CN103420802A - Novel method for separating phenolic compound from oil - Google Patents
Novel method for separating phenolic compound from oil Download PDFInfo
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- CN103420802A CN103420802A CN2012101640260A CN201210164026A CN103420802A CN 103420802 A CN103420802 A CN 103420802A CN 2012101640260 A CN2012101640260 A CN 2012101640260A CN 201210164026 A CN201210164026 A CN 201210164026A CN 103420802 A CN103420802 A CN 103420802A
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- 238000000034 method Methods 0.000 title claims abstract description 51
- 150000002989 phenols Chemical class 0.000 title claims abstract description 38
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002608 ionic liquid Substances 0.000 claims abstract description 62
- 238000000605 extraction Methods 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 22
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003245 coal Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 239000011280 coal tar Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- -1 phenols compounds Chemical class 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 7
- 239000012188 paraffin wax Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 150000008442 polyphenolic compounds Polymers 0.000 claims description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 3
- 150000004780 naphthols Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 229940094933 n-dodecane Drugs 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 229910052786 argon Inorganic materials 0.000 claims 1
- 230000001351 cycling effect Effects 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000011261 inert gas Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000003929 acidic solution Substances 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 150000001299 aldehydes Chemical class 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 235000013824 polyphenols Nutrition 0.000 description 4
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a novel method for separating phenolic compounds from oil. The method uses an imidazole ionic liquid as an extractant to separate phenolic compounds in coal tar, coal liquefaction oil and oil phenol mixtures, so as to realize recovery utilization of ionic liquid. The method avoids the usage of a large amount of acidic solution and aqueous alkali and generation of phenol-containing waste water in a traditional method, and has extremely high efficiency of separation. After extraction, a reverse extraction or inert gas stripping mode can be used to realize separation of a separating agent and phenols, and the separating agent can be repeatedly used and maintain almost unreduced extraction efficiency. Application of the method can effectively reduce production cost and equipment requirements and substantially simplify the traditional oil phenol separation technology, and has important practical significance and environmental significance.
Description
Technical field
The present invention relates to Coal Chemical Industry, petrochemicals separation field, be specifically related to from coal tar, liquefied coal coil, and the method for the middle separating phenols compounds of the mixture of other oil and phenol (by aromatic hydrocarbon, straight-chain paraffin or its mixture and phenolic compound form).
Background technology
Phenolic compound is the hydroxyl derivative of aromatic hydrocarbons, can be divided into monohydric phenol and polyphenol, or rudimentary phenol, higher phenols, and it forms according to source different and different.Phenolic compound main source refinery products, coal tar, liquefied coal coil, in the three, the composition of phenolic compound has very large similarity.Coal tar, oxygen acid material main in liquefied coal coil is phenolic compound, and its content is subject to coal, the processing condition impact is very large, and the phenol content in the low temperature fraction section is higher, can reach 20%-30%, so high phenol content can significantly increase the hydrogen consumption of subsequent process, causes the increase of production cost; In addition, the existence of phenolic compound has a certain impact to the stability of oil product, is unfavorable for storage and the transportation of oil product; Phenolic compound, as a kind of important organic intermediate and raw materials for production, is applied to medicine, and the numerous areas such as dyestuff are described as " valuable phenol ", thereby have sizable market requirement and using value.Yet, all there is larger breach in the phenols supply in China market every year, along with the more attention of country to the coal resources utilization, extract the demand that phenolic compound not only meets the national energy strategy from coal tar and liquefied coal coil product, widen the comprehensive Utilization Ways of coal tar and liquefied coal coil, there is sizable economic worth and social value simultaneously.
The method of separation and Extraction phenolic compound from coal tar or liquefied coal coil that at present many bibliographical informations arranged, mainly comprise chemical method and solvent extraction process, and wherein chemical method comprises alkali wash, Sodium sulfhydrate extraction process and sodium carbonate solution extraction process; Solvent extraction process comprises superheated water extraction process, alcohol solution extraction process and salts solution extraction process.Alkali wash is the slightly acidic of utilizing aldehydes matter, uses aqueous sodium hydroxide solution and its neutralization, and the sodium phenolate of generation is insoluble to oil phase and is transferred to water, re-uses carbonic acid gas or sulfuric acid and makes sodium phenolate be reduced to aldehydes matter.This method is simple to operate, and percentage extraction is relatively high, be most widely used, but this process is used a large amount of soda acids, serious to equipment corrosion, does not meet the requirement of friendly process, is badly in need of making improvements.The Sodium sulfhydrate extraction process is similar with the sodium carbonate solution extraction process, all under comparatively high temps and pressure, to use the strong base weak acid salt brine solution to react with aldehydes matter, make it to be converted into sodium phenolate, transferring under normal temperature makes sodium phenolate be reduced to aldehydes matter, this method is limited to chemical equilibrium, low to high boiling point phenols extraction efficiency; Sodium sulfhydrate is expensive and larger toxicity and corrodibility arranged.Superheated water extracting ratio juris is to utilize the solubility with temperature of phenols in water raise and increase, therefore comparatively strict for equipment requirements under higher service temperature, limitation is larger.The advantage of alcohol solution extraction process is that extractant is with low cost, easily reclaim, but percentage extraction is lower.The salts solution extraction process is to utilize the solvability extracting aldehydes matter of the aqueous solution of some salt to aldehydes matter, but the same with other extraction process, this process inevitably produces a large amount of phenolic wastewater to be needed to process, and has increased undoubtedly difficulty and the production cost of subsequent disposal.
At present existing lot of documents report ionic liquid is for the research of extracting and separating.Ionic liquid is a kind of in room temperature or approach under room temperature condition the salt be in a liquid state consisted of zwitterion.Ionic liquid is widely used at numerous areas, as electrochemistry, and liquid-liquid extraction, organic synthesis, this has benefited from ionic liquid zero vapour pressure, non-volatile, the characteristics such as high boiling point.Many bibliographical information ionic liquids and oil do not dissolve each other, and so just likely use ionic liquid extracting and separating phenol from oily phenol mixture, thereby realize that dry oily phenol separates.In addition, we can improve effect of extracting targetedly by the combination that changes zwitterion.Than traditional organic solvent, ionic liquid has high boiling point, nonvolatile characteristics, thereby be described as " green solvent ", can realize the recycling of ionic liquid by simple underpressure distillation.
In sum, for the shortcomings existed in current oil/phenol sepn process, such as highly basic, strong acid consumption are large, seriously polluted, percentage extraction is low, the condition harshness, equipment requirements height etc., present method intends adopting eco-friendly ionic liquid as separating medium, and ionic liquid is carried out to modification, improves the dissolving power of ionic liquid to phenol.Dissolved the ionic liquid of phenol by the method for underpressure distillation, rare gas element extracting or back extraction, by phenol and ionic liquid separately, thereby obtained aldehydes matter, the ionic liquid simultaneously removed after phenol can recycle.This Track character is that extraction efficiency is high, does not use strong acid and highly basic, does not have a large amount of waste water to produce, the process environment close friend.Present method can reuse separating agent, reduces separation costs, has simplified separation process, has certain reality and environment protection significance.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of from coal tar, in the mixture of liquefied coal coil and other oil and phenol (by aromatic hydrocarbon, straight-chain paraffin or its mixture and phenolic compound composition), take the method for glyoxaline ion liquid phenolic compound in separating agent extracting and separating oil.The method has been avoided a large amount of acid, the use of alkaline solution; Avoided the generation of phenolic wastewater; Can realize that separating agent reuses, and separation efficiency does not almost descend; Effectively reduce production cost; There is very high separation efficiency.
Enforcement of the present invention realizes by the following technical solutions:
A kind of novel from oil the method for separating phenols compounds, the method comprises with true coal tar and liquefied coal coil, the mixture of other oil and phenol is (by aromatic hydrocarbon, straight-chain paraffin or its mixture and phenolic compound form) be separate object, the glyoxaline ion liquid of take carrys out the step of phenolic compound in separating oil as separating agent.
In aforesaid method, described aromatic hydrocarbon and straight-chain paraffin are benzene, toluene, p-Xylol, m-xylene, o-Xylol, normal hexane, normal heptane, octane, one or more in n-dodecane; In the oil phenol mixture, phenol content is 1%-40%.
The above-mentioned coal tar phenol content containing phenol cut section is 5%-35%, and the phenol content that contains the liquefied coal coil of phenol cut section is 5%-40%.
In aforesaid method, ionic liquid and phenolic compound mol ratio are 0.1-5.0, are preferably 0.5-3.0.
In aforesaid method, the general formula of described glyoxaline ion liquid is [C
nMim]
+X
-, C wherein
nRepresent C
1-C
20One or more of alkyl, haloalkyl or hydroxyl substituted alkyl, be preferably ethyl and butyl; Wherein X means chlorine, bromine, iodine, tetrafluoroborate or hexafluoro-phosphate radical, is preferably chlorine, bromine or hexafluoro-phosphate radical.
In aforesaid method, described phenolic compound is phenol, alkylphenol, naphthols or dihydroxyl or polyhydroxy phenol as one or more in Resorcinol.
In aforesaid method, separation temperature is 0-150 ℃, is preferably 10-40 ℃; Disengaging time is 1-300min, is preferably 2-30min.
After aforesaid method also comprises that separation finishes, ionic liquid forms 2 phases with the mixture of oil and phenol, and upper is oil phase (phenol is removed) mutually, and lower is the solution that phenol and ionic liquid form mutually, is called the ionic liquid phase.Remove the neutral oil that upper organic phase has obtained taking off phenol.The lower ionic liquid that contains mutually phenol contains a small amount of neutral oil mutually, adopts the mode of rare gas element air lift under vacuum-evaporation or low temperature to remove contained a small amount of neutral oil.Then will adopt mutually containing the ionic liquid of phenol 2 kinds of mode separating ionic liquids and phenol: (1) carries out back extraction with ether compound, obtains ether compound phase and ionic liquid containing phenol, realizes the recovery of ionic liquid.The ether compound adopted during back extraction comprises ether, methyl ethyl ether, one or more of butyl ether.Back extraction temperature 0-100 ℃, be preferably 5-30 ℃; Back extraction ether phase and ionic liquid are in a ratio of 1-5, back extraction number of times 1-4 time.(2) adopt the mode of high temperature inert gas air lift to separate phenol and ionic liquid.Rare gas element is for being preferably nitrogen, and the air lift temperature is 120-220 ℃, is preferably 150-180 ℃.
Aforesaid method comprises the steps:
(1) phenols of preparation different concns-aromatic hydrocarbons solution, phenols-straight-chain paraffin solution, or phenols-hydrocarbon mixture solution, be required oily phenol mixture;
(2) take ionic liquid as separating agent, after phenolic compound is combined in oil, separate with organic phase, form the ionic liquid phase of phenolic compound enrichment;
(3) after separating end, to lower floor's ionic liquid, use mutually ethers to carry out back extraction, ionic liquid is separated with phenols, realize the recycling of ionic liquid, perhaps use method separating ionic liquid and the phenol of rare gas element air lift, realize the recycling of ionic liquid.
Below will describe the present invention.
The invention provides and take glyoxaline ion liquid as separating agent, the aldehydes matter of ionic liquid in oil is combined and formed the ionic liquid phase with multiple weak bond power, and due to the special construction of ionic liquid, it is insoluble to neutral oil phase, thereby realizes phenol and neutral oil separating.Phenolic compound is phenol, alkylphenol, naphthols or dihydroxyl or polyhydroxy phenol as one or more in Resorcinol; The sepn process the present invention relates to, in oil, content of phenolic compounds is 1%-40%, ionic liquid and phenolic compound mol ratio are 0.1-5.0, are preferably 0.5-3.0; Separation temperature is 0-150 ℃, is preferably 10-40 ℃; Disengaging time is 1-300min, is preferably 2-30min.Use ethers back extraction ionic liquid to separate phenol and ionic liquid, ethers comprises one or more of ether, methyl ethyl ether, butyl ether, is preferably ether; While using ethers back extraction ionic liquid, service temperature is 0-100 ℃, is preferably 5-30 ℃, and the time is 5-60min; Back extraction ether phase and ionic liquid are in a ratio of 1-5, back extraction number of times 1-4 time.Perhaps adopt the mode of high temperature inert gas air lift to separate phenol and ionic liquid.Rare gas element is for being preferably nitrogen, and the air lift temperature is 120-220 ℃, is preferably 150-180 ℃.
Compared with prior art, the present invention at least possesses following beneficial effect:
For phenolic compound separation in oil provides, a kind of technique is simple, separation costs is low, energy consumption is low, environment amenable disjunctive path in the present invention;
With traditional basic solution elution method, compare, it is extraction agent that the present invention adopts glyoxaline ion liquid, has avoided the use of a large amount of acid-base solutions and the generation of phenolic wastewater, has simplified separating step, has reduced equipment requirements;
The present invention has also adopted ether compound back extraction ionic liquid separating ionic liquid and the phenol dissolved, and regeneration of ionic liquid, realized the ionic liquid recycling; Perhaps use method separating ionic liquid and the phenol of rare gas element air lift, realize the recycling of ionic liquid and the use of minimizing organic solvent.
The present invention uses glyoxaline ion liquid as extraction agent, efficient extracting and separating oil and phenol, and extraction efficiency is 90-99.5%, can realize the single percentage extraction more than 99% under optimal conditions, its separation efficiency is far away higher than conventional organic solvents.
Claims (8)
- One kind novel from oil the method for separating phenols compounds, the method comprises take glyoxaline ion liquid as separating agent, thus ionic liquid is combined with phenolic compound and is formed the ionic liquid phase and realize the step that oily phenol separates.
- 2. method according to claim 1, is characterized in that, described oily phenol mixture consist of aromatic hydrocarbon and straight-chain paraffin.
- 3. aromatic hydrocarbon and straight-chain paraffin are one or more in benzene, toluene, p-Xylol, m-xylene, o-Xylol, normal hexane, normal heptane, octane, n-dodecane; Described phenolic compound is phenol, alkylphenol, naphthols or dihydroxyl or polyhydroxy phenol as one or more in Resorcinol, and the content of phenolic compound is 1%-40%; Described oily phenol mixture can be also the coal direct liquefaction oil that contains the coal tar of phenol cut section or contain phenol cut section, and described coal tar phenol content is 5%-35%, and the phenol content of liquefied coal coil is 5%-40%.
- 4. according to the method described in claim 1, it is characterized in that, the general formula of described glyoxaline ion liquid is [C nMim] +X -, C wherein nRepresent C 1-C 20Alkyl, haloalkyl or hydroxyl substituted alkyl, be preferably ethyl and butyl; Wherein X means fluorine, chlorine, bromine, iodine, tetrafluoroborate or hexafluoro-phosphate radical, is preferably chlorine, bromine, hexafluoro-phosphate radical.
- 5. according to the method in any one of claims 1 to 3, it is characterized in that, in oil, content of phenolic compounds is 1%-40%, and ionic liquid and phenolic compound mol ratio are 0.1-5.0, are preferably 0.5-3; Separation temperature is 0-150 ℃, and preferred temperature is 10-40 ℃; Disengaging time is 1-300min, is preferably 2-30min.
- 6. according to the method described in claim 1, it is characterized in that, the ethers adopted that separates of the mixture formed with phenol for ionic liquid comprises ether, methyl ethyl ether, and one or more of butyl ether, be preferably ether; While using ethers back extraction ionic liquid, service temperature is 0-100 ℃, is preferably 5-30 ℃, and the time is 5-60min; Back extraction ether phase and ionic liquid are in a ratio of 1-5, back extraction number of times 1-4 time.
- 7. according to the described method of any one in claim 1 to 7, it is characterized in that, for ionic liquid and the separating also of mixture that phenol forms adopting rare gas element, nitrogen, argon gas at high temperature carry out gas delivery ionic liquid and phenol, the temperature of air lift is 120 ℃-220 ℃, is preferably 150-180 ℃.
- 8. according to the described method of any one in claim 1 to 6, it is characterized in that, described method comprises the steps:(1) the preparation content of phenolic compounds is 1%-40% oil phenol mixture;(2) take glyoxaline ion liquid as extraction agent, the phenolic compound in the oily phenol mixture of the true coal tar of extracting and separating, liquefied coal coil or step (1) preparation, obtain oil phase and ionic liquid and phenol mixture phase;(3) after separating end, ionic liquid and phenol mixture are used mutually to the way of ether compound back extraction ionic liquid phase or nitrogen air lift, ionic liquid is separated with phenol, realize the ionic liquid cycling and reutilization.
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| CN201210164026.0A CN103420802B (en) | 2012-05-24 | 2012-05-24 | A kind of method of novel separating phenols compounds from oil |
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| CN103420802B CN103420802B (en) | 2016-04-13 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965950A (en) * | 2014-04-29 | 2014-08-06 | 神华集团有限责任公司 | Method for separating phenols in coal liquefaction oil |
| CN105176556A (en) * | 2015-09-11 | 2015-12-23 | 波露明（北京）科技有限公司 | Method for separating phenol from coal tar phenol-containing distillate oil |
| CN106831455A (en) * | 2016-12-09 | 2017-06-13 | 北京化工大学 | A kind of method of the neutral oil in removal eutectic solvent |
| CN107501051A (en) * | 2017-09-14 | 2017-12-22 | 北京化工大学 | A kind of method that phenolic compound in oily phenol mixture is separated with quaternary ammonium dication liquid extraction |
| CN107673435A (en) * | 2017-10-20 | 2018-02-09 | 南京大学金陵学院 | A kind of method that aromatic compound is extracted using Hydroxyl-functionalized Ionic Liquids |
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| CN1712093A (en) * | 2004-06-22 | 2005-12-28 | 中国科学院过程工程研究所 | Organic substance extraction in water with ionic liquid as extractant |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965950A (en) * | 2014-04-29 | 2014-08-06 | 神华集团有限责任公司 | Method for separating phenols in coal liquefaction oil |
| CN103965950B (en) * | 2014-04-29 | 2015-07-15 | 神华集团有限责任公司 | Method for separating phenols in coal liquefaction oil |
| CN105176556A (en) * | 2015-09-11 | 2015-12-23 | 波露明（北京）科技有限公司 | Method for separating phenol from coal tar phenol-containing distillate oil |
| CN106831455A (en) * | 2016-12-09 | 2017-06-13 | 北京化工大学 | A kind of method of the neutral oil in removal eutectic solvent |
| CN107501051A (en) * | 2017-09-14 | 2017-12-22 | 北京化工大学 | A kind of method that phenolic compound in oily phenol mixture is separated with quaternary ammonium dication liquid extraction |
| CN107501051B (en) * | 2017-09-14 | 2020-09-04 | 北京化工大学 | Method for extracting and separating phenolic compounds in oil-phenol mixture by using quaternary amino dicationic ionic liquid |
| CN107673435A (en) * | 2017-10-20 | 2018-02-09 | 南京大学金陵学院 | A kind of method that aromatic compound is extracted using Hydroxyl-functionalized Ionic Liquids |
| CN107673435B (en) * | 2017-10-20 | 2021-01-12 | 南京大学金陵学院 | Method for extracting aromatic compound by using hydroxyl functionalized ionic liquid |
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| CN103420802B (en) | 2016-04-13 |
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