, but the volume ratio of ionic liquid and diesel oil
Should be not less than 0.05, the molar ratio of oxidant and sulphur is 10:1 ~ 50:1, but the volume ratio of oxidant and diesel oil should be not less than
0.01, diesel oil-residence time of three phase materials of ionic liquid-oxidant in micro passage reaction is 30 ~ 60 min.
11. according to the method described in claim 8, it is characterized by: microring array channel equivalent diameter be 0.5 ~ 0.8 mm,
Length is 100 ~ 200 mm.
12. according to the method described in claim 9, it is characterized by: micro- reaction channel equivalent diameter be 0.5 ~ 0.8 mm,
Length is 5000 ~ 20000 mm.
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| CN113322094B (en) * | 2021-05-24 | 2023-06-09 | 江苏大学 | Reactive extraction desulfurization and denitrification and high value-added product recovery process |
| CN113880066B (en) * | 2021-11-12 | 2023-07-21 | 深圳市研一新材料有限责任公司 | Method for preparing lithium difluorophosphate by flow chemistry method |
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| CN114602553B (en) * | 2022-03-31 | 2023-01-17 | 南京大学 | Macroporous weak-base anion resin supported tungsten-based catalyst, micro-channel continuous flow oxidation system thereof and application |
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