CN107312565B - A kind of method of three components eutectic agent abstraction desulfurization - Google Patents
A kind of method of three components eutectic agent abstraction desulfurization Download PDFInfo
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- CN107312565B CN107312565B CN201710770155.7A CN201710770155A CN107312565B CN 107312565 B CN107312565 B CN 107312565B CN 201710770155 A CN201710770155 A CN 201710770155A CN 107312565 B CN107312565 B CN 107312565B
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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
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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
- C10G21/16—Oxygen-containing compounds
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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
- C10G21/20—Nitrogen-containing compounds
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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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- 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
The invention discloses a kind of methods of three component eutectic agent extraction fuel desulfuration being made of alkylol, quaternary alkylammonium halides and Bronsted acid, agent oil quality is mixed than the fuel oil for being 100~600ppm for the three component eutectic agent of 1:1~1:3 and sulfur content, 5~30min is extracted at 440~880r/min of stirring rate, 20~30 DEG C.Present invention introduces Bronsted acids as third component, not only significantly increases the desulfurization degree of eutectic agent, but also significantly reduces the mutual solubility of eutectic agent and fuel oil, realizes efficiently separating and being recycled for desulfurizing agent.The sulfur method is easy to operate, is easily achieved, and at low cost, environmental pollution is small, has a good application prospect.
Description
Technical field
The present invention relates to a kind of new methods of desulfurization of fuel oil, specifically using one kind by alkylol, tetraalkyl halogen
Change three component low-temperature eutectic solvents of ammonium and Bronsted acid composition as extractant, efficiently extraction removes thiophene-type sulfide in fuel oil
Method.
Background technique
Catalyst mechanism that sulfur-containing compound in oil product can destroy in motor vehicle causes the waste of resource and the row of pollutant
It puts, converted product oxygen sulfur compound can generate the environmental problems such as acid rain and air smog, jeopardize the health of human and animal.Face
To increasingly harsh environmental standard, the developed countries such as America and Europe carry out Europe V standard in succession, that is, realize zero sulphur emissions of fuel oil.At present
Although China has also promulgated the state V standard similar with Europe V, limited by desulfurization technology, it can not strict implement this standard.
Therefore, carry out practicable high efficiency fuel desulfurization technology in China, it is very urgent.
The traditional handicraft of fuel desulfuration technology is hydrodesulfurization, it is still the major way of industrial fuel desulfuration at present.
Hydrodesulfurization can eliminate the alkyl sulfur compounds such as thioether, mercaptan, but the thiophene-based fragrance sulfide being difficult to remove in fuel oil, and
Equipment energy consumption is big, and operating cost is high, there is significant limitation.The fuel desulfuration technology developed at present mainly has oxidation sweetening, inhales
Attached desulfurization, biological desulphurization, alkylating desulfurization and abstraction desulfurization etc..
Abstraction desulfurization is the difference of the distribution coefficient using the sulfide in oil product in oil product and extractant, by sulfide
(petroleum refining and chemical industry, 2012,43 (5): 98-102) are extracted from fuel oil.Abstraction desulfurization is because its is easy to operate, energy consumption
The advantages that low, at low cost, is to be easiest to realize one of industrialized desulfurization technology, is current research hotspot.Abstraction desulfurization skill
The key of art is the selection of extractant.Extractant, which generally requires, meets the following conditions: immiscible with fuel oil；Sulfide is extracting
Take dissolubility difference in agent and fuel oil larger；Extractant stability is good；Extractant and fuel oil can be easily separated.
Abstraction desulfurization includes traditional acid-alkali washing extraction and organic solvent extraction and develops faster ion in recent years
Liquid extraction etc..Acid-alkali washing extraction generally rinses fuel oil using inorganic acid or inorganic alkali solution, makes mercaptan therein, thioether
Deng or acid sulphide etc. be rinsed out, it is more difficult to remove the thiophene-type sulfides such as benzothiophene, dibenzo thiophene phenol.Organic solvent
Extract the residual very big in oily Xiang Zhongyou, it is easy to cause the pollution of oil product, and organic solvent is readily volatilized, be a kind of acyclic
Border friendly extractant.Ionic liquid steam forces down, designability is strong, conductivity is high, recycling is good, leads in fuel desulfuration
There is unique advantage in domain and has obtained very fast progress (modern chemical industry, 2013,33 (4): 33-37).However, ionic liquid raw material
Costly, synthesis step is complicated, and purification is difficult, and biodegradability is poor, cannot strictly be known as green fuel oil desulfurizing agent.
2003, Abbott etc. synthesized a kind of congruent melting being in a liquid state at room temperature using choline chloride and urea for the first time
Object opens the research epoch (Chemical communications, 2002,9 (1): 70-71) of low-temperature eutectic solvent.Low temperature
Congruent melting solvent (Deep eutectic solvent, DES) abbreviation eutectic agent, usually by hydrogen bond donor (HBD) and hydrogen bond receptor
(HBA) two components being composed or three component eutectic mixtures, hydrogen bond donor and hydrogen bond receptor are connected to one by hydrogen bond
Rise, thus the lattice energy both reduced, form fusing point close to room temperature eutectic.DES is as ionic liquid analog, no
Only there is the physicochemical properties equally excellent with ionic liquid, and the advantage for having its incomparable, as raw material are simply easy
, synthesis step is simple, atom utilization 100%, advantages of environment protection, gradually replaces ionic liquid, wide in recent years
It is general to be applied to many research fields (Chemicalreviews, 2014,114 (21), 11060-11082).
2013, DES was introduced into abstraction desulfurization field for the first time by Li et al., with tetrabutylammonium chloride (TBAC), tetramethyl chlorine
Change ammonium (TMAC) etc. as hydrogen bond receptor and has synthesized a series of DES, and be used for using malonic acid, glycerine etc. as hydrogen bond donor
Fuel desulfuration is extracted, preferable desulfurization effect (Green Chemistry, 2013,15 (10): 2793-2799) are achieved.Hereafter
DES gradually develops in desulfuration field, but that mainly study in recent years is application (Rsc of the two component DES in abstraction desulfurization
Advances,2016,6(36):30345-30352；Energy&Fuels 2016,30(7):5411-5418；Energy&
Fuels2016,30(10):8164-8170).2016, Li et al. was using TBAC as hydrogen bond receptor, using PEG as hydrogen bond donor,
Then suitable anhydrous metal halide is introduced, has synthesized the three component eutectic desulfurizing agent (Green containing metal for the first time
Chemistry,2016,18(13):3789-3795).Not only desulfurization degree is high by synthesized DES, but also largely enriches
The type of eutectic desulfurizing agent.But since there is metal halide anion such as Fe in such DES2Cl7 -/FeCl4 -,
It will cause oil product and isomerization occur.
Summary of the invention
The present invention is low for traditional sulfur method desulfurization degree, is difficult to remove thiophene-type sulfide and mesh in fuel oil
Two preceding component eutectic desulfurizing agents exist with oil product mutual solubility it is big, the disadvantages of effect is poor is recycled, invented three groups a kind of
The method for dividing the efficient abstraction desulfurization of eutectic agent, not only can efficiently remove the thiophene-type sulfide in fuel oil, realize high
Desulfurization degree, and the efficient circulation that eutectic desulfurizing agent may be implemented uses.
Research finds that small molecule alcohol can preferably remove thiophene-type sulfide, stronger because that can be formed between the two
Hydrogen bond.But small molecule alcohol is readily volatilized, and the solubility in oil product is excessive, is not readily separated.Using small molecule alcohol as hydrogen
The mixing such as key donor and hydrogen bond receptor such as quaternary alkylammonium halides, can form small molecule alcohol eutectic agent, the extraction for fuel oil
Take desulfurization.The study found that small molecule alcohol eutectic agent can reduce the vapour pressure of desulfurizing agent significantly, small molecular alcohol is overcome
The volatile disadvantage of class；In addition, reducing the mutual solubility of desulfurizing agent and fuel oil to a certain extent, but still can not achieve de-
Sulphur agent and fuel oil efficiently separate and the efficient circulation of desulfurizing agent uses.Accordingly, the present invention is low total in two component small molecule alcohols
On the basis of flux, Bronsted acid is introduced as third component, synthesizes three component eutectic desulfurizing agents, not only significantly increases de-
Sulphur rate, and the mutual solubility of desulfurizing agent and fuel oil is significantly reduced, realize efficiently separating and being recycled for desulfurizing agent.
The structural formula for the three component eutectic desulfurizing agents that the present invention synthesizes is as follows:
Component A is alkylol, and B component is quaternary alkylammonium halides, and component C is Bronsted acid (inorganic acid or organic acid).Three
Eutectic agent is formed by hydrogen bond 1 and hydrogen bond 2.Because the third component of addition is Bronsted acid, contain active Hydrogen Proton, it is easy to
Thiophenes are protonated, and form hydrogen bond between thiophene-type sulfide, therefore desulfurization degree can be increased；In addition, proton
The addition of acid can significantly increase the polarity of eutectic agent, the i.e. mutual solubility of significant decrease desulfurizing agent and fuel oil, it can be achieved that desulfurizing agent
With fuel oil efficiently separate and the efficient circulation of desulfurizing agent use.
Technical scheme is as follows:
Quantitative thiophene-type sulfide is dissolved in normal octane, is made into certain density sulfur-bearing simulation fuel oil.Into reaction flask
The three component eutectic agent and simulation fuel oil of a certain amount of dose of oil quality ratio is added, heating water bath simultaneously opens magnetic agitation, certain
Certain time is extracted under stirring rate, certain temperature.After liquid to be extracted cools down completely, upper layer oil product is isolated in suction of inclining, and uses microcoulomb
Logical sequence instrument measures remaining sulfur content in oil product, and three component eutectic desulfurizing agents of lower layer can direct reuse.
Thiophene-type sulfide as described in the above technical scheme mainly includes 4,6- dimethyl Dibenzothiophene, dibenzo thiophene
Pheno, benzothiophene, 2- methylthiophene, thiophene etc..
Sulfide concentration as described in the above technical scheme is generally 100~600ppm, agent oil quality than be generally 1:1~
1:3, stirring rate are generally 440~880r/min, and extraction temperature is generally 20~30 DEG C, and extraction time is generally 5~
30min。
Three components eutectic agent as described in the above technical scheme, preparation method are as follows: by the alkylol of certain mol proportion,
Quaternary alkylammonium halides and Bronsted acid are uniformly mixed, and 1h are stirred at 90 DEG C, solid gradually dissolves, and finally obtains transparent uniform oil
Shape liquid.
In the preparation method of above-mentioned three components eutectic agent, alkylol mainly include be n-butanol, n-amyl alcohol, n-hexyl alcohol,
N-heptanol, n-octyl alcohol etc..
Quaternary alkylammonium halides are mainly tetraethylammonium bromide, tetrapropyl bromine in the preparation method of above-mentioned three components eutectic agent
Change ammonium, tetrabutylammonium bromide etc..
Bronsted acid mainly includes concentrated hydrochloric acid, concentrated nitric acid, salicylic acid etc. in the preparation method of above-mentioned three components eutectic agent.
Characteristic and innovation of the invention:
1, for the first time using alkylol, quaternary alkylammonium halides and Bronsted acid as component, synthesize three component eutectic agent, raw material letter
It is singly easy to get, synthesis step is easy.
2, three component eutectic agent of synthesis are used for the abstraction desulfurization of fuel oil for the first time, it not only can efficient removing thiophene
Pheno class sulfide, and because the mutual solubility of desulfurizing agent and fuel oil is extremely low, convenient for disconnected from each other, realize fuel oil deep desulfuration and
The efficient circulation of desulfurizing agent uses.
3, the sulfur method is easy to operate, is easily achieved, and at low cost, environmental pollution is small, has a good application prospect.
Specific embodiment
The method of the present invention is further illustrated combined with specific embodiments below, but is not limitation of the invention.
The preparation of (1) three component eutectic agent (DES)
Embodiment 1
Weigh 32.2g (0.10mol) tetrabutylammonium bromide (TBAB), 14.8g n-butanol (n-BA) and 6.3g (0.10mol)
Concentrated nitric acid (65%HNO3), it is added in the round-bottomed flask of 100mL, 1h is heated and stirred at 90 DEG C, form claret oily
Liquid, as synthesized low-temperature eutectic solvent [TBAB] [n-BA] [HNO3]。
Embodiment 2
Weigh 32.2g (0.10mol) tetrabutylammonium bromide (TBAB), 14.8g (0.20mol) n-butanol (n-BA) and 3.6g
(0.10mol) concentrated hydrochloric acid (36%HCl), is added in the round-bottomed flask of 100mL, and 1h is heated and stirred at 90 DEG C, is formed bright
Yellow oily liquid, as synthesized low-temperature eutectic solvent [TBAB] [n-BA] [HCl].
Embodiment 3
Weigh 32.2g (0.10mol) tetrabutylammonium bromide (TBAB), 14.8g (0.20mol) n-butanol (n-BA) and
13.8g (0.10mol) salicylic acid (OHBA), is added in the round-bottomed flask of 100mL, and 1h is heated and stirred at 90 DEG C, is formed
Claret oily liquids, as synthesized low-temperature eutectic solvent [TBAB] [n-BA] [OHBA].
Embodiment 4
Weigh 21.0g (0.10mol) tetraethylammonium bromide (TEAB), 14.8g (0.20mol) n-butanol (n-BA) and
21.9g (0.60mol) concentrated hydrochloric acid (36%HCl), is added in the round-bottomed flask of 100mL, 1h, shape is heated and stirred at 90 DEG C
Yellowly oily liquids, as synthesized low-temperature eutectic solvent [TEAB] [n-BA] [HCl].
Embodiment 5
Weigh 26.6g (0.10mol) 4-propyl bromide (TPAB), 17.6g (0.20mol) n-amyl alcohol (n-PA) and
21.9g (0.60mol) concentrated hydrochloric acid (36%HCl), is added in the round-bottomed flask of 100mL, 1h, shape is heated and stirred at 90 DEG C
Yellowly oily liquids, as synthesized low-temperature eutectic solvent [TPAB] [n-PA] [HCl].
Embodiment 6
Weigh 26.6g (0.10mol) 4-propyl bromide (TPAB), 20.4g (0.20mol) n-hexyl alcohol (n-HA) and
21.9g (0.60mol) concentrated hydrochloric acid (36%HCl), is added in the round-bottomed flask of 100mL, 1h, shape is heated and stirred at 90 DEG C
Yellowly oily liquids, as synthesized low-temperature eutectic solvent [TPAB] [n-HA] [HCl].
Embodiment 7
Weigh 32.2 (0.10mol) tetrabutylammonium bromide (TBAB), 20.4g (0.20mol) n-hexyl alcohol (n-HA) 29.2g
(0.60mol) concentrated hydrochloric acid (36%HCl), is added in the round-bottomed flask of 100mL, and 1h is heated and stirred at 90 DEG C, is formed yellow
Color oily liquids, as synthesized low-temperature eutectic solvent [TBAB] [n-HA] [HCl].
Embodiment 8
Weigh 32.2g (0.10mol) tetrabutylammonium bromide (TBAB), 21.9g (0.20mol) n-heptanol (n-HEA) and
21.9g (0.60mol) concentrated hydrochloric acid (36%HCl), is added in the round-bottomed flask of 100mL, and 1h is heated at 90 DEG C, forms yellow
Oily liquids, as synthesized low-temperature eutectic solvent [TBAB] [n-HEA] [HCl].
Embodiment 9
Weigh 32.2g (0.10mol) tetrabutylammonium bromide (TBAB), 26.0g (0.20mol) n-butanol (n-BA) and
29.2g (0.60mol) concentrated hydrochloric acid (36%HCl), is added in the round-bottomed flask of 100mL, 1h, shape is heated and stirred at 90 DEG C
Yellowly oily liquids, as synthesized low-temperature eutectic solvent [TBAB] [n-OA] [HCl].
(2) the single-stage extraction desulfurization of DES
Embodiment 10
Quantitative benzothiophene is dissolved in normal octane, is made into the sulfur-bearing simulation fuel oil of 500ppm.Into 50mL round-bottomed flask
Addition agent oil quality is than low-temperature eutectic solvent [TBAB] [n-BA] [HNO for 1:13] and simulate fuel oil, heating water bath is simultaneously opened
Magnetic agitation is 880r/min, extracts 30min at 30 DEG C in stirring rate.After liquid to be extracted cools down completely, suction of inclining is isolated
Layer oil product, with remaining sulfur content in Microcoulomb instrument measurement oil product, calculating desulfurization degree is 81.49%.
Embodiment 11
Quantitative benzothiophene is dissolved in normal octane, is made into the sulfur-bearing simulation fuel oil of 500ppm.Into 50mL round-bottomed flask
Addition agent oil quality is than the low-temperature eutectic solvent [TBAB] [n-BA] [HCl] for 1:1 and simulates fuel oil, and heating water bath simultaneously opens magnetic
Power stirring is 880r/min, extracts 30min at 30 DEG C in stirring rate.After liquid to be extracted cools down completely, upper layer is isolated in suction of inclining
Oil product, with remaining sulfur content in Microcoulomb instrument measurement oil product, calculating desulfurization degree is 88.75%.
Embodiment 12
Quantitative benzothiophene is dissolved in normal octane, is made into the sulfur-bearing simulation fuel oil of 500ppm.Into 50mL round-bottomed flask
Addition agent oil quality is than the low-temperature eutectic solvent [TBAB] [n-BA] [OHBA] for 1:1 and simulates fuel oil, and heating water bath is simultaneously opened
Magnetic agitation is 880r/min, extracts 30min at 30 DEG C in stirring rate.After liquid to be extracted cools down completely, suction of inclining is isolated
Layer oil product, with remaining sulfur content in Microcoulomb instrument measurement oil product, calculating desulfurization degree is 67.71%.
Embodiment 13
Quantitative benzothiophene is dissolved in normal octane, is made into the sulfur-bearing simulation fuel oil of 500ppm.Into 50mL round-bottomed flask
Addition agent oil quality is than the low-temperature eutectic solvent [TEAB] [n-BA] [HCl] for 1:2 and simulates fuel oil, and heating water bath simultaneously opens magnetic
Power stirring is 880r/min, extracts 30min at 30 DEG C in stirring rate.After liquid to be extracted cools down completely, upper layer is isolated in suction of inclining
Oil product, with remaining sulfur content in Microcoulomb instrument measurement oil product, calculating desulfurization degree is 67.78%.
Embodiment 14
Quantitative benzothiophene is dissolved in normal octane, is made into the sulfur-bearing simulation fuel oil of 500ppm.Into 50mL round-bottomed flask
Addition agent oil quality is than the low-temperature eutectic solvent [TBAB] [n-HA] [HCl] for 1:2 and simulates fuel oil, and heating water bath simultaneously opens magnetic
Power stirring is 880r/min, extracts 30min at 20 DEG C in stirring rate.After liquid to be extracted cools down completely, upper layer is isolated in suction of inclining
Oil product, with remaining sulfur content in Microcoulomb instrument measurement oil product, calculating desulfurization degree is 73.51%.
Embodiment 15
Quantitative benzothiophene is dissolved in normal octane, is made into the sulfur-bearing simulation fuel oil of 500ppm.Into 50mL round-bottomed flask
Addition agent oil quality ratio is 1:2 low-temperature eutectic solvent [TBAB] [n-OA] [HCl] and simulation fuel oil, heating water bath simultaneously open magnetic force
Stirring is 880r/min, extracts 30min at 30 DEG C in stirring rate.After liquid to be extracted cools down completely, upper layer oil is isolated in suction of inclining
Product, with remaining sulfur content in Microcoulomb instrument measurement oil product, calculating desulfurization degree is 92%.
Embodiment 16
Quantitative benzothiophene is dissolved in normal octane, is made into the sulfur-bearing simulation fuel oil of 500ppm.Into 50mL round-bottomed flask
Addition agent oil quality is than the low-temperature eutectic solvent [TBAB] [n-HA] [HCl] for 1:2 and simulates fuel oil, and heating water bath simultaneously opens magnetic
Power stirring is 880r/min, extracts 5min at 30 DEG C in stirring rate.After liquid to be extracted cools down completely, upper layer is isolated in suction of inclining
Oil product, with remaining sulfur content in Microcoulomb instrument measurement oil product, calculating desulfurization degree is 75.84%.
Embodiment 17
Quantitative benzothiophene is dissolved in normal octane, is made into the sulfur-bearing simulation fuel oil of 500ppm.Into 50mL round-bottomed flask
Addition agent oil quality is than the low-temperature eutectic solvent [TBAB] [n-HA] [HCl] for 1:2 and simulates fuel oil, and heating water bath simultaneously opens magnetic
Power stirring is 880r/min, extracts 30min at 30 DEG C in stirring rate.After liquid to be extracted cools down completely, upper layer is isolated in suction of inclining
Oil product, with remaining sulfur content in Microcoulomb instrument measurement oil product, calculating desulfurization degree is 74.23%.
Embodiment 18
Quantitative benzothiophene is dissolved in normal octane, is made into the sulfur-bearing simulation fuel oil of 500ppm.Into 50mL round-bottomed flask
Addition agent oil quality is than the low-temperature eutectic solvent [TBAB] [n-HA] [HCl] for 1:2 and simulates fuel oil, and heating water bath simultaneously opens magnetic
Power stirring is 440r/min, extracts 10min at 30 DEG C in stirring rate.After liquid to be extracted cools down completely, upper layer is isolated in suction of inclining
Oil product, with remaining sulfur content in Microcoulomb instrument measurement oil product, calculating desulfurization degree is 70.29%.
Embodiment 19
Quantitative benzothiophene is dissolved in normal octane, is made into the sulfur-bearing simulation fuel oil of 500ppm.Into 50mL round-bottomed flask
Addition agent oil quality is than the low-temperature eutectic solvent [TBAB] [n-HA] [HCl] for 1:2 and simulates fuel oil, and heating water bath simultaneously opens magnetic
Power stirring is 880r/min, extracts 10min at 30 DEG C in stirring rate.After liquid to be extracted cools down completely, upper layer is isolated in suction of inclining
Oil product, with remaining sulfur content in Microcoulomb instrument measurement oil product, calculating desulfurization degree is 75.30%.
Embodiment 20
Quantitative benzothiophene is dissolved in normal octane, is made into the sulfur-bearing simulation fuel oil of 100ppm.Into 50mL round-bottomed flask
Addition agent oil quality is than the low-temperature eutectic solvent [TBAB] [n-HA] [HCl] for 1:2 and simulates fuel oil, and heating water bath simultaneously opens magnetic
Power stirring is 880r/min, extracts 10min at 30 DEG C in stirring rate.After liquid to be extracted cools down completely, upper layer is isolated in suction of inclining
Oil product, with remaining sulfur content in Microcoulomb instrument measurement oil product, calculating desulfurization degree is 100%.
Embodiment 21
Quantitative benzothiophene is dissolved in normal octane, is made into the sulfur-bearing simulation fuel oil of 600ppm.Into 50mL round-bottomed flask
Addition agent oil quality is than the low-temperature eutectic solvent [TBAB] [n-HA] [HCl] for 1:2 and simulates fuel oil, and heating water bath simultaneously opens magnetic
Power stirring is 880r/min, extracts 10min at 30 DEG C in stirring rate.After liquid to be extracted cools down completely, upper layer is isolated in suction of inclining
Oil product, with remaining sulfur content in Microcoulomb instrument measurement oil product, calculating desulfurization degree is 68.61%.
Embodiment 22
Quantitative benzothiophene is dissolved in normal octane, is made into the sulfur-bearing simulation fuel oil of 500ppm.Into 50mL round-bottomed flask
Addition agent oil quality is than the low-temperature eutectic solvent [TBAB] [n-HA] [HCl] for 1:3 and simulates fuel oil, and heating water bath simultaneously opens magnetic
Power stirring is 880r/min, extracts 10min at 30 DEG C in stirring rate.After liquid to be extracted cools down completely, upper layer is isolated in suction of inclining
Oil product, with remaining sulfur content in Microcoulomb instrument measurement oil product, calculating desulfurization degree is 58.63%.
Embodiment 23
Quantitative benzothiophene is dissolved in normal octane, is made into the sulfur-bearing simulation fuel oil of 500ppm.Into 50mL round-bottomed flask
Addition agent oil quality is than the low-temperature eutectic solvent [TBAB] [n-HA] [HCl] for 1:2 and simulates fuel oil, and heating water bath simultaneously opens magnetic
Power stirring is 880r/min, extracts 10min at 20 DEG C in stirring rate.After liquid to be extracted cools down completely, upper layer is isolated in suction of inclining
Oil product, with remaining sulfur content in Microcoulomb instrument measurement oil product, calculating desulfurization degree is 71.38%.
Embodiment 24
Quantitative thiophene is dissolved in normal octane, is made into the sulfur-bearing simulation fuel oil of 500ppm.It is added into 50mL round-bottomed flask
Agent oil quality is simultaneously opened magnetic force and is stirred than the low-temperature eutectic solvent [TBAB] [n-HA] [HCl] and simulation fuel oil for 1:2, heating water bath
It mixes, is 880r/min, extracts 10min at 30 DEG C in stirring rate.After liquid to be extracted cools down completely, upper layer oil is isolated in suction of inclining
Product, with remaining sulfur content in Microcoulomb instrument measurement oil product, calculating desulfurization degree is 95%.
Embodiment 25
Quantitative dibenzothiophenes is dissolved in normal octane, is made into the sulfur-bearing simulation fuel oil of 500ppm.To 50mL round-bottomed flask
Middle addition agent oil quality is than the low-temperature eutectic solvent [TBAB] [n-HA] [HCl] for 1:2 and simulates fuel oil, and heating water bath is simultaneously opened
Magnetic agitation is 880r/min, extracts 10min at 30 DEG C in stirring rate.After liquid to be extracted cools down completely, suction of inclining is isolated
Layer oil product, with remaining sulfur content in Microcoulomb instrument measurement oil product, calculating desulfurization degree is 80.91%.
Embodiment 26
Quantitative 4,6- dimethyl Dibenzothiophene is dissolved in normal octane, is made into the sulfur-bearing simulation fuel oil of 500ppm.To
Addition agent oil quality is than the low-temperature eutectic solvent [TBAB] [n-HA] [HCl] and simulation fuel oil for 1:2, water in 50mL round-bottomed flask
Magnetic agitation is heated and is opened in bath, is 880r/min, is extracted 10min at 30 DEG C in stirring rate.After liquid to be extracted cools down completely,
Upper layer oil product is isolated in suction of inclining, and with remaining sulfur content in Microcoulomb instrument measurement oil product, calculating desulfurization degree is 73.27%.
(3) the saturation extracting power of DES
Embodiment 27
In embodiment 19, extraction terminates, and after isolating upper layer oil product, continuously adds the mould with 19 phase homogenous quantities of embodiment
Quasi- fuel oil, with extracted next time under 19 the same terms of embodiment.Same steps, extractant after continuous extraction 10 times
[TBAB] [n-HA] [HCl] close saturation.
(4) the multitple extraction ability of DES
Embodiment 28
In embodiment 19, extraction terminates, and takes out the desulfurization fuel oil on upper layer, rejoins and 19 phase homogenous quantities of embodiment
Fresh low-temperature eutectic solvent [TBAB] [n-HA] [HCl] in, with extracted again under 19 the same terms of embodiment.Phase
Same step, after 3 grades of extractions, sulfur content can be lower than 10ppm.
(5) the recycling performance of DES
Embodiment 29
In embodiment 19, extraction terminates, and 6mL is added into the low-temperature eutectic solvent [TBAB] [n-HA] [HCl] of lower layer
Isometric water/alcohol mixture adds the isometric normal octane of 4mL/acetonitrile mixture and carries out Hui Cui after mixing evenly.
Vacuum is outstanding after returning extraction 6 times, at 50 DEG C is evaporated off water, finally obtains fresh DES.With under 19 the same terms of embodiment, with living again
DES carry out abstraction desulfurization again.Same steps, DES are recycled 5 times, and desulfurization degree does not change substantially.
(6) comparative example
Comparative example 1
With tetrabutylammonium bromide (TBAB) for hydrogen bond receptor, concentrated hydrochloric acid (36%HCl) is used as hydrogen bond donor, with rubbing for 1:2
You synthesize corresponding low-temperature eutectic solvent [TBAB] [HCl] at ratio.Quantitative benzothiophene is dissolved in normal octane, is made into
The sulfur-bearing of 500ppm simulates fuel oil.Into 50mL round-bottomed flask, addition agent oil quality is than the low-temperature eutectic solvent [TBAB] for 1:3
[HCl] and simulation fuel oil, heating water bath simultaneously open magnetic agitation, are 880r/min, extract 10min at 30 DEG C in stirring rate.
After liquid to be extracted cools down completely, upper layer oil product is isolated in suction of inclining, and with remaining sulfur content in Microcoulomb instrument measurement oil product, calculates desulfurization
Rate is 28.24%.
Comparative example 2
With tetrabutylammonium bromide (TBAB) for hydrogen bond receptor, n-hexyl alcohol (n-HA) is used as hydrogen bond donor, with the molar ratio of 1:2
Example synthesizes corresponding low-temperature eutectic solvent [TBAB] [n-HA].Into 50mL round-bottomed flask, addition agent oil quality is than for 1:1's
Low-temperature eutectic solvent [TBAB] [n-HA] and simulation fuel oil are 880r/min, stir 30min at 30 DEG C in stirring rate.Wait stir
Mix liquid it is completely cooling after, be not layered, i.e., low-temperature eutectic solvent dissolves each other completely with fuel oil, desulfurization degree 0.
Comparative example 3
With tetrabutylammonium bromide (TBAB) for hydrogen bond receptor, acetic acid (AC) is used as hydrogen bond donor, is closed with the molar ratio of 1:2
At corresponding low-temperature eutectic solvent [TBAB] [AC] out.Quantitative thiophene is dissolved in normal octane, is made into the sulfur-bearing simulation of 500ppm
Fuel oil.Into 50mL round-bottomed flask, addition agent oil quality is than the low-temperature eutectic solvent [TBAB] [AC] and simulation fuel oil for 1:2, water
Magnetic agitation is heated and is opened in bath, is 880r/min, is extracted 30min at 30 DEG C in stirring rate.After liquid to be extracted cools down completely,
Upper layer oil product is isolated in suction of inclining, and with remaining sulfur content in Microcoulomb instrument measurement oil product, calculating desulfurization degree is 42%.
Claims (3)
1. thiophene in a kind of three component eutectic agent extraction removing fuel oil being made of alkylol, tetraalkyl ammonium bromide and Bronsted acid
The method of class sulfide, it is characterized in that: by agent oil quality than be 100 for the three component eutectic agent of 1:1~1:3 and sulfur content~
The fuel oil of 600ppm is mixed, and is 440~880r/min, is extracted 5~30min at 20~30 DEG C in stirring rate, mixing
Liquid stands natural layering in cooling procedure, takes upper layer fuel oil mutually to measure remaining sulfur content and calculates desulfurization degree, and three groups of lower layer
Divide eutectic agent can direct reuse；Alkylol is n-butanol, n-amyl alcohol, n-hexyl alcohol, n-heptanol or n-octyl alcohol；Tetraalkyl bromine
Change ammonium is tetraethylammonium bromide, 4-propyl bromide or tetrabutylammonium bromide；Bronsted acid is concentrated hydrochloric acid, concentrated nitric acid or salicylic acid.
2. according to the method for claim 1, it is characterized in that: three component eutectic agent the preparation method comprises the following steps: by certain mole
Alkylol, tetraalkyl ammonium bromide and the Bronsted acid mixing of ratio, stir 1h at 90 DEG C, finally obtain transparent uniform liquid.
3. according to the method for claim 1, it is characterized in that: thiophene-type sulfide mainly includes 4,6- dimethylbiphenyl thiophene
Pheno, dibenzothiophenes, benzothiophene, 3 methyl thiophene or thiophene.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333037A (en) * | 2013-06-08 | 2013-10-02 | 大连大学 | Method for extracting benzothiophene by utilizing deep co-melting solvent composed of tetrabutylammonium chloride and polyethylene glycol |
| EP2650345A1 (en) * | 2012-04-13 | 2013-10-16 | King Saud University | Method for removal of sulfur containing compounds from hydrocarbon mixtures |
| CN103361107A (en) * | 2013-06-03 | 2013-10-23 | 大连大学 | Extraction method of benzothiophene |
| CN106753514A (en) * | 2016-12-27 | 2017-05-31 | 江苏大学 | A kind of method of choline eutectic solvent abstraction desulfurization |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2650345A1 (en) * | 2012-04-13 | 2013-10-16 | King Saud University | Method for removal of sulfur containing compounds from hydrocarbon mixtures |
| CN103361107A (en) * | 2013-06-03 | 2013-10-23 | 大连大学 | Extraction method of benzothiophene |
| CN103333037A (en) * | 2013-06-08 | 2013-10-02 | 大连大学 | Method for extracting benzothiophene by utilizing deep co-melting solvent composed of tetrabutylammonium chloride and polyethylene glycol |
| CN106753514A (en) * | 2016-12-27 | 2017-05-31 | 江苏大学 | A kind of method of choline eutectic solvent abstraction desulfurization |
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