CN108893137A - A kind of water base eutectic solvent and preparation method thereof and a kind of oil product extraction desulphurization method - Google Patents
A kind of water base eutectic solvent and preparation method thereof and a kind of oil product extraction desulphurization method Download PDFInfo
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- CN108893137A CN108893137A CN201810788241.5A CN201810788241A CN108893137A CN 108893137 A CN108893137 A CN 108893137A CN 201810788241 A CN201810788241 A CN 201810788241A CN 108893137 A CN108893137 A CN 108893137A
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- eutectic solvent
- water base
- water
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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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/27—Organic compounds not provided for in a single one of groups C10G21/14 - C10G21/26
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/28—Recovery of used solvent
-
- 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
Abstract
The present invention provides a kind of water base eutectic solvents and preparation method thereof and a kind of oil product extraction desulphurization method, belong to the technical field of desulfurization.The hydrogen bond receptor of water base eutectic solvent provided by the invention is quaternary ammonium salt and/or quaternary alkylphosphonium salt, hydrogen bond donor is water, using organic solvent compared to traditional eutectic solvent is hydrogen bond donor, water base eutectic solvent provided by the invention is more environmentally protective, and it is non-corrosive, desulphurizing ability is strong, and reproducibility is good；When carrying out desulfurizing oil using water base eutectic solvent provided by the invention for extractant, sweetening process and extractant regeneration process can be regulated and controled by the content to hydrogen bond donor water, it is not necessary that other substances such as strippant are added, so that either oil product or the extractant pollution that not will receive strippant in entire desulphurization system, and it is also pollution-free to environment, and entire sweetening process and extractant regeneration process condition are mild, easy serialization easy to operate is suitable for industrial production.
Description
Technical field
The present invention relates to the technical field of desulfurizing oil, in particular to a kind of water base eutectic solvent and preparation method thereof and
A kind of oil product extraction desulphurization method.
Background technique
The fast development of industry is increasingly severe to the pollution of environment bring, and wherein the burning of sulfur-containing compound is to environment
Pollution is particularly acute.The SOx that sulfur-containing compound burning generates in fuel oil can the mucous membrane of mucous membrane and respiratory tract to human body have by force
Strong stimulation can seriously cause bronchitis even pulmonary edema respiratory paralysis.In addition, being discharged into the SO in air2Meeting and water
Vapour reacts to form sulfate type acid rain, seriously pollutes environment.
In the case where environmental problem is urgently to be resolved now, country gives the content of sulphur in fuel oil increasingly strict
Standard so far requires to be lower than 10ppm.Industrial widely used sulfur method is hydrodesulfurization at present, and hydrodesulfurization is
Refer to that reaction is converted into the reaction of hydrogen sulfide under the atmosphere of hydrogen by the highly selective catalyst action of sulfur-containing compound.So
And due to the space steric effect of catalyst surface absorption, this sulfur method sloughs effect for armaticity organic sulfur compound
Fruit is bad, and sweetening process is carried out under the harsh conditions of high temperature and pressure.These limitations make the side of hydrodesulfurization
Method has been difficult to meet the needs of current people are for high-quality fuel oil, it is necessary to look for new sulfur method.
Nowadays, the method for non-hydrodesulfurization mainly has absorption desulfurization, biological desulphurization, oxidation sweetening and abstraction desulfurization.Wherein,
Abstraction desulfurization has obtained the favor of researchers with mild operating condition and shirtsleeve operation process, and become has prospect very much
Novel desulphurization technology.Common desulfurization is generally n,N-Dimethylformamide, N-Methyl pyrrolidone etc. with extractant at present, this
A little extractants itself have toxic, and extractant regeneration is difficult, sulfur method is complicated.
Eutectic solvent refers to that the eutectic mixture being made of two or three of compound, freezing point are substantially less than each
The fusing point of a component pure material.Compared to traditional organic solvent, eutectic solvent have extremely-low vapor pressure, high thermodynamics and
Many advantages, such as chemical stability, extremely low toxic；And for ionic liquid, eutectic solvent, which also has, to be more easier
The advantages that preparation, raw material sources are more extensive, more cheap.But current eutectic solvent is mostly using organic solvent as hydrogen bond
Donor does not have the feature of environmental protection, and it is not high to be applied to desulfurization degree when abstraction desulfurization.In addition, being often added has when extractant regeneration
The strippants such as solvent such as ether are stripped sulphur component, and the addition of organic solvent will cause environment dirt in regenerative process
The pollution of extractant after dye and regeneration.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of water base eutectic solvents and preparation method thereof and a kind of oil product to extract
Take sulfur method.Water base eutectic solvent provided by the invention using water as hydrogen bond donor, it is environmentally protective, have it is biodegradable
Property；Abstraction desulfurization is carried out to oil product using the water base eutectic solvent, sulfur method is simple, and effect is good, and reproducibility is good, can follow
Ring uses.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
A kind of water base eutectic solvent, including hydrogen bond donor and hydrogen bond receptor, the hydrogen bond receptor are quaternary ammonium salt and/or season
Microcosmic salt, the hydrogen bond donor are water；The molar ratio of the hydrogen bond receptor and hydrogen bond donor is 1:0.5~20.
Preferably, the cation of the quaternary ammonium salt has structure shown in Formulas I；
In Formulas I, R1、R2、R3And R4It independently is C1~C10Alkyl；
The anion of the quaternary ammonium salt is chloride ion or bromide ion.
Preferably, the cation of the quaternary alkylphosphonium salt has structure shown in formula II；
In formula II, R5、R6、R7And R8It independently is C1~C10Alkyl；
The anion of the quaternary alkylphosphonium salt is chloride ion or bromide ion.
The present invention provides the preparation methods of water base eutectic solvent described in above scheme, include the following steps：
Hydrogen bond receptor is mixed with water under the conditions of 20~80 DEG C, obtains water base eutectic solvent, the hydrogen bond receptor packet
Include quaternary ammonium salt and/or quaternary alkylphosphonium salt.
Preparation method described in water base eutectic solvent or above scheme described in above scheme is utilized the present invention provides a kind of
The method that the water base eutectic solvent of preparation carries out oil product abstraction desulfurization, includes the following steps：
Water base eutectic solvent and sour product are mixed and carry out abstraction desulfurization, obtains extraction phase and sweet oil after liquid separation
Product.
Preferably, the mass ratio of the water base eutectic solvent and sour product is 1:10~10:1.
Preferably, the temperature of the abstraction desulfurization is 20~80 DEG C.
Preferably, the abstraction desulfurization includes the stirring and standing successively carried out；The revolving speed of the stirring be 500~
1400rpm, the time of the stirring are 0.2~3h；
The time of the standing is 0.2~5h.
It preferably, further include the regeneration of water base eutectic solvent after the liquid separation；The regeneration includes the following steps：
The extraction phase and water, which are mixed, is precipitated sulfide, and it is molten to obtain eutectic after the sulfide of the precipitation is separated
Agent solution phase；
The eutectic solvent solution is mutually distilled, obtains regenerating water base eutectic solvent.
Preferably, the additional amount of the water with add to extraction phase and water mixed solution molar aqueous amount be 20~
Subject to 99.1%.
The present invention provides a kind of water base eutectic solvent, including hydrogen bond donor and hydrogen bond receptor, the water base eutectic
The hydrogen bond receptor of solvent is quaternary ammonium salt and/or quaternary alkylphosphonium salt, and hydrogen bond donor is water；The molar ratio of the hydrogen bond receptor and hydrogen bond donor
It is 1:0.5~20.Water base eutectic solvent provided by the invention has using water as hydrogen bond donor compared to traditional eutectic solvent use
Solvent is hydrogen bond donor, and water base eutectic solvent provided by the invention has very high green environmental protection；It is provided by the invention
Water base eutectic solvent toxicity is extremely low, has biodegradable, and preparation method is simple, and non-corrosive, desulphurizing ability is strong,
Reproducibility is good, when carrying out desulfurizing oil using water base eutectic solvent provided by the invention for extractant, to equipment and behaviour
Make mode without particular/special requirement.
The present invention provides it is a kind of using water base eutectic solvent described in above scheme carry out oil product abstraction desulfurization method,
Include the following steps：Water base eutectic solvent and sour product are mixed and carry out abstraction desulfurization, extraction phase is obtained after liquid separation and is taken off
Sulphur oil product.Extraction desulphurization method provided by the invention is using water base eutectic solvent as extractant, the hydrogen bond of water base eutectic solvent
Receptor is quaternary ammonium salt and/or quaternary alkylphosphonium salt, and quaternary ammonium salt and quaternary alkylphosphonium salt can be mutual with the generation hydrogen bond of the sulfide in oil product and/or CH- π
Effect, so that sulfide is extracted into water base eutectic solvent phase, sulfur method provided by the invention is simple, and effect is good.
Further, the present invention can regenerate extractant by the way that hydrogen bond donor (water) is added into extraction phase, whole
A extractant regeneration process, it is not necessary that other substances such as strippant are added, so that oil product and extractant be all in entire desulphurization system
Other pollutions are not will receive, and pollution-free to environment yet；And while extractant regeneration, the sulphur of high-purity can be isolated
Compound is recycled.The entire sweetening process of method provided by the invention and extractant regeneration process condition are mild, easy to operate
And easy serialization, is suitable for industrial production.
Embodiment the result shows that, the single-stage desulfurization degree of extraction desulphurization method provided by the invention can reach 70.4%, and pass through
After crossing level Four desulfurization, sulfur content in oil products can be down to 5.1ppm；Desulfurization degree and fresh eutectic solvent after extractant regeneration 8 times
Desulfurization degree is almost the same.
Detailed description of the invention
Fig. 1 is extraction procedure schematic diagram of the invention.
In Fig. 1：1- sink, 2- raw material tank, 3- stirred tank, 4- extractor system, 5- sedimentation basin, 6- drying box.
Specific embodiment
The present invention provides a kind of water base eutectic solvent, including hydrogen bond receptor and hydrogen bond donor, the water base eutectic
The hydrogen bond receptor of solvent is quaternary ammonium salt and/or quaternary alkylphosphonium salt, and hydrogen bond donor is water；The molar ratio of the hydrogen bond receptor and hydrogen bond donor
It is 1:0.5~20.
The hydrogen bond receptor of water base eutectic solvent provided by the invention is quaternary ammonium salt and/or quaternary alkylphosphonium salt.In the present invention, institute
The cation for stating quaternary ammonium salt preferably has structure shown in Formulas I；
In the present invention, R in Formulas I1、R2、R3And R4It is independently preferably C1~C10Alkyl, more preferably C1~C8Alkane
Base, more preferably methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl, n-hexyl, 2- methyl
Amyl, 3- methyl amyl, n-heptyl or n-octyl.
In the present invention, the cation of the quaternary ammonium salt is preferably tetraethylammonium cation, tetraethyl phosphorus cation, four fourths
Base ammonium cation, tetrabutyl phosphorus cation, tetrahexyl ammonium cation or four hexyl phosphorus cations.
In the present invention, the anion of the quaternary ammonium salt is preferably chloride ion or bromide ion；In the present invention, the quaternary ammonium
Salt is specifically preferably tetrabutylammonium chloride and/or tetrabutylammonium bromide.
In the present invention, the cation of the quaternary alkylphosphonium salt preferably has structure shown in formula II；
In the present invention, the R5、R6、R7And R8Type it is independent preferably with R described in above scheme1、R2、R3And R4's
Type is consistent, and details are not described herein.
In a specific embodiment of the present invention, the anion of the quaternary alkylphosphonium salt is preferably chloride ion or bromide ion；In this hair
In bright, the quaternary alkylphosphonium salt is specifically preferably tetrabutyl phosphorus chloride and/or tetrabutyl phosphonium bromide phosphorus.
In the present invention, the hydrogen bond donor of the water base eutectic solvent is water.The present invention does not have special want to the water
It asks, uses water well known to those skilled in the art.
In the present invention, the molar ratio of the hydrogen bond receptor and hydrogen bond donor is preferably 1:0.5~20, more preferably 1:
0.5~10.The present invention controls the molar ratio of hydrogen bond receptor and hydrogen bond donor within this range, it is ensured that hydrogen bond donor and hydrogen bond
Hydrogen bond is formed between receptor, and has preferable extracting power to sulfide.
The present invention provides the preparation methods of water base eutectic solvent described in above scheme, include the following steps：
Hydrogen bond receptor and water are mixed under the conditions of 20~80 DEG C, obtain water base eutectic solvent；The hydrogen bond receptor is
Quaternary ammonium salt and/or quaternary alkylphosphonium salt.
In the present invention, the mixed temperature is 20~80 DEG C, preferably 30~60 DEG C, more preferably 40 DEG C；This hair
Bright preferably to be mixed under agitation, the revolving speed of the stirring is preferably 100~1000rpm, preferably 300~
600rpm；The mixing time is preferably 0.01~3h, more preferably 0.2~1h.The present invention is directly in 20~80 DEG C of conditions
Lower to mix hydrogen bond donor and hydrogen bond receptor, preparation method is simple.
In a specific embodiment of the present invention, preferably will hydrogen bond receptor and water mix after be warming up to 20 under agitation~
80℃；Mixing time of the invention is calculated since when being warming up to required mixing temperature.
The present invention provides it is a kind of using water base eutectic solvent described in above scheme carry out oil product abstraction desulfurization method,
Include the following steps：
Water base eutectic solvent and sour product are mixed and carry out abstraction desulfurization, obtains extraction phase and sweet oil after liquid separation
Product.
In the present invention, the oil product of the sulfur-bearing is preferably the oil product of this field routine, such as without deep desulfuration
The oil product of processing, preferably to one of deep desulfuration gasoline, diesel oil, kerosene, naphtha, heavy oil or a variety of, more preferably
Gasoline and/or diesel oil to deep desulfuration；The present invention does not have particular/special requirement to the content of sulfide in the sour product, institute
The oil product for needing deep desulfuration can use method of the invention to carry out desulfurization, in a specific embodiment of the present invention, described
The content of the sulfide of sour product is preferably in 10ppm or more.
In the present invention, the mass ratio of the water base eutectic solvent and sour product is preferably 1:10~10:1, it is more excellent
It is selected as 1:5~5:1, further preferably 1:3~3:1.
In the present invention, the temperature of the abstraction desulfurization is preferably 20~80 DEG C, and more preferably 25~65 DEG C, the extraction
Desulfurization preferably includes the stirring and standing successively carried out；The revolving speed of the stirring is preferably 500~1400rpm, and more preferably 600
~1100rpm；The time of the stirring is preferably 0.2~3h, more preferably 0.5~2h；The time of the standing is preferably 0.2
~5h, more preferably 0.5~2h.In the present invention, the stirring and standing carry out under the conditions of 20~80 DEG C, after standing
To the sour product on upper layer and the extraction phase of lower layer.
After stratification, the present invention carries out liquid separation.The present invention does not have particular/special requirement to the specific method of the liquid separation, can
Two phases were separated.In a specific embodiment of the present invention, it is preferable to use decantation two phases were separated.
In the present invention, the hydrogen bond receptor in extraction process in water base eutectic solvent and testing sulphide interaction, thus
Sulfide is extracted into water base eutectic solvent phase.The desulfurization oil product obtained after extraction can directly be made according to the level of sulfur content
For product or enter next stage abstraction desulfurization, subsequent extraction process is consistent with above scheme, and details are not described herein；The present invention mentions
Multitple extraction desulfurization can be repeated in the method for confession, until the sulfur content in oil product complies with standard.
It in the present invention, further include the regeneration of water base eutectic solvent after the liquid separation；The regeneration includes the following steps：
The extraction phase and water, which are mixed, is precipitated sulfide, and it is molten to obtain eutectic after the sulfide of the precipitation is separated
Agent solution phase；
The eutectic solvent solution is mutually distilled, obtains regenerating water base eutectic solvent.
The present invention, which mixes the extraction phase and water, is precipitated sulfide, is vulcanized after the sulfide separation of the precipitation
Object and eutectic solvent solution phase.In the present invention, mixed solution of the additional amount of the water preferably to add to extraction phase and water
Molar aqueous amount be 20~99.1% subject to, more preferably 30~90%；Hydrogen bond donor water is added into extraction phase by the present invention,
The hydrogen bond and/or CH- π combination for destroying sulfide and hydrogen bond receptor, so that sulfide be made to be precipitated.
After sulfide is precipitated, the present invention separates the sulfide of the precipitation.The present invention is preferably precipitated in sulfide laggard
Row is stood, and is separated again after sulfide is precipitated completely；The time of the standing is preferably 0.5~48h, more preferably 2~
45h, most preferably 5~36h；The temperature of the standing is preferably -10~30 DEG C, more preferably 10~25 DEG C.In the present invention,
When the fusing point of the sulfide in the sour product is higher, stands after cure object and be precipitated with solid, the present invention preferably passes through
Sedimentation and/or filtering separate solid sulfide；When the fusing point of the sulfide in the sour product is lower, sulphur after standing
Compound is precipitated with liquid, and the present invention preferably passes through decantation and separates sulfide.The isolated sulfide of the present invention is high purity sulphur
Compound can be recycled directly.
After sulfide is separated, the present invention mutually distills obtained eutectic solvent solution, obtains regenerating water base eutectic
Solvent.In the present invention, the temperature of the distillation is preferably 50~100 DEG C, and more preferably 60~80 DEG C；The pressure of the distillation
Preferably 1~101kPa, more preferably 10~100kPa, further preferably 30~80kPa；The time of the distillation processing is excellent
It is selected as 0.5~8h, more preferably 1~6h.
The water in the eutectic solvent solution phase is evaporated off by distilling by the present invention, in specific embodiments of the present invention
In, excessive water in eutectic solvent solution phase is evaporated off by distilling, if the molar ratio of hydrogen bond receptor and water accords in residue
Close 1:0.5~20 ratio, the then namely regenerated water base eutectic solvent of residue；It, can be to surplus if water content is less in residue
Part water is added in excess, and the molar ratio of hydrogen bond receptor and water is made to meet 1:0.5~20 ratio；Or, if distillation make it is low total
Water in molten solvent solution phase is substantially all to be steamed, and hydrogen bond receptor is precipitated with solid-state, at this time can be by solid-state hydrogen bond receptor and water
Mixing prepares water base eutectic solvent again, to obtain regenerating water base eutectic solvent.
In the present invention, regenerating water base eutectic solvent can be used as the abstraction desulfurization that extractant continues sour product.
The entire sweetening process and extractant regeneration process condition of extraction desulphurization method provided by the invention are mild, operation letter
Single, easy serialization is suitable for industrial production；In a specific embodiment of the present invention, industry preferably is carried out according to system shown in Figure 1
Change continuous extraction desulfurization.
System shown in Figure 1 includes that sink (1), raw material tank (2), entrance and sink and raw material tank export the stirred tank being connected
(3), entrance exports the extractor system (4) being connected with stirred tank；It is connected with extraction tower outlet at bottom each in extractor system
Sedimentation basin (5) and sedimentation basin export the drying box (6) being connected；The sedimentation basin is provided with sulfide outlet；The sedimentation basin
It is provided with and exports the water inlet being connected with sink；
The extractor system includes n extraction tower, is followed successively by the first extraction tower to the n-th extraction tower, wherein n >=1, and n
Extraction tower is connected in series, and n-th of extraction tower is provided with qualified oil export.
When carrying out abstraction desulfurization using system shown in Figure 1, hydrogen bond receptor is placed in raw material tank (2) and in sink (1)
Water enter in stirred tank (3) together and be stirred, obtain extractant (i.e. water base eutectic solvent), then extractant enters extraction
Take and carry out abstraction desulfurization in Tower System (4), qualified oil product is obtained after extraction, extraction phase enters in sedimentation basin (5), while sink to
Water is inputted in sedimentation basin, sulfide is made to be precipitated and separate, and the water base eutectic solvent solution after separation mutually enters in drying box (6)
It is dry, regenerated hydrogen bond receptor is obtained, regeneration hydrogen bond receptor, which enters in stirred tank (3), to be recycled.
Water base eutectic solvent provided by the invention and preparation method thereof and a kind of oil product are extracted below with reference to embodiment
Sulfur method is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
It in following embodiments, is tested accordingly using mould oil, the preparation method of the mould oil is：It will be certain
The sulfide (thiophene, benzothiophene, dibenzothiophenes) of amount is dissolved in the mixing of a certain proportion of normal heptane, normal octane and toluene
In liquid；The initial content of sulfide is that (sulfide is normal in the oil product of sulfur compound by 500ppm~600ppm in the mould oil
Advising content is 500~600ppm).
Embodiment 1
5g tetrabutyl phosphonium bromide phosphorus and 0.53g water are added in flask, 40 DEG C are warming up under atmospheric agitation, speed of agitator
The water base eutectic solvent of clear can be obtained in 500rpm, stirring 30min.
The mould oil of the water base eutectic solvent of 5g synthesis and 5g sulfur-bearing (dibenzothiophenes) 500ppm is added to flask
In, in the case where normal pressure, temperature are 25 DEG C, 30min, speed of agitator 800rpm are stirred, 30min layering is stood, by being decanted oily phase
It is separated with extraction phase, wherein extraction phase recycles eutectic solvent by subsequent regenerative operation and reused.
The sulfur content of upper oil phase is accurately detected with sulphur blood urea/nitrogen analyzer, upper oil phase sulfur content is down to as the result is shown
148ppm, single-stage desulfurization degree are 70.4%.
Embodiment 2
5g tetrabutyl phosphonium bromide phosphorus and 0.79g water are added in flask, 40 DEG C are warming up under atmospheric agitation, speed of agitator
The water base eutectic solvent of clear can be obtained in 500rpm, stirring 30min.
The mould oil of the water base eutectic solvent of 5g synthesis and 5g sulfur-bearing (dibenzothiophenes) 500ppm is added to flask
In, in the case where normal pressure, temperature are 25 DEG C, 30min, speed of agitator 800rpm are stirred, 30min layering is stood, by being decanted oily phase
It is separated with extraction phase, wherein extraction phase recycles eutectic solvent by subsequent regenerative operation and reused.
The sulfur content of upper oil phase is accurately detected with sulphur blood urea/nitrogen analyzer, upper oil phase sulfur content is down to as the result is shown
166ppm, single-stage desulfurization degree are 66.8%.
Embodiment 3
5g tetrabutyl phosphonium bromide phosphorus and 1.33g water are added in flask, 40 DEG C are warming up under atmospheric agitation, speed of agitator
The water base eutectic solvent of clear can be obtained in 500rpm, stirring 30min.
The mould oil of the water base eutectic solvent of 5g synthesis and 5g sulfur-bearing (dibenzothiophenes) 500ppm is added to flask
In, in the case where normal pressure, temperature are 25 DEG C, 30min, speed of agitator 800rpm are stirred, 30min layering is stood, by being decanted oily phase
It is separated with extraction phase, wherein extraction phase recycles eutectic solvent by subsequent regenerative operation and reused.
The sulfur content of upper oil phase is accurately detected with sulphur blood urea/nitrogen analyzer, upper oil phase sulfur content is down to as the result is shown
214ppm, single-stage desulfurization degree are 57.3%.
Embodiment 4
5g tetrabutylammonium chloride and 0.65g water are added in flask, 40 DEG C are warming up under atmospheric agitation, speed of agitator
The water base eutectic solvent of clear can be obtained in 500rpm, stirring 30min.
The mould oil of the water base eutectic solvent of 5g synthesis and 5g sulfur-bearing (dibenzothiophenes) 500ppm is added to flask
In, in the case where normal pressure, temperature are 25 DEG C, 30min, speed of agitator 800rpm are stirred, 30min layering is stood, by being decanted oily phase
It is separated with extraction phase, wherein extraction phase recycles eutectic solvent by subsequent regenerative operation and reused.
The sulfur content of upper oil phase is accurately detected with sulphur blood urea/nitrogen analyzer, upper oil phase sulfur content is down to as the result is shown
138ppm, single-stage desulfurization degree are 72.4%.
Embodiment 5
5g tetrabutyl phosphonium bromide phosphorus and 0.53g water are added in flask, 40 DEG C are warming up under atmospheric agitation, speed of agitator
The water base eutectic solvent of clear can be obtained in 500rpm, stirring 30min.
The mould oil of water base eutectic solvent synthesized by 5g and 5g sulfur-bearing (benzothiophene) 500ppm is added to flask
In, in the case where normal pressure, temperature are 25 DEG C, 30min, speed of agitator 800rpm are stirred, 30min layering is stood, by being decanted oily phase
It is separated with extraction phase, wherein extraction phase recycles eutectic solvent by subsequent regenerative operation and reused.
The sulfur content of upper oil phase is accurately detected with sulphur blood urea/nitrogen analyzer, upper oil phase sulfur content is down to as the result is shown
155ppm, single-stage desulfurization degree are 69.1%.
Embodiment 6
5g tetrabutyl phosphonium bromide phosphorus and 0.53g water are added in flask, 40 DEG C are warming up under atmospheric agitation, speed of agitator
The water base eutectic solvent of clear can be obtained in 500rpm, stirring 30min.
The mould oil of water base eutectic solvent synthesized by 5g and 5g sulfur-bearing (thiophene) 500ppm is added in flask,
Normal pressure, temperature are magnetic agitation 30min, speed of agitator 800rpm at 25 DEG C, stand 30min layering, by decantation by it is oily mutually with
Extraction phase separation, wherein extraction phase recycles eutectic solvent by subsequent regenerative operation and is reused.
The sulfur content of upper oil phase is accurately detected with sulphur blood urea/nitrogen analyzer, upper oil phase sulfur content is down to as the result is shown
166ppm, single-stage desulfurization degree are 66.8%.
Embodiment 7
5g tetrabutyl phosphonium bromide phosphorus and 0.53g water are added in flask, 40 DEG C are warming up under atmospheric agitation, speed of agitator
The water base eutectic solvent of clear can be obtained in 500rpm, stirring 30min.
The mould oil of the water base eutectic solvent of 5g synthesis and 5g sulfur-bearing (dibenzothiophenes) 600ppm is added to flask
In, in the case where normal pressure, temperature are 25 DEG C, 30min, speed of agitator 800rpm are stirred, 30min layering is stood, by being decanted oily phase
It is separated with extraction phase, wherein extraction phase recycles eutectic solvent by subsequent regenerative operation and reused.
The sulfur content of upper oil phase is accurately detected with sulphur blood urea/nitrogen analyzer.Upper oil phase sulfur content is down to 177ppm, and single-stage is de-
Sulphur rate is 70.5%.
For the feasibility for probing into multitple extraction, raffinate phase is imported into next stage and carries out extracting operation, extracting operations at different levels
Condition is consistent with step and the first order, and the abstraction desulfurization operation by continuous level Four, sulfur content in oil products is down to 5.1ppm, full
The requirement of sufficient deep desulfuration, desulfurization degrees at different levels keep stablizing, the first order to fourth stage desulfurization degree is respectively 70.5%, 69.8%,
69.3% and 69.0%.
Embodiment 8
5g tetrabutyl phosphonium bromide phosphorus and 0.53g water are added in flask, 40 DEG C are warming up under atmospheric agitation, speed of agitator
The water base eutectic solvent of clear can be obtained in 500rpm, stirring 30min.
The mould oil of water base eutectic solvent synthesized by 5g and 5g sulfur-bearing (dibenzothiophenes) 600ppm is added to burning
In bottle.Under normal pressure, 30min, speed of agitator 800rpm are stirred at being respectively 20 DEG C, 25 DEG C, 30 DEG C, 40 DEG C, 50 DEG C in temperature,
30min layering is stood, is mutually separated with extraction phase by decantation by oily.
The sulfur content of upper oil phase is accurately detected with sulphur blood urea/nitrogen analyzer, the desulfurization degree under the conditions of each temperature is listed in Table 1 below.
Desulfurization degree under the conditions of the different desulfurization temperatures of table 1
| Temperature/DEG C | 20 | 25 | 30 | 40 | 50 |
| Desulfurization degree % | 69.4 | 70.1 | 68.7 | 66.9 | 62.5 |
Can be seen that according to the data in table 1 has higher desulfurization degree under the conditions of 20~50 DEG C, and with temperature
It increases, desulfurization degree has downward trend after a first rising, and desulfurization degree is best under the conditions of 25 DEG C.
Embodiment 9
5g tetrabutyl phosphonium bromide phosphorus and 0.53g water are added in flask, 40 DEG C are warming up under atmospheric agitation, speed of agitator
The water base eutectic solvent of clear can be obtained in 500rpm, stirring 30min.
The mould oil of the eutectic solvent of 5g synthesis and 5g sulfur-bearing (dibenzothiophenes) 500ppm is added in flask,
Normal pressure, temperature are at 25 DEG C, and stirring 30min, speed of agitator 800rpm stand 30min layering, by being decanted oily phase and extraction
Mutually separate.
The sulfur content of upper oil phase is accurately detected with sulphur blood urea/nitrogen analyzer, upper oil phase sulfur content is down to as the result is shown
148ppm, single-stage desulfurization degree are 70.4%.
12.73g water is added into extraction phase, 12h is stood at being then 25 DEG C in normal pressure, temperature, after standing in solution
There are apparent white needle-like crystals to be precipitated, the crystal of precipitation is dibenzothiophenes, is with filter opening diameter by the solution after standing
0.22 micron of filter filtering；Filtrate is then rotated to 5h at 80 DEG C, 1kPa and obtains white solid realization tetrabutyl phosphonium bromide phosphorus
Regeneration, by after regeneration tetrabutyl phosphonium bromide phosphorus continue with hydration at water base eutectic solvent carry out abstraction desulfurization operation, operation
Condition be consistent before.Desulfurization degree after regeneration is 68.4%, and the desulfurization degree of comparatively fresh eutectic solvent only slightly drops
It is low.
Embodiment 10
5g tetrabutyl phosphonium bromide phosphorus and 0.53g water are added in flask, 40 DEG C are warming up under atmospheric agitation, speed of agitator
The water base eutectic solvent of clear can be obtained in 500rpm, stirring 30min.
The mould oil of the water base eutectic solvent of 5g synthesis and 5g sulfur-bearing (dibenzothiophenes) 500ppm is added to flask
In, in the case where normal pressure, temperature are 25 DEG C, 30min, speed of agitator 800rpm are stirred, stands 30min layering.
The sulfur content of upper oil phase is accurately detected with sulphur blood urea/nitrogen analyzer, upper oil phase sulfur content is down to as the result is shown
147.5ppm, single-stage desulfurization degree are 70.5%.
After the completion of desulfurization operations, is mutually separated with extraction phase by decantation by oily, 15.38g water is added into extraction phase, then
12h is stood at being 25 DEG C in normal pressure, temperature, there are apparent white needle-like crystals to be precipitated in solution after standing, the crystal of precipitation
For dibenzothiophenes, the filter that the solution filter opening diameter after standing is 0.22 micron is filtered；Then by filtrate 80 DEG C,
5h is rotated under 1kPa obtains the regeneration that white solid realizes tetrabutyl phosphonium bromide phosphorus.By after regeneration tetrabutyl phosphonium bromide phosphorus continue and water
Synthesize water base eutectic solvent and carry out abstraction desulfurization operation, operating condition be consistent before.Desulfurization degree after regeneration is
69.11%, slightly some reductions of the desulfurization degree of comparatively fresh eutectic solvent.
Embodiment 11
5g tetrabutyl phosphonium bromide phosphorus and 0.53g water are added in flask, 40 DEG C are warming up under atmospheric agitation, speed of agitator
The water base eutectic solvent of clear can be obtained in 500rpm, stirring 30min.
The mould oil of the water base eutectic solvent of 5g synthesis and 5g sulfur-bearing (dibenzothiophenes) 500ppm is added to flask
In, in the case where normal pressure, temperature are 25 DEG C, 30min, speed of agitator 800rpm are stirred, stands 30min layering.
The sulfur content of upper oil phase is accurately detected with sulphur blood urea/nitrogen analyzer.Upper oil phase sulfur content is down to 149ppm, and single-stage is de-
Sulphur rate is 70.2%.
After the completion of desulfurization operations, mutually mutually separated with extraction phase by decantation by oily.20.69g water is added into extraction phase, so
12h is stood at being afterwards 25 DEG C in normal pressure, temperature, there are apparent white needle-like crystals to be precipitated in solution after standing, the crystalline substance of precipitation
Body is dibenzothiophenes, and the filter that the solution filter opening diameter after standing is 0.22 micron is filtered；Then by filtrate 80 DEG C,
1.5h is rotated under 1kPa, the molar ratio 1 of hydrogen bond receptor and water in obtained liquid:2, realize the regeneration of water base eutectic solvent.
By after regeneration water base eutectic solvent carry out abstraction desulfurization operation, operating condition be consistent before.It is de- after regeneration
Sulphur rate is 69.88%, almost the same with the desulfurization degree of fresh eutectic solvent.
Embodiment 12
5g tetrabutyl phosphonium bromide phosphorus and 0.53g water are added in flask, 40 DEG C are warming up under atmospheric agitation, speed of agitator
The water base eutectic solvent of clear can be obtained in 500rpm, stirring 30min.
The mould oil of the water base eutectic solvent of 5g synthesis and 5g sulfur-bearing (dibenzothiophenes) 500ppm is added to flask
In, in the case where normal pressure, temperature are 25 DEG C, 30min, speed of agitator 800rpm are stirred, stands 30min layering.
The sulfur content of upper oil phase is accurately detected with sulphur blood urea/nitrogen analyzer, upper oil phase sulfur content is down to as the result is shown
148.5ppm, single-stage desulfurization degree are 70.3%.
After the completion of desulfurization operations, mutually mutually separated with eutectic solvent by decantation by oily.25.99g is added into extraction phase
Water stands 12h at being then 25 DEG C in normal pressure, temperature.There are apparent white needle-like crystals to be precipitated after standing in solution, is precipitated
Crystal be dibenzothiophenes.The filter that solution filter opening diameter after standing is 0.22 micron is filtered；Then filtrate is existed
80 DEG C, revolving 5h obtains the regeneration that white solid realizes tetrabutyl phosphonium bromide phosphorus under 1kPa.By the tetrabutyl phosphonium bromide phosphorus after regeneration after
It is continuous to carry out abstraction desulfurization operation at water base eutectic solvent and water with hydration, operating condition be consistent before.After regeneration
Desulfurization degree be 70.2%, it is consistent with the desulfurization degree of fresh eutectic solvent.
Embodiment 13
5g tetrabutyl phosphonium bromide phosphorus and 0.53g water are added in flask, 40 DEG C are warming up under atmospheric agitation, speed of agitator
The water base eutectic solvent of clear can be obtained in 500rpm, magnetic agitation 30min.
The mould oil of the water base eutectic solvent of 5g synthesis and 5g sulfur-bearing (dibenzothiophenes) 500ppm is added to flask
In, in the case where normal pressure, temperature are 25 DEG C, magnetic agitation 30min, speed of agitator 800rpm stand 30min layering.
The sulfur content of upper oil phase is accurately detected with sulphur blood urea/nitrogen analyzer, upper oil phase sulfur content is down to as the result is shown
148ppm, single-stage desulfurization degree are 70.4%.
After the completion of desulfurization operations, mutually mutually separated with eutectic solvent by decantation by oily.12.73g is added into extraction phase
Water stands 12h at being then 25 DEG C in normal pressure, temperature.There are apparent white needle-like crystals to be precipitated after standing in solution, is precipitated
Crystal be dibenzothiophenes.The filter that solution filter opening diameter after standing is 0.22 micron is filtered；Then filtrate is existed
80 DEG C, revolving 5h obtains the regeneration that white solid realizes tetrabutyl phosphonium bromide phosphorus under 1kPa.By operation before, by four after regeneration
Butyl phosphonium bromide and water continue to synthesize water base eutectic solvent progress abstraction desulfurization operation, and it is regenerated to repeat above-mentioned extraction-
Process 8 times, each secondary extraction conditions is consistent, and by the desulfurization of cycling extraction, the results are shown in Table 2.
2 cycling extraction desulfurization result of table
| Regeneration period | 0 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Desulfurization degree/% | 70.4 | 68.4 | 68.6 | 67.9 | 68.9 | 68.3 | 68.5 | 69.1 | 68.1 |
In table 2,0 represents fresh water base eutectic solvent, and 1~8 represents regeneration times.
It is still with higher de- to can be seen that the water base eutectic solvent being recycled after regeneration according to data in table 2
Sulphur rate illustrates that water base eutectic solvent reproducibility provided by the invention is good, can be recycled.
Above embodiments show that water base eutectic solvent desulphurizing ability provided by the invention is strong, pollution-free to oil product, can be again
Natural disposition is good；Extraction desulphurization method step provided by the invention is simple, and effect is good, and extractant regeneration process is without being added back extraction
Other substances such as agent, so that oil product and extractant not will receive other pollutions in entire desulphurization system.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of water base eutectic solvent, including hydrogen bond donor and hydrogen bond receptor, which is characterized in that the hydrogen bond receptor is quaternary ammonium
Salt and/or quaternary alkylphosphonium salt, the hydrogen bond donor are water；The molar ratio of the hydrogen bond receptor and hydrogen bond donor is 1:0.5~20.
2. water base eutectic solvent according to claim 1, which is characterized in that the cation of the quaternary ammonium salt has Formulas I
Shown structure；
In Formulas I, R1、R2、R3And R4It independently is C1~C10Alkyl；
The anion of the quaternary ammonium salt is chloride ion or bromide ion.
3. water base eutectic solvent according to claim 1, which is characterized in that the cation of the quaternary alkylphosphonium salt has formula II
Shown structure；
In formula II, R5、R6、R7And R8It independently is C1~C10Alkyl；
The anion of the quaternary alkylphosphonium salt is chloride ion or bromide ion.
4. the preparation method of water base eutectic solvent, includes the following steps described in claims 1 to 3 any one：
Hydrogen bond receptor is mixed with water under the conditions of 20~80 DEG C, obtains water base eutectic solvent, the hydrogen bond receptor includes season
Ammonium salt and/or quaternary alkylphosphonium salt.
5. a kind of utilize preparation method system described in water base eutectic solvent or claim 4 described in 3 any one of claims 1 to 3
The method that standby water base eutectic solvent carries out oil product abstraction desulfurization, includes the following steps：
Water base eutectic solvent and sour product are mixed and carry out abstraction desulfurization, extraction phase and desulfurization oil product are obtained after liquid separation.
6. according to the method described in claim 5, it is characterized in that, the mass ratio of the water base eutectic solvent and sour product
It is 1:10~10:1.
7. according to the method described in claim 5, it is characterized in that, the temperature of the abstraction desulfurization is 20~80 DEG C.
8. according to method described in claim 5~7 any one, which is characterized in that the abstraction desulfurization includes successively carrying out
Stirring and standing；The revolving speed of the stirring is 500~1400rpm, and the time of the stirring is 0.2~3h；
The time of the standing is 0.2~5h.
9. according to the method described in claim 5, it is characterized in that, further include after the liquid separation water base eutectic solvent again
It is raw；The regeneration includes the following steps：
The extraction phase and water, which are mixed, is precipitated sulfide, and it is molten to obtain eutectic solvent after the sulfide of the precipitation is separated
Liquid phase；
The eutectic solvent solution is mutually distilled, obtains regenerating water base eutectic solvent.
10. according to the method described in claim 9, it is characterized in that, the additional amount of the water is to add to the mixed of extraction phase and water
The molar aqueous amount for closing solution is subject to 20~99.1%.
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