CN112569633A

CN112569633A - Method for separating, enriching or producing phenolic compounds, and method and equipment for processing oil products

Info

Publication number: CN112569633A
Application number: CN201910943130.1A
Authority: CN
Inventors: 李青松; 范雯阳; 崔鹏; 闫厚春; 郭之辉
Original assignee: Qingdao Hadely Nano Technology Co ltd
Current assignee: Qingdao Hadely Nano Technology Co ltd
Priority date: 2019-09-30
Filing date: 2019-09-30
Publication date: 2021-03-30

Abstract

The present application provides a method of separating, enriching or producing phenolic compounds or a method of processing an oil product comprising: adding an auxiliary agent into an oil product; extracting the oil product added with the auxiliary agent by using a solvent I to obtain a phenolic compound enriched in the obtained extract phase I; wherein the oil is selected from: coal tar, biomass pyrolysis liquids, and any combination thereof; the auxiliary agent is selected from a non-polar solvent and a weak-polar solvent; the solvent I is a polar solvent and contains at least one organic solvent. The present application also provides an apparatus for separating, enriching or producing phenolic compounds or an apparatus for processing oil.

Description

Method for separating, enriching or producing phenolic compounds, and method and equipment for processing oil products

Technical Field

The application belongs to the field of biochemical energy processing. In particular, the present application relates to a method of separating, enriching or producing phenolic compounds or a method and apparatus for processing oil.

Background

Worldwide, coal consumption accounts for a large proportion of the total energy consumption. Medium and low temperature coal tar is a by-product of semi coke, coke and coal gasification, and has considerable yield. At present, the processing mode of medium, low and high temperature coal tar mainly adopts a distillation method to cut fractions with different boiling points, and then different fractions are further processed, for example, light component fractions are separated by an acid-base method to obtain crude phenol products, and heavy components are processed to obtain coal pitch. However, some components are widely distributed along with the boiling point, cutting is only carried out on the coal tar preliminarily according to the boiling point, and target fractions are not accurately and efficiently separated and enriched, so that the separation steps of subsequent products are complicated, and the energy consumption is high.

In addition, with the gradual decrease of reserves of fossil resources such as petroleum and coal, the conversion of low-value biomass resources into energy and chemical raw materials to supplement and replace fossil raw materials has become an important development direction of all countries in the world. The pyrolysis technology can convert and prepare biomass materials into high-quality bio-oil, fuel gas and biochar, and has wide market prospect and important social value.

The biomass pyrolysis liquid and the low, medium and high temperature coal tar contain phenolic compounds in a certain proportion of about 2-35%. The medium-temperature coal tar, the low-temperature coal tar and the biomass pyrolysis liquid contain abundant and considerable phenolic compounds, the separated and identified phenolic compounds comprise more than 70 types of phenol, naphthol, alkylphenol and the like, and the content of the phenolic compounds accounts for 20-35% of the total mass of the coal tar. The presence of these phenolic compounds can produce a series of influences on the coal tar hydrogenation and utilization processes, and it can deactivate the catalyst, increase the carbon residue of the oil product, make the oil product smelly and discolor, and has the disadvantages of corrosivity and poor combustion condition. Meanwhile, the phenolic compound is an important chemical raw material and has wide application in the aspects of synthetic fibers, engineering plastics, pesticides, medicines, explosives, plasticizers, preservatives, spices, dye intermediates and the like. Therefore, the development of the process technology for extracting the phenolic compounds from the coal tar can not only broaden the comprehensive utilization way of the coal tar, but also reduce the hydrogen consumption and the severity in the subsequent upgrading process, improve the economy and enhance the competitive advantage of enterprises.

The efficient and economic separation of phenolic compounds from medium and low temperature coal tar is an important research direction. Various methods of extracting phenolic compounds have been explored to date, such as chemical methods, selective solvent extraction, supercritical fluid extraction, and the like. However, these methods suffer from one or more of the following problems: the recovery rate of phenol is low; the corrosion to equipment is serious; the influence on the environment is large; the application conditions are harsh, the energy consumption is high, the requirement on equipment materials is high, and the investment cost is high; the entrainment of neutral oil is serious, and the purity of crude phenol is low; the extractant is expensive, the operation cost is high and the like.

Disclosure of Invention

In one aspect, the present application provides a method of separating, enriching or producing phenolic compounds or a method of processing an oil product, comprising:

adding an auxiliary agent into an oil product;

extracting the oil product added with the auxiliary agent by using a solvent I to obtain a phenolic compound enriched in the obtained extract phase I;

wherein the oil is selected from: coal tar, biomass pyrolysis liquids, and any combination thereof;

the auxiliary agent is selected from a non-polar solvent and a weak-polar solvent;

the solvent I is a polar solvent and contains at least one organic solvent.

In another aspect, the present application provides another method of separating, enriching or producing phenolic compounds or a method of processing an oil product, comprising:

extracting the oil product by using a solvent I to obtain an extraction phase I enriched with phenolic compounds;

further extracting the extract phase I by using a solvent II to obtain a phenolic compound which is further enriched in the obtained raffinate phase II;

the solvent I is a polar solvent and contains at least one organic solvent;

the solvent II is a weak polar or non-polar solvent.

In some embodiments of the another method, the another method further comprises: before extraction with solvent I, an adjuvant is added to the oil, wherein the adjuvant is selected from the group consisting of weakly polar solvents and non-polar solvents.

In some embodiments of the other method, the adjuvant is the same as or different from the solvent II.

In some embodiments of the alternative process, the extract phase I is separated or recovered from the solvent and/or auxiliary agent before extraction with solvent II.

In some embodiments of the process of any of the above aspects, the extraction temperature during the extraction with solvent I and/or during the extraction with solvent II is between 0 ℃ and 200 ℃; in some embodiments, the extraction temperature is from 20 ℃ to 150 ℃; in some embodiments, the extraction temperature is from 25 ℃ to 120 ℃; in some embodiments, the extraction temperature is from 25 ℃ to 100 ℃.

In some embodiments of the process of any of the above aspects, during the extraction with solvent I, the extraction pressure is from 0.01MPa to 15MPa absolute; in some embodiments, the extraction pressure is from 0.05MPa to 5MPa absolute; in some embodiments, the extraction pressure is between 0.1MPa and 0.5MPa absolute.

In some embodiments of the process of any of the above aspects, during the extraction with solvent II, the extraction pressure is from 0.01MPa to 15MPa absolute; in some embodiments, the extraction pressure is from 0.05MPa to 5MPa absolute; in some embodiments, the extraction pressure is from 0.1MPa to 1MPa absolute.

In some embodiments of the process of any of the above aspects, the ratio of extracted liquid to corresponding extraction solvent during extraction with solvent I and/or during extraction with solvent II is from 0.02 to 50: 1; in some embodiments, the ratio is 0.1 to 10: 1; in some embodiments, the ratio is 0.2 to 5: 1; in some embodiments, the ratio is 0.25 to 4: 1.

In some embodiments of the method of any of the above aspects, the ratio of the starting oil to the adjuvant is from 0.02 to 50: 1; in some embodiments, the ratio is 0.1 to 10: 1; in some embodiments, the ratio is 0.2 to 5: 1; in some embodiments, the ratio is 0.25 to 4: 1.

In some embodiments of the process of any of the above aspects, the extraction apparatus used is selected from the group consisting of a mixer-settler, an extraction column, a centrifugal extractor, and combinations thereof.

In some embodiments of the process of any of the above aspects, the extraction column comprises a packed extraction column, a sieve plate extraction column, a rotating disc extraction column, a vibrating sieve plate column, and combinations thereof.

In some embodiments of the process of any of the above aspects, the process further comprises the step of removing or recovering solvent and/or auxiliary agent from said extract phase I and/or said raffinate phase II enriched in phenolic compounds.

In some embodiments of the process of any of the above aspects, the step of removing or recovering the solvent and/or auxiliary agent comprises a step selected from the group consisting of extraction, distillation, and combinations thereof.

In some embodiments of the process of any of the above aspects, the removed or recovered adjunct, solvent I and/or solvent II is returned to the extraction process for recycling.

In yet another aspect, the present application provides an apparatus for separating, enriching or producing phenolic compounds or an apparatus for processing oil products comprising: a raw oil product tank, an auxiliary agent tank, a solvent I tank and an extraction device I; wherein:

the raw oil tank is filled with a material selected from: coal tar, biomass pyrolysis liquids, and oils of any combination thereof;

the auxiliary agent tank is filled with an auxiliary agent selected from a non-polar solvent and a weak-polar solvent;

the solvent I tank is filled with a solvent I which is a polar solvent and contains at least one organic solvent;

the raw oil product tank, the auxiliary agent tank and the solvent I tank are respectively connected with the extraction device I;

in some embodiments of the above apparatus, the extraction device I is provided with a discharge port for the phenol-containing extract phase I.

In some embodiments of the above apparatus, the phenol-containing extract phase I discharge port is disposed in a sidewall, an upper portion, or a bottom portion of the extraction device I.

In some embodiments of the above apparatus, the apparatus further comprises a desolventizing and/or auxiliary device I, and the discharge port is connected to the desolventizing and/or auxiliary device I, so that the phenol-containing extract phase I enters the desolventizing and/or auxiliary device I after being discharged from the discharge port.

In some embodiments of the above apparatus, the solvent and/or auxiliary removing device I is connected to the solvent I tank and/or the auxiliary tank, so that the removed solvent I and/or auxiliary is recycled to the solvent I tank and/or the auxiliary tank or returned to the extraction process for recycling;

in some embodiments of the above apparatus, the desolventizing and/or adjuvanting device I is selected from the group consisting of an extraction device, a distillation device, and combinations thereof.

In some embodiments of the above apparatus, the apparatus further comprises a valve to control the flow of the fluid.

In another aspect, the present application provides another apparatus for separating, enriching or producing phenolic compounds or for processing oils, comprising: a raw oil product tank, a solvent I tank, a solvent II tank, an extraction device I and an extraction device II; wherein:

the solvent II tank is filled with a solvent II, and the solvent II is a weak polar or non-polar solvent;

the raw oil product tank and the solvent I tank are respectively connected with the extraction device I;

the solvent II tank is connected with the extraction device II;

a discharge port of the phenol-containing extract phase I is arranged on the extraction device I, and the phenol-containing extract phase I is discharged from the discharge port of the phenol-containing extract phase I and then enters the extraction device II.

In some embodiments of the further apparatus, the phenol-containing extract phase I discharge is located in the side wall, upper portion or bottom of the extraction device I.

In some embodiments of the alternative apparatus, the extract phase I is discharged from the outlet of the phenol-containing extract phase I directly into the extraction unit II.

In some embodiments of the further apparatus, the apparatus further comprises an auxiliary agent tank connected to the extraction unit I, the auxiliary agent tank containing an auxiliary agent selected from the group consisting of non-polar solvents and less-polar solvents.

In some embodiments of the further apparatus, the adjuvant is the same as or different from the solvent II.

In some embodiments of the other apparatus, when the auxiliary agent is the same as the solvent II, an additional auxiliary agent tank is not required, and the solvent II tank is used as an auxiliary agent tank at the same time; and in this case the solvent II tank is also connected to the extraction unit I, so that solvent II is also fed to the extraction unit I as an auxiliary agent.

In some embodiments of the further apparatus, the apparatus further comprises a desolventizing and/or auxiliary device I, the phenol-containing extract phase I discharge port being connected to the desolventizing and/or auxiliary device I such that the phenol-containing extract phase I is discharged from the phenol-containing extract phase I discharge port into the desolventizing and/or auxiliary device I; and the solvent and/or auxiliary removal device I is connected to the extraction device II, so that the crude phenol with the solvent and/or auxiliary removed enters the extraction device II.

In some embodiments of the further apparatus, the feed inlet for the phenol-containing extract phase I or the crude phenol stripped of solvent and/or auxiliary agent into the extraction unit II is located in the upper side wall or upper part of the extraction unit II.

In some embodiments of the further apparatus, the solvent removal and/or auxiliary agent device I is connected to the solvent I tank and/or the auxiliary agent tank, respectively, so that the removed solvent I and/or auxiliary agent is recycled to the solvent I tank and/or the auxiliary agent tank, respectively, or returned to the extraction process for recycling.

In some embodiments of the another apparatus, the extraction device II is provided with a discharge port for phenol-containing raffinate phase II.

In some embodiments of the another apparatus, the phenol-containing raffinate phase II discharge outlet is disposed at a lower sidewall or bottom of the extraction device II.

In some embodiments of the further apparatus, the apparatus further comprises a desolventizing and/or auxiliary device II, and the phenol-containing raffinate phase II outlet is connected to the desolventizing and/or auxiliary device II, such that the phenol-containing raffinate phase II enters the desolventizing and/or auxiliary device II after being discharged from the phenol-containing raffinate phase II outlet.

In some embodiments of the further apparatus, the solvent removal and/or auxiliary agent device II is connected to the solvent I tank, the solvent II tank and/or the auxiliary agent tank, such that the removed solvent I, solvent II and/or auxiliary agent is recycled to the solvent I tank, the solvent II tank and/or the auxiliary agent tank, respectively, or returned to the extraction process for recycling;

in some embodiments of said further apparatus, said desolventizing and/or adjuvanting device I and said desolventizing and/or adjuvanting device II are selected from the group consisting of an extraction device, a distillation device, and combinations thereof.

In some embodiments of the another apparatus, the apparatus further comprises a valve to control the flow of fluid.

In some embodiments of any of the above aspects, the coal tar is selected from the group consisting of low temperature coal tar, medium temperature coal tar, high temperature coal tar, and combinations thereof.

Examples of any of the above aspectsIn one embodiment, solvent I has a dielectric constant at 20 deg.C>2.5 and dipole moment>2×10^-30C.m；

In some embodiments of any of the aspects above, solvent II has a dielectric constant at 20 ℃<2.3 or dipole moment<1.5×10^-30C.m。

In some embodiments of any of the above aspects, the adjuvant has a dielectric constant at 20 ℃<2.3 or dipole moment<1.5×10^-30C.m。

In some embodiments of any of the foregoing aspects, the low temperature coal tar is coal tar obtained by pyrolyzing coal at 450 ℃ to 650 ℃, the medium temperature coal tar is coal tar obtained by pyrolyzing coal at 650 ℃ to 800 ℃, and the high temperature coal tar is coal tar obtained by pyrolyzing coal at 800 ℃ to 1200 ℃.

In some embodiments of any of the above aspects, the oil as a starting material is selected from untreated low temperature coal tar, untreated medium temperature coal tar, untreated high temperature coal tar, untreated biomass pyrolysis liquids, or their rectified or extracted fractions, and any combination thereof. The term "untreated" merely means that the components thereof have not been subjected to further separation treatment such as distillation, rectification, extraction, etc.

In some embodiments of any of the above aspects, the fraction of the oil that is rectified is selected from: the low-temperature coal tar distillate at 170-400 ℃, the medium-temperature coal tar distillate at 170-400 ℃, the high-temperature coal tar distillate at 170-360 ℃, the biomass pyrolysis liquid distillate at 170-400 ℃ and any combination thereof.

In some embodiments of any of the above aspects, the adjuvant is selected from the group consisting of benzene, toluene, xylene, C₉～C₂₀Aromatic hydrocarbon, C₉～C₂₀Aromatic ether, C₁～C₂₀Halogenated alkanes, C₃～C₂₀Alkane, C₅～C₂₀Cycloalkanes, C₂～C₂₀Fatty ethers, C₁～C₂₀Esters of fatty acids, mineral spirits, and combinations thereof.

In some embodiments of any of the above aspects, the solvent I is selected from the group consisting of nitrogen-containing compounds, sulfur-containing compounds, alcohols, ketones, ethers, carboxylic acids, esters, aromatic hydrocarbons, aldehydes, water, and combinations thereof.

In some embodiments of any of the above aspects, the solvent II is selected from the group consisting of aromatic hydrocarbons, alkanes, haloalkanes, ethers, carboxylic acids, esters, mineral spirits, and combinations thereof.

In some embodiments of any of the foregoing aspects, the nitrogen-containing compound-based solvent in solvent I is selected from acetonitrile, butyronitrile, succinonitrile, formamide, acetamide, benzamide, N-methylformamide, N-dimethylformamide, N-ethylformamide, N-diethylformamide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidone, and combinations thereof.

In some embodiments of any of the above aspects, the sulfur compound-based solvent in solvent I is selected from the group consisting of dimethyl sulfoxide, sulfolane, dimethyl sulfone, and combinations thereof.

In some embodiments of any of the foregoing aspects, the alcoholic solvent in solvent I is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, pentanol, isopentanol, fusel oil, hexanol, heptanol, octanol, isooctanol, phenethyl alcohol, cyclohexanol, methylcyclohexanol, ethylene glycol, glycerol, propylene glycol, butylene glycol, pentanediol, hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, furfuryl alcohol, tetrahydrofurfuryl alcohol, and combinations thereof.

In some embodiments of any of the above aspects, the ketone solvent in solvent I is selected from the group consisting of acetone, methyl acetone, butanone, methyl isobutyl ketone, 2-pentanone, 3-pentanone, isophorone, cyclopentanone, cyclohexanone, methylcyclohexanone, acetophenone, and combinations thereof.

In some embodiments of any of the foregoing aspects, the ethereal solvent in solvent I is selected from hydroxyl-containing ethers. In some embodiments, the hydroxyl-containing ether is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-tertiary-butyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, and combinations thereof.

In some embodiments of any of the above aspects, the carboxylic acid-based solvent in solvent I is selected from the group consisting of acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, hexanoic acid, heptanoic acid, and combinations thereof.

In some embodiments of any of the foregoing aspects, the ester-based solvent in solvent I is selected from the group consisting of methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, hexyl acetate, dimethyl carbonate, tributyl phosphate, tricresyl phosphate, bis (2-ethylhexyl) phosphate, tris (2-ethylhexyl) phosphate, diisobutyl phthalate, dibutyl phthalate, diethyl phthalate, and combinations thereof.

In some embodiments of any of the foregoing aspects, the aromatic hydrocarbon solvent in solvent I is selected from benzene, toluene, xylene, C₉～C₂₀Aromatic hydrocarbons and combinations thereof.

In some embodiments of any of the foregoing aspects, the aldehyde solvent in solvent I is selected from furfural.

In some embodiments of any of the foregoing aspects, the aromatic hydrocarbon solvent in solvent II is selected from benzene, toluene, xylene, C₉～C₂₀Aromatic hydrocarbons, pyridine, picoline, furan, methylfuran, thiophene, methylthiophene, and combinations thereof.

In some embodiments of any of the foregoing aspects, the alkane solvent in solvent II is selected from C₃～C₂₀Alkane, C₅～C₂₀Cycloalkanes, and combinations thereof.

In some embodiments of any of the above aspects, the haloalkanes in solvent II are selected from the group consisting of methyl chloride, ethyl chloride, methylene chloride, ethylene dichloride, chlorobutane, and combinations thereof.

In some embodiments of any of the aspects above, the solvent is solvent IIThe ether solvent is selected from diethyl ether, propyl ether, and C₆～C₂₀Aliphatic ethers and combinations thereof.

In some embodiments of any of the above aspects, the carboxylic acid-based solvent in solvent II is selected from the group consisting of octanoic acid, 2-ethylhexanoic acid, tetradecanoic acid, oleic acid, and combinations thereof.

In some embodiments of any of the above aspects, the ester solvent in solvent II is selected from the group consisting of methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, hexyl acetate, and combinations thereof.

Drawings

FIG. 1 is a schematic diagram of an apparatus of the present invention.

FIG. 2 is a schematic view showing the structure of another apparatus of the present invention, and FIG. 2 shows a specific example of an apparatus in which the solvent II used is the same as the auxiliary. As shown in fig. 2, the two-line intersections are only for convenience in drawing and reading, and the two-line intersections are not connected.

Detailed Description

Definition of

The following definitions and methods are provided to better define the present application and to guide those of ordinary skill in the art in the practice of the present application. Unless otherwise indicated, terms are to be understood in accordance with their ordinary usage by those of ordinary skill in the relevant art. All patent documents, academic papers, and other publications cited herein are incorporated by reference in their entirety.

The term "optional" or "optionally" as used herein means that the subsequently described event or circumstance may, but need not, occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

The term "alkane" as used herein includes saturated paraffins and saturated naphthenes, unless otherwise indicated herein.

The term "halo" as used herein means that one or more hydrogen atoms in a given molecule are replaced by a halogen atom (e.g., a chlorine, fluorine, bromine or iodine atom).

As used hereinBy the term "C₉～C₂₀The aromatic hydrocarbon "means a monocyclic, polycyclic, or fused ring aromatic hydrocarbon having 9 to 20 carbon atoms, such as benzene, naphthalene, or the like.

The term "C" as used herein_n"means that a given molecule has n carbon atoms, where n is a positive integer, e.g., C₁～C₂₀It is meant that the number of carbon atoms in a given molecule may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20. E.g. C₂～C₂₀It is meant that the number of carbon atoms in a given molecule may be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20. E.g. C₃～C₂₀It is meant that the number of carbon atoms in a given molecule may be 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20. E.g. C₅～C₂₀It is meant that the number of carbon atoms in a given molecule may be 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20. E.g. C₆～C₂₀It is meant that the number of carbon atoms in a given molecule may be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20. E.g. C₉～C₂₀It is meant that the number of carbon atoms in a given molecule may be 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

The term "polar solvent" as used herein refers to a solvent containing a polar group (e.g., hydroxyl group or carbonyl group, etc.), which generally has an asymmetric molecular structure, so that an electron cloud is shifted and concentrated near a certain functional group, thereby exhibiting polarity.

The term "low temperature coal tar" used herein is coal tar obtained by pyrolyzing coal at 450-650 deg.C, "medium temperature coal tar" is coal tar obtained by pyrolyzing coal at 650-800 deg.C, and high temperature coal tar "is coal tar obtained by pyrolyzing coal at 800-1200 deg.C.

Those skilled in the art will appreciate that the term "connected" as used herein in the context of the apparatus is in fluid communication.

The biomass pyrolysis liquid refers to a liquid product (bio-oil) mainly obtained by thermally decomposing biomass in an anoxic state and rapidly condensing the biomass. Biomass includes various naturally occurring and derived materials such as coal, woody and weed-like plants, wood waste, bagasse, various agricultural and forestry residues, waste paper, municipal solid waste, sawdust, weeds, waste from food processing, animal waste, aquatic plants, algae, and the like.

Where a range of numerical values is recited herein, the range includes the endpoints thereof, and all the individual integers and fractions within the range, and also includes each of the narrower ranges therein formed by all the various possible combinations of those endpoints and internal integers and fractions to form subgroups of the larger group of values within the stated range to the same extent as if each of those narrower ranges were explicitly recited. For example, an extraction temperature of 0 ℃ to 200 ℃ means that the extraction temperature can be 0 ℃, 3 ℃, 5 ℃, 7 ℃, 8 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ and the like, and ranges formed by the same, and the like.

Detailed description of the embodiments

adding an auxiliary agent into an oil product;

the solvent I is a polar solvent and contains at least one organic solvent.

the solvent I is a polar solvent and contains at least one organic solvent;

the solvent II is a weak polar or non-polar solvent.

In some embodiments of the other process, the adjuvant may be the same as or different from the solvent II.

In some embodiments of the alternative process, the extract phase I is separated or recovered from the solvent and/or auxiliary agent prior to extraction with solvent ii.

In some embodiments of the method of any of the above aspects, the extraction temperature during extraction with solvent I and/or during extraction with solvent II is 0 ℃ to 200 ℃ (e.g., 0 ℃, 3 ℃, 5 ℃, 7 ℃, 8 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, or 200 ℃, etc.); in some embodiments, the extraction temperature is from 20 ℃ to 150 ℃; in some embodiments, the extraction temperature is from 25 ℃ to 120 ℃; in some embodiments, the extraction temperature is from 25 ℃ to 100 ℃. In some embodiments of the method of any of the above aspects, the extraction pressure is from 0.01MPa to 15MPa absolute (e.g., 0.01MPa, 0.05MPa, 0.08MPa, 0.1MPa, 0.11MPa, 0.15MPa, 0.3MPa, 0.35MPa, 0.5MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1MPa, 2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, 11MPa, 12MPa, 13MPa, 14MPa, or 15MPa, etc.) during the extraction with solvent I; in some embodiments, the extraction pressure is from 0.05MPa to 5MPa absolute; in some embodiments, the extraction pressure is between 0.1MPa and 0.5MPa absolute.

In some embodiments of the method of any of the above aspects, the extraction pressure is from 0.01MPa to 15MPa absolute (e.g., 0.01MPa, 0.05MPa, 0.08MPa, 0.1MPa, 0.11MPa, 0.15MPa, 0.3MPa, 0.35MPa, 0.5MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1MPa, 2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, 11MPa, 12MPa, 13MPa, 14MPa, or 15MPa, etc.) during the extraction with solvent II; in some embodiments, the extraction pressure is from 0.05MPa to 5MPa absolute; in some embodiments, the extraction pressure is from 0.1MPa to 1MPa absolute.

In some embodiments of the methods of any of the above aspects, the ratio of extracted fluid to corresponding extraction solvent during extraction with solvent I and/or during extraction with solvent II is 0.02 to 50:1 (e.g., 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 6:1, 1:1, 2.5:1, 1:1, 1:1, 1 21:1, 22:1, 23:1, 24:1, 25:1, 26:1, 27:1, 28:1, 29:1, 30:1, 31:1, 32:1, 33:1, 34:1, 35:1, 36:1, 37:1, 38:1, 39:1, 40:1, 41:1, 42:1, 43:1, 44:1, 45:1, 46:1, 47:1, 48:1, 49:1, 50:1, etc.); in some embodiments, the ratio is 0.1 to 10: 1; in some embodiments, the ratio is 0.2 to 5: 1; in some embodiments, the ratio is 0.25 to 4: 1. It will be understood by those skilled in the art that the extracted liquid is an oil, a phenol-containing extract phase I or crude phenol as described herein.

In some embodiments of the methods of any of the above aspects, the ratio of the starting oil to the adjuvant is 0.02 to 50:1 (e.g., 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 1.5:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 1:1, 13:1, 1:1, 15: 20:1, 1:1, 30:1, 31:1, 32:1, 33:1, 34:1, 35:1, 36:1, 37:1, 38:1, 39:1, 40:1, 41:1, 42:1, 43:1, 44:1, 45:1, 46:1, 47:1, 48:1, 49:1, 50:1, etc.); in some embodiments, the ratio is 0.1 to 10: 1; in some embodiments, the ratio is 0.2 to 5: 1; in some embodiments, the ratio is 0.25 to 4: 1. In some embodiments of the process of any of the above aspects, the extraction apparatus used is selected from the group consisting of a mixer-settler, an extraction column, a centrifugal extractor, and combinations thereof.

In some embodiments of the above apparatus, the apparatus further comprises a desolventizing and/or auxiliary device I, and the discharge port is connected to the desolventizing and/or auxiliary device I, so that the phenol-containing extract phase I enters the desolventizing and/or auxiliary device I after being discharged from the discharge port. It will be appreciated by those skilled in the art that the desolventizing and/or adjuvant device I may be a device that can remove solvent, or adjuvant, or both solvent and adjuvant.

In some embodiments of the above apparatus, the apparatus further comprises a valve (e.g., a two-way valve, a three-way valve, etc.) to control the flow of fluid. The fluid is controlled to make and break by opening and closing the valve.

In some embodiments of the above apparatus, the extraction unit I is selected from the group consisting of a mixer-settler, an extraction column, a centrifugal extractor, and combinations thereof. In some embodiments, the extraction column comprises a packed extraction column, a sieve plate extraction column, a rotating disc extraction column, a vibrating sieve plate column, and combinations thereof.

the solvent II tank is connected with the extraction device II;

In some embodiments of said further apparatus, said solvent and/or auxiliary removal device I is connected to said solvent I tank and/or said auxiliary tank, respectively, so that the removed solvent I and/or auxiliary is recycled to said solvent I tank and/or said auxiliary tank, respectively, or returned to the extraction process for recycling.

In some embodiments of the further apparatus, the solvent removal and/or auxiliary agent device II is connected to the solvent I tank, the solvent II tank and/or the auxiliary agent tank, such that the removed solvent I, solvent II and/or auxiliary agent is recycled to the solvent I tank, the solvent II tank and/or the auxiliary agent tank, respectively, or returned to the extraction process for recycling. It will be appreciated by those skilled in the art that the desolventizing and/or adjuvant device II may be a device that can remove solvent I, or solvent II, or adjuvant, or a combination of two or more thereof.

In some embodiments of the another apparatus, the apparatus further comprises a valve (e.g., a two-way valve, a three-way valve, etc.) to control the flow of fluid. The fluid is controlled to make and break by opening and closing the valve.

In some embodiments of the another apparatus, the extraction unit I and the extraction unit II are each independently selected from a mixer-settler, an extraction column, a centrifugal extractor, and combinations thereof. In some embodiments, the extraction column comprises a packed extraction column, a sieve plate extraction column, a rotating disc extraction column, a vibrating sieve plate column, and combinations thereof.

In some embodiments of any of the aspects above, solvent I has a dielectric constant at 20 ℃>2.5 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, etc.) and a dipole moment>2×10^-30C.m (e.g., 2.3X 10)^-30C.m、2.5×10^-30C.m、2.8×10^-30C.m、3.0×10^-30C.m、4.2×10^-30C.m、4.5×10^-30C.m、4.7×10^-30C.m、5.0×10^- ³⁰C.m、5.1×10^-30C.m、5.2×10^-30C.m、5.3×10^-30C.m、5.4×10^-30C.m、5.5×10^-30C.m、5.6×10^-30C.m、5.7×10^-30C.m、5.8×10^-30C.m、5.9×10^-30C.m、6.0×10^-30C.m、7.0×10^-30C.m、7.8×10^-30C.m、8×10^-30C.m、9×10^-30C.m、10×10^-30C.m、11×10^-30C.m、12×10^-30C.m or 13X 10^- ³⁰C.m, etc.).

In some embodiments of any of the aspects above, solvent II has a dielectric constant at 20 ℃<2.3 (e.g., 2.29, 2.28, 2.27, 2.26, 2.25, 2.24, 2.23, 2.22, 2.21, 2.20, 2.19, 2.18, 2.17, 2.16, 2.15, 2.14, 2.13, 2.12, 2.11, 2.10, 2.00, 1.95, 1.92, 1.90, 1.88, 1.86, 1.83, 1.81, 1.79, 1.77, 1.75, 1.72, 1.70, 1.68, 1.66, 1.63, 1.61, or 1.6, etc.) or dipole moment<1.5×10^-30C.m (e.g. 1.4X 10)^-30C.m、1.3×10^-30C.m、1.2×10^-30C.m、1.1×10^-30C.m、1.0×10^-30C.m or 0, etc.).

In some embodiments of any of the above aspects, the adjuvant has a dielectric constant at 20 ℃<2.3 (e.g., 2.29, 2.28, 2.27, 2.26, 2.25, 2.24, 2.23, 2.22, 2.21, 2.20, 2.19, 2.18, 2.17, 2.16, 2.15, 2.14, 2.13, 2.12, 2.11, 2.10, 2.00, 1.95, 1.92, 1.90, 1.88, 1.86, 1.83, 1.81, 1.79, 1.77, 1.75, 1.72, 1.70, 1.68, 1.66, 1.63, 1.61, or 1.6, etc.) or dipole moment<1.5×10^-30C.m (e.g. 1.4X 10)^-30C.m、1.3×10^-30C.m、1.2×10^-30C.m、1.1×10^-30C.m、1.0×10^-30C.m or 0, etc.).

In some embodiments of any of the above aspects, the oil as a starting material is selected from untreated low temperature coal tar, untreated medium temperature coal tar, untreated high temperature coal tar, untreated biomass pyrolysis liquids, or their rectified or extracted fractions, and any combination thereof.

In some embodiments of any of the above aspects, the adjuvant includes, but is not limited to, benzene, toluene, xylene, C₉～C₂₀Aromatic hydrocarbon, C₉～C₂₀Aromatic ether, C₁～C₂₀Halogenated alkanes, C₃～C₂₀Alkane, C₅～C₂₀Cycloalkanes, C₂～C₂₀Fatty ethers, C₁～C₂₀Esters of fatty acids, mineral spirits, and combinations thereof.

In some embodiments of any of the above aspects, the solvent I includes, but is not limited to, nitrogen-containing compounds, sulfur-containing compounds, alcohols, ketones, ethers, carboxylic acids, esters, aromatic hydrocarbons, aldehydes, water, and combinations thereof.

In some embodiments of any of the above aspects, the solvent II includes, but is not limited to, aromatic hydrocarbons, alkanes, haloalkanes, ethers, carboxylic acids, esters, mineral spirits, and combinations thereof.

In some embodiments of any of the foregoing aspects, the nitrogen-containing compound-based solvent in solvent I includes, but is not limited to, acetonitrile, butyronitrile, succinonitrile, formamide, acetamide, benzamide, N-methylformamide, N-dimethylformamide, N-ethylformamide, N-diethylformamide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidone, and combinations thereof.

In some embodiments of any of the above aspects, the sulfur compound-based solvent in solvent I includes, but is not limited to, dimethyl sulfoxide, sulfolane, dimethyl sulfone, and combinations thereof.

In some embodiments of any of the foregoing aspects, the alcoholic solvent in solvent I includes, but is not limited to, methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, pentanol, isopentanol, fusel oil, hexanol, heptanol, octanol, isooctanol, phenethyl alcohol, cyclohexanol, methylcyclohexanol, ethylene glycol, glycerol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, furfuryl alcohol, tetrahydrofurfuryl alcohol, and combinations thereof.

In some embodiments of any of the above aspects, the ketone-based solvent in solvent I includes, but is not limited to, acetone, methyl acetone, butanone, methyl isobutyl ketone, 2-pentanone, 3-pentanone, isophorone, cyclopentanone, cyclohexanone, methylcyclohexanone, acetophenone, and combinations thereof.

In some embodiments of any of the above aspects, the ethereal solvent in solvent I includes, but is not limited to, a hydroxyl-containing ether. In some embodiments, the hydroxyl-containing ethers include, but are not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-tertiary-butyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, and combinations thereof.

In some embodiments of any of the above aspects, the carboxylic acid-based solvent in solvent I includes, but is not limited to, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, hexanoic acid, heptanoic acid, and combinations thereof.

In some embodiments of any of the foregoing aspects, the ester-based solvent in solvent I includes, but is not limited to, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, hexyl acetate, dimethyl carbonate, tributyl phosphate, tricresyl phosphate, bis (2-ethylhexyl) phosphate, tris (2-ethylhexyl) phosphate, diisobutyl phthalate, dibutyl phthalate, diethyl phthalate, and combinations thereof.

In some embodiments of any of the foregoing aspects, the aromatic hydrocarbon solvent in solvent I includes, but is not limited to, benzene, toluene, xylene, C₉～C₂₀Aromatic hydrocarbons and combinations thereof.

In some embodiments of any of the above aspects, the aldehyde solvent in solvent I includes, but is not limited to, furfural.

In some embodiments of any of the above aspects, the alkane solvent in solvent II includes, but is not limited to, C₃～C₂₀Alkane, C₅～C₂₀Cycloalkanes, and combinations thereof.

In some embodiments of any of the above aspects, the haloalkanes in solvent II include, but are not limited to, methyl chloride, ethyl chloride, methylene chloride, ethylene dichloride, chlorobutane, and combinations thereof.

In some embodiments of any of the above aspects, the ethereal solvent in solvent II includes, but is not limited to, diethyl ether, propyl ether, C₆～C₂₀Aliphatic ethers and combinations thereof.

In some embodiments of any of the above aspects, the carboxylic acid-based solvent in solvent II includes, but is not limited to, octanoic acid, 2-ethylhexanoic acid, tetradecanoic acid, oleic acid, and combinations thereof.

In some embodiments of any of the above aspects, the ester-based solvent in solvent II includes, but is not limited to, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, hexyl acetate, and combinations thereof.

In some embodiments of any of the above aspects, examples of the adjuvant include, but are not limited to: 3-methylpentane, n-decane, dichloroethane, amyl ether, xylene + cyclohexane (e.g., 50% xylene + 50% cyclohexane), hexyl acetate, pentane + heptane (e.g., 80% pentane + 20% heptane), cumene + n-heptane (e.g., 50% cumene + 50% n-heptane), 2-methylpentane, mineral spirits, xylene, n-hexane, n-butane, cyclohexane + pentane (e.g., 20% cyclohexane + 80% pentane), n-heptane, dichloromethane, pentane + nonane (e.g., 10% pentane + 90% nonane), octane, and the like.

In some embodiments of any of the above aspects, examples of the solvent I include, but are not limited to: the solvent I may be diethylene glycol + N-methylpyrrolidone (e.g., a mixture of 65% diethylene glycol + 35% N-methylpyrrolidone), a mixture of cyclohexanone + acetamide, N-methylacetamide + triethylene glycol (e.g., a mixture of 60% N-methylacetamide + 40% triethylene glycol), succinonitrile + acetic acid (e.g., a mixture of 60% succinonitrile + 40% acetic acid), an aqueous N, N-diethylformamide solution (e.g., an aqueous 70% N, N-diethylformamide solution), N-butanol + N-methylpyrrolidone (e.g., a mixture of 85% N-butanol + 15% N-methylpyrrolidone), triethylene glycol + acetic acid (e.g., a mixture of 75% triethylene glycol + 25% acetic acid), a mixture of cyclopentanone + N, N-dimethylformamide + water (e.g., 10% cyclopentanone + 50% N, a mixture of N-dimethylformamide and 40% water), glycerol + propionic acid (e.g., a mixture of 80% glycerol + 20% propionic acid), a mixture of furfural + butanone (e.g., a mixture of 90% furfural + 10% butanone), a mixture of N-octanol + N, N-dimethylformamide (e.g., a mixture of 40% N-octanol + 60% N, N-dimethylformamide), an aqueous solution of ethylene glycol monomethyl ether (e.g., a 60% aqueous solution of ethylene glycol monomethyl ether), dimethyl sulfoxide + N-methylpyrrolidone (e.g., a mixture of 80% dimethyl sulfoxide and 20% N-methylpyrrolidone), sulfolane + diethylene glycol monoethyl ether (e.g., a mixture of 70% sulfolane and 30% diethylene glycol monoethyl ether), an aqueous solution of ethylene glycol (e.g., an 85% aqueous solution of ethylene glycol), dimethyl sulfoxide + propionic acid (e.g., a mixture of 85% dimethyl sulfoxide and 15% propionic acid), and mixtures thereof, An aqueous acetone solution (e.g., a 60% aqueous acetone solution), an aqueous acetonitrile solution (e.g., an 80% aqueous acetonitrile solution), an aqueous isopropanol solution (e.g., a 60% aqueous isopropanol solution), an aqueous furfural solution (e.g., a 90% aqueous furfural solution), an aqueous dimethyl sulfoxide solution (e.g., an 80% aqueous dimethyl sulfoxide solution), an aqueous diethylene glycol solution (e.g., an 80% aqueous diethylene glycol solution), ethylene glycol, an aqueous sulfolane solution (e.g., a 75% aqueous sulfolane solution), a mixture of furfural and ethanol (e.g., a mixture of 80% furfural and 20% ethanol), a mixture of triethylene glycol monomethyl ether and N-methylpyrrolidone (e.g., a mixture of 60% triethylene glycol monomethyl ether and 40% N-methylpyrrolidone), and the.

In some embodiments of any of the above aspects, examples of the solvent II include, but are not limited to: pentane + heptane + ethylcyclohexane (e.g., 20% pentane + 30% heptane + 50% ethylcyclohexane), tridecane, p-xylene + pentane (e.g., 10% p-xylene + 90% pentane), n-pentane, p-xylene, methylcyclopentane, methylcyclohexane + toluene (e.g., 80% methylcyclohexane + 20% toluene), 2-methylpentane, nonane, decane, oleic acid + sec-hexyl acetate (e.g., 5% oleic acid + 95% sec-hexyl acetate), n-hexane, n-heptane, hexadecane, pentane + nonane (e.g., 10% pentane + 90% nonane), octane, and the like.

In some embodiments of any of the above aspects, in some embodiments where both an adjuvant and solvent I are used, the adjuvant may be 3-methylpentane and the solvent I may be diethylene glycol + N-methylpyrrolidone (e.g., a mixture of 65% diethylene glycol + 35% N-methylpyrrolidone), as an example. As an example, the auxiliary agent may be n-decane, and the solvent I may be a mixture of cyclohexanone and acetamide (e.g., a mixture of 40% cyclohexanone and 60% acetamide). By way of example, the auxiliary agent may be dichloroethane, and the solvent I may be a mixture of N-methylacetamide and triethylene glycol (e.g., a mixture of 60% N-methylacetamide and 40% triethylene glycol). As an example, the auxiliary agent may be amyl ether, and the solvent I may be a mixture of succinonitrile and acetic acid (e.g., a mixture of 60% succinonitrile and 40% acetic acid). By way of example, the auxiliary may be xylene + cyclohexane (e.g., 50% xylene + 50% cyclohexane) and the solvent I may be an aqueous N, N-diethylformamide solution (e.g., 70% aqueous N, N-diethylformamide solution). By way of example, the auxiliary may be hexyl acetate and the solvent I may be N-butanol + N-methylpyrrolidone (e.g., a mixture of 85% N-butanol + 15% N-methylpyrrolidone). By way of example, the aid may be pentane + heptane (e.g., 80% pentane + 20% heptane) and the solvent I may be triethylene glycol + acetic acid (e.g., a mixture of 75% triethylene glycol + 25% acetic acid). As an example, the adjuvant may be cumene + N-heptane (e.g., 50% cumene + 50% N-heptane) and the solvent I may be a mixture of cyclopentanone + N, N-dimethylformamide + water (e.g., a mixture of 10% cyclopentanone + 50% N, N-dimethylformamide + 40% water). By way of example, the auxiliary agent may be 2-methylpentane and the solvent I may be glycerol + propionic acid (e.g. a mixture of 80% glycerol + 20% propionic acid). By way of example, the auxiliary agent may be a solvent oil, and the solvent I may be a mixture of furfural and butanone (e.g., a mixture of 90% furfural and 10% butanone).

In some embodiments of any of the above aspects, in some embodiments where both solvent I and solvent II are used simultaneously, as an example, the solvent I can be a mixture of N-octanol + N, N-dimethylformamide (e.g., a mixture of 40% N-octanol + 60% N, N-dimethylformamide), and the solvent II can be pentane + heptane + ethylcyclohexane (e.g., 20% pentane + 30% heptane + 50% ethylcyclohexane). By way of example, the solvent I may be an aqueous solution of ethylene glycol monomethyl ether (e.g., a 60% aqueous solution of ethylene glycol monomethyl ether), and the solvent II may be tridecane. By way of example, the solvent I may be dimethylsulfoxide + N-methylpyrrolidinone (e.g., a mixture of 80% dimethylsulfoxide + 20% N-methylpyrrolidinone), and the solvent II may be p-xylene + pentane (e.g., 10% p-xylene + 90% pentane). As an example, the solvent I can be sulfolane + diethylene glycol monoethyl ether (e.g., a mixture of 70% sulfolane + 30% diethylene glycol monoethyl ether), and the solvent II can be n-pentane. As an example, the solvent I may be an aqueous ethylene glycol solution (e.g., 85% aqueous ethylene glycol solution) and the solvent II may be para-xylene. As an example, the solvent I can be dimethyl sulfoxide + propionic acid (e.g., a mixture of 85% dimethyl sulfoxide + 15% propionic acid), and the solvent II can be methylcyclopentane. As an example, the solvent I may be an aqueous acetone solution (e.g., a 60% aqueous acetone solution), and the solvent II may be methylcyclohexane + toluene (e.g., 80% methylcyclohexane + 20% toluene).

In some embodiments of any of the above aspects, in some embodiments where an adjuvant, solvent I, and solvent II are used simultaneously, the adjuvant may be xylene, the solvent I may be an aqueous acetonitrile solution (e.g., 80% aqueous acetonitrile), and the solvent II may be 2-methylpentane; in some embodiments, as an example, the adjuvant can be n-hexane, the solvent I can be an aqueous isopropanol solution (e.g., a 60% aqueous isopropanol solution), and the solvent II can be nonane; in some embodiments, as an example, the adjuvant may be n-butane, the solvent I may be an aqueous furfural solution (e.g., a 90% aqueous furfural solution), and the solvent II may be decane. In some embodiments, as examples, the adjuvant can be cyclohexane + pentane (e.g., 20% cyclohexane + 80% pentane), the solvent I can be an aqueous dimethyl sulfoxide solution (e.g., 80% aqueous dimethyl sulfoxide solution), and the solvent II can be oleic acid + sec-hexyl acetate (e.g., 5% oleic acid + 95% sec-hexyl acetate). In some embodiments, as an example, the adjuvant may be hexyl acetate, the solvent I may be an aqueous solution of diethylene glycol (e.g., an 80% aqueous solution of diethylene glycol), and the solvent II may be n-hexane. In some embodiments, as an example, the adjuvant may be n-heptane, the solvent I may be ethylene glycol, and the solvent II may be n-heptane. In some embodiments, as an example, the adjuvant can be methylene chloride, the solvent I can be an aqueous sulfolane solution (e.g., a 75% aqueous sulfolane solution), and the solvent II can be hexadecane. In some embodiments, as examples, the adjuvant may be pentane + nonane (e.g., 10% pentane + 90% nonane), the solvent I may be a mixture of furfural + ethanol (e.g., a mixture of 80% furfural + 20% ethanol), and the solvent II may be pentane + nonane (e.g., 10% pentane + 90% nonane). In some embodiments, the auxiliary agent may be octane, the solvent I may be a mixture of triethylene glycol monomethyl ether and N-methylpyrrolidone (e.g., a mixture of 60% triethylene glycol monomethyl ether and 40% N-methylpyrrolidone), and the solvent II may be octane, as examples.

In the solvent and the auxiliary agent, the percentage% is weight percentage. In light of the present disclosure, it will be understood by those skilled in the art that when a solvent or adjuvant alone fails to meet its corresponding polarity requirements (including dielectric constant, dipole moment), it may be combined with other optional solvents or adjuvants to yield a solvent or adjuvant that meets the requirements, and thus, the scope of each of the solvents and adjuvants in the present disclosure should not be interpreted solely from its respective alternatives.

The inventions of the present application provide one or more of the following advantages:

(1) the extraction rate is high, and the yield and the purity of phenol are improved;

(2) the solvent can be recycled, acid and alkali are avoided, the method belongs to an environment-friendly method for producing phenol, and the problems of low extraction rate of the phenol compound, equipment corrosion in an acid-alkali separation method in crude phenol production, serious pollution and the like in the prior art are solved.

(3) The method is simple to operate and low in cost, and does not influence the subsequent processing process.

Examples

The following examples are for the purpose of illustration only and are not intended to limit the scope of the present application.

The specific implementation mode is as follows:

example 1:

according to the extraction operation requirement, mixing low-temperature coal tar and an auxiliary agent (xylene) according to a mass ratio of 0.5:1 as a raw material liquid. Mixing a solvent I (80% acetonitrile aqueous solution) and a raw material solution according to a solvent-oil ratio of 5: the extraction phase I is obtained by multistage continuous countercurrent extraction at the extraction temperature of 30 ℃ and the extraction pressure of 0.1Mpa in a vibration sieve plate extraction tower from the bottom and the top of the tower respectively according to the proportion of 1. Then, mixing the solvent II (2-methylpentane) and the extract phase I according to the ratio of solvent to oil of 0.2:1, respectively entering a pulse filler extraction tower from the bottom and the top of the tower, carrying out multistage continuous countercurrent extraction at the extraction temperature of 50 ℃ and the extraction pressure of 0.1Mpa to obtain a raffinate phase II rich in crude phenol, and separating the solvents I and II and the auxiliary agent to obtain the phenolic compound with the yield higher than 90%.

Example 2:

according to the extraction operation requirement, mixing low-temperature coal tar and an auxiliary agent (n-hexane) according to the mass ratio of 1:1 as a raw material liquid. Mixing a solvent I (60% isopropanol aqueous solution) and a raw material solution according to a solvent-oil ratio of 3: the extraction phase I is obtained by multistage continuous countercurrent extraction at 20 deg.C and 0.1 MPa. Then mixing the solvent II (nonane) and the extract phase I according to the solvent-oil ratio of 2: the ratio of 1 is respectively fed into a sieve plate extraction tower from the tower bottom and the tower top, the extraction temperature is 30 ℃, the extraction pressure is 0.3Mpa, multistage continuous countercurrent extraction is carried out, a raffinate phase II rich in crude phenol is obtained, solvents I, II and an auxiliary agent are separated, a phenolic compound with high yield and purity is obtained, and the phenol purity is more than 98.1%.

Example 3:

according to the extraction operation requirement, under the pressure, the medium temperature coal tar and the auxiliary agent (n-butane) are mixed according to the mass ratio of 12:1 as a raw material liquid. Mixing a solvent I (90% furfural aqueous solution) and a raw material solution according to a solvent-oil ratio of 0.8:1, respectively entering a sieve plate extraction tower from the top and the bottom of the tower, extracting at the temperature of 80 ℃ and the extraction pressure of 12Mpa, and carrying out multistage continuous countercurrent extraction to obtain an extract phase I. And then mixing the solvent II (decane) with the extract phase I according to the ratio of the solvent II to the extract phase I of 2:1, respectively entering a filler extraction tower from the tower bottom and the tower top, extracting at the temperature of 80 ℃ and under the extraction pressure of 1.3Mpa, performing multistage continuous countercurrent extraction to obtain a raffinate phase II enriched in crude phenol, and separating the solvents I, II and the auxiliary agent to obtain the high-purity phenolic compound with the yield of 98.6%.

Example 4:

according to the extraction operation requirement, medium-temperature coal tar and an auxiliary agent (20% cyclohexane and 80% pentane) are mixed according to the mass ratio of 9:1 as a raw material liquid. Mixing a solvent I (80% dimethyl sulfoxide aqueous solution) and a raw material solution according to a ratio of agent to oil of 0.6:1, respectively entering a filler extraction tower from the top and the bottom of the tower, extracting at 140 ℃ and under 10Mpa, and performing multistage continuous countercurrent extraction to obtain an extract phase I enriched in crude phenol. After the auxiliary agent of the extract phase I is removed, the extract phase I is extracted by a solvent II (5% oleic acid and 95% sec-hexyl acetate), and the extract phase I enters a rotating disc extraction tower from the bottom and the top of the tower respectively, wherein the ratio of the solvent to the oil is 2:1, extracting at 180 ℃ under the extraction pressure of 6Mpa, performing multistage continuous countercurrent extraction to obtain a raffinate phase II enriched with crude phenol, and separating and recovering solvents I and II to obtain a phenolic compound with high yield, wherein the purity of the crude phenol is more than 98%.

Example 5:

according to the extraction operation requirements, mixing a solvent I (a mixed solution of 40% of N-octanol and 60% of N, N-dimethylformamide) with low-temperature coal tar according to a solvent-oil ratio of 6:1, respectively entering a sieve plate extraction tower from the tower bottom and the tower top, extracting at the temperature of 60 ℃ and the extraction pressure of 0.85Mpa, and carrying out multistage continuous countercurrent extraction to obtain an extract phase I. After the solvent I is removed from the extract phase I, the extract phase I and a solvent II (20% pentane, 30% heptane and 50% ethylcyclohexane) respectively enter a vibrating sieve plate extraction tower from the top and the bottom of the tower, and the solvent-oil ratio is 0.7:1, extracting at 50 ℃ under the extraction pressure of 0.8Mpa, performing multistage continuous countercurrent extraction to obtain a raffinate phase II enriched with crude phenol, and separating and recovering the solvents I and II to obtain the phenolic compound with high yield, wherein the purity of the crude phenol is not lower than 98%.

Example 6:

according to the extraction operation requirement, mixing a solvent I (60% ethylene glycol monomethyl ether aqueous solution) and a fraction of low-temperature coal tar above 180 ℃ and above 210 ℃ according to a solvent-oil ratio of 3.5:1, respectively entering a rotary disc extraction tower from the top and the bottom of the tower, extracting at the temperature of 160 ℃ and the extraction pressure of 7Mpa, and obtaining an extract phase I through multi-stage continuous countercurrent extraction. And then mixing the solvent II (tridecane) and the extract phase I according to the solvent-oil ratio of 1.5:1, respectively entering a vibrating sieve plate extraction tower from the tower bottom and the tower top, extracting at the temperature of 70 ℃ and under the extraction pressure of 0.3Mpa, performing multistage continuous countercurrent extraction to obtain a raffinate phase II enriched with crude phenol, and separating and recovering the solvents I and II to obtain the phenolic compound with the yield higher than 90%.

Example 7:

the method comprises the following steps of (1) mixing the fraction of medium temperature coal tar above 220 ℃ with an auxiliary agent (3-methylpentane) according to a mass ratio of 0.1:1 as a raw material liquid. According to the extraction operation requirements, mixing a solvent I (a mixed solution of 65% of diethylene glycol and 35% of N-methyl pyrrolidone) and a raw material solution according to a solvent-oil ratio of 6: the proportion of 1 is respectively fed into a pulse filler extraction tower from the top and the bottom of the tower, the extraction temperature is 180 ℃, the extraction pressure is 3Mpa, multistage continuous countercurrent extraction is carried out to obtain an extraction phase I rich in crude phenol, a solvent I and an auxiliary agent are separated to obtain a phenolic compound with high yield, and the extraction rate is not lower than 99.3%. Operation can be performed with reference to the apparatus shown in figure 1.

Example 8:

mixing the biomass pyrolysis liquid with an auxiliary agent (n-decane) according to a mass ratio of 0.2:1 as a raw material liquid. According to the extraction operation requirement, mixing a solvent I (mixed solution of 40% cyclohexanone and 60% acetamide) and a raw material solution according to a solvent-oil ratio of 0.4:1, respectively entering a rotary disc extraction tower from the tower bottom and the tower top, extracting at the temperature of 60 ℃, under the extraction pressure of 0.8Mpa, and separating an extract phase from a solvent I and an auxiliary agent to obtain the phenolic compound with high yield, wherein the extraction rate is not lower than 95.3%.

Example 9:

mixing the biomass pyrolysis liquid with an auxiliary agent (dichloroethane) according to a mass ratio of 0.3:1 as a raw material liquid. According to the extraction operation requirements, mixing a solvent I (a mixed solution of 60% of N-methylacetamide and 40% of triethylene glycol) and a raw material solution according to a solvent-oil ratio of 4:1, respectively entering a rotary disc extraction tower from the top and the bottom of the tower, extracting at the temperature of 130 ℃ and under the extraction pressure of 2Mpa, and carrying out multistage continuous countercurrent extraction to obtain an extract phase containing crude phenol. Separating the solvent I and the auxiliary agent to obtain the phenolic compound with high yield, wherein the extraction rate is more than 99 percent.

Example 10:

according to the extraction operation requirement, mixing low-temperature coal tar and an auxiliary agent (amyl ether) according to the mass ratio of 1.5:1 as a raw material liquid. Mixing a solvent I (a mixed solution of 60% of succinonitrile and 40% of acetic acid) and a raw material solution according to a ratio of 5:1, respectively entering a sieve plate extraction tower from the top and the bottom of the tower, extracting at the temperature of 5 ℃ and the extraction pressure of 0.5Mpa, and performing multistage continuous countercurrent extraction to obtain an extract phase rich in crude phenol. Separating the solvent I and the auxiliary agent to obtain the phenolic compound with high yield.

Example 11:

according to the extraction operation requirement, mixing low-temperature coal tar and an auxiliary agent (hexyl acetate) according to the mass ratio of 1:1 as a raw material liquid. Mixing a solvent I (80% diethylene glycol aqueous solution) and a raw material solution according to a solvent-oil ratio of 0.5: the extraction phase I is obtained by multistage continuous countercurrent extraction at the extraction temperature of 30 ℃ and the extraction pressure of 0.1Mpa in a vibration sieve plate extraction tower from the top and the bottom of the tower respectively according to the proportion of 1. And then mixing the solvent II (normal hexane) and the extract phase I according to a solvent-oil ratio of 0.5: the ratio of 1 is respectively fed into a pulse filler extraction tower from the tower bottom and the tower top, the extraction temperature is 50 ℃, the extraction pressure is 0.1Mpa, and the raffinate phase II rich in crude phenol is obtained by multi-stage continuous countercurrent extraction. And separating the solvent I, the solvent II and the auxiliary agent from the raffinate phase II to obtain the phenolic compound with high yield.

Example 12:

according to the extraction operation requirement, medium-temperature coal tar and an auxiliary agent (n-heptane) are mixed according to the mass ratio of 1: 5 as a raw material liquid. Mixing a solvent I (ethylene glycol) and a raw material liquid according to a solvent-oil ratio of 2: the extraction phase I is obtained by multistage continuous countercurrent extraction at the extraction temperature of 50 ℃ and the extraction pressure of 1Mpa in the ratio of 1 by entering the rotary disc extraction tower from the top and the bottom of the tower respectively. And mixing the solvent II (n-heptane) and the extract phase I according to the solvent-oil ratio of 1: the proportion of 1 is respectively fed into a vibrating sieve plate extraction tower from the bottom and the top of the tower, the extraction temperature is 40 ℃, the extraction pressure is 2Mpa, multistage continuous countercurrent extraction is carried out, a raffinate phase II rich in crude phenol is obtained, solvents I, II and an auxiliary agent are separated, a phenolic compound with high yield is obtained, and the purity of the separated crude phenol is not lower than 98.8%. Operation can be performed with reference to the apparatus shown in figure 2.

Example 13:

according to the extraction operation requirement, the fraction of high-temperature coal tar at the temperature of less than 250 ℃ and an auxiliary agent (50% dimethylbenzene and 50% cyclohexane) are mixed according to the mass ratio of 1:2 to be used as a raw material liquid. Mixing a solvent I (70% N, N-diethylformamide aqueous solution) and a raw material solution according to a ratio of solvent to oil of 3:1, respectively entering a pulse filler extraction tower from the top and the bottom of the tower, extracting at the temperature of 110 ℃ and the extraction pressure of 6Mpa, and performing multistage continuous countercurrent extraction to obtain an extract phase rich in crude phenol. Separating the solvent I and the auxiliary agent to obtain the phenolic compound with the yield higher than 97 percent.

Example 14:

according to the extraction operation requirement, the medium temperature coal tar fraction at the temperature of less than 250 ℃ and an auxiliary agent (dichloromethane) are mixed according to the mass ratio of 1:1 to be used as a raw material liquid. Mixing a solvent I (75% sulfolane aqueous solution) and a raw material solution according to a solvent-oil ratio of 5:1, respectively entering a pulse filler extraction tower from the tower bottom and the tower top, extracting at the temperature of 40 ℃ and the extraction pressure of 0.2Mpa, and performing multistage continuous countercurrent extraction to obtain an extract phase I rich in crude phenol products. Separating the solvent I and the auxiliary agent from the extract phase I, and feeding the obtained phenolic compound and a solvent II (hexadecane) into a vibrating sieve plate extraction tower from the bottom and the top of the tower respectively, wherein the ratio of the solvent to the oil is 1.5:1, extracting at 70 ℃ under the extraction pressure of 0.15Mpa, performing multistage continuous countercurrent extraction to obtain a raffinate phase II enriched in crude phenol, and separating and recovering a solvent II to obtain the phenolic compound with high yield and purity.

Example 15:

according to the extraction operation requirements, mixing a solvent I (a mixed solution of 80% dimethyl sulfoxide and 20% N-methyl pyrrolidone) and low-temperature coal tar according to a solvent-oil ratio of 1: the extraction phase I is obtained by multistage continuous countercurrent extraction at 160 ℃ and 1.1Mpa in a vibrating sieve plate extraction tower from the top and the bottom of the tower respectively according to the proportion of 1. Then, mixing a solvent II (10% p-xylene and 90% pentane) and an extract phase I according to a solvent-oil ratio of 2: the proportion of 1 is respectively fed into a pulse filler extraction tower from the bottom and the top of the tower, the extraction temperature is 80 ℃, the extraction pressure is 1Mpa, the extraction is obtained by multistage continuous countercurrent extraction, a raffinate phase II rich in crude phenol is obtained, solvents I and II are separated, the phenolic compound with high yield is obtained, and the purity of the separated crude phenol is not lower than 98.7%.

Example 16:

according to the extraction operation requirements, mixing a solvent I (a mixed solution of 70% sulfolane and 30% diethylene glycol monoethyl ether) and a biomass pyrolysis solution according to a solvent-oil ratio of 11:1, respectively entering a pulse filler extraction tower from the top and the bottom of the tower, extracting at 90 ℃ and under 0.05Mpa, and performing multistage continuous countercurrent extraction to obtain an extract phase I. And mixing the solvent II (n-pentane) and the extract phase I according to the solvent-oil ratio of 5: the proportion of 1 is respectively fed into a vibrating sieve plate extraction tower from the bottom and the top of the tower, the extraction temperature is 30 ℃, the extraction pressure is 0.1Mpa, the extraction is obtained by multistage continuous countercurrent extraction, a raffinate phase II rich in crude phenol is obtained, solvents I and II are separated, the phenolic compound with high yield is obtained, and the purity of the separated crude phenol is not lower than 98.4%.

Example 17:

mixing low-temperature coal tar and an auxiliary agent (10% pentane + 90% nonane) according to a mass ratio of 1:1 as a raw material liquid. According to the extraction operation requirement, mixing a solvent I (a mixed solution of 80% of furfural and 20% of ethanol) and a raw material solution according to a solvent-oil ratio of 3:1, respectively entering a rotary disc extraction tower from the top and the bottom of the tower, extracting at the temperature of 5 ℃ and the extraction pressure of 0.8Mpa, and obtaining an extract phase I through multi-stage continuous countercurrent extraction. Then, mixing a solvent II (10% pentane + 90% nonane) and an extract phase I according to a solvent-oil ratio of 0.5:1, respectively entering a pulse filler extraction tower from the tower bottom and the tower top, carrying out multistage continuous countercurrent extraction at the extraction temperature of 40 ℃ and the extraction pressure of 0.35Mpa to obtain a raffinate phase II rich in crude phenol. And separating the solvents I and II from the raffinate phase II to obtain the phenolic compound with the purity higher than 98 percent.

Example 18:

mixing low-temperature coal tar and an auxiliary agent (hexyl acetate) according to a mass ratio of 1:1 as a raw material liquid. According to the extraction operation requirements, mixing a solvent I (a mixed solution of 85% N-butanol and 15% N-methyl pyrrolidone) and a raw material solution according to a solvent-oil ratio of 4.5: the extraction temperature is 180 ℃, the extraction pressure is 4Mpa, the extraction phase rich in crude phenol is obtained by multistage continuous countercurrent extraction, the solvent I and the auxiliary agent are separated, the phenol compound with high yield is obtained, and the extraction rate is more than 99%.

Example 19:

mixing medium-temperature coal tar and an auxiliary agent (80% pentane + 20% heptane) according to a mass ratio of 1:1 as a raw material liquid. According to the extraction operation requirements, mixing a solvent I (a mixed solution of 75% triethylene glycol and 25% acetic acid) and a raw material liquid according to a solvent-oil ratio of 5:1, respectively entering a vibrating sieve plate extraction tower from the top and the bottom of the tower, carrying out multistage continuous countercurrent extraction at the extraction temperature of 60 ℃ and the extraction pressure of 0.4Mpa to obtain an extract phase rich in crude phenol, and separating a solvent I and an auxiliary agent to obtain the phenolic compound with the yield higher than 99%.

Example 20:

mixing the biomass pyrolysis liquid with an auxiliary agent (50% of cumene and 50% of n-heptane) according to a mass ratio of 1:1 as a raw material liquid. According to the extraction operation requirements, mixing a solvent I (a mixed solution of 10% cyclopentanone, 50% N, N-dimethylformamide and 40% water) and a raw material solution according to a solvent-oil ratio of 2.5: the ratio of 1 is respectively fed into a vibrating sieve plate extraction tower from the tower bottom and the tower top, the extraction temperature is 150 ℃, the extraction pressure is 0.9Mpa, crude phenol is enriched in an extraction phase, a solvent I and an auxiliary agent are separated, the phenolic compound with high yield is obtained, and the extraction rate is more than 96.8%.

Example 21:

mixing low-temperature coal tar and an auxiliary agent (octane) according to a mass ratio of 1:1 as a raw material liquid. According to the extraction operation requirements, raw material liquid and a solvent I (a mixed solution of 60% triethylene glycol monomethyl ether and 40% N-methyl pyrrolidone) are respectively fed into two ends of a tower and enter a filler extraction tower for extraction, the temperature is 30 ℃, the pressure is 0.1MPa, and the feeding agent-oil ratio is 1.5:1, obtaining an extract phase I through multi-stage continuous countercurrent extraction. Then extracting the extract phase I and a solvent II (octane) by using a sieve plate extraction tower at the temperature of 50 ℃, the pressure of 0.1MPa and the feed-agent-oil ratio of 0.3:1, obtaining raffinate phase II through multi-stage continuous countercurrent extraction. And separating the solvent I, the solvent II and the auxiliary agent by using the raffinate phase II to obtain the phenolic compound with the yield higher than 95%.

Example 22:

mixing high-temperature coal tar and an auxiliary agent (2-methylpentane) according to a mass ratio of 1: 3 as a raw material liquid. According to the extraction operation requirements, a rotary disc extraction tower is used, raw material liquid and a solvent I (a mixed solution of 80% of glycerol and 20% of propionic acid) are respectively fed to two ends of the tower, the temperature of the extraction tower is 120 ℃, the pressure is 0.11Mpa, and the feeding agent-oil ratio is 1:1, obtaining an extract phase I through multistage continuous countercurrent extraction, and separating a solvent I to obtain the phenolic compound with high yield.

Example 23:

mixing biomass pyrolysis liquid and an auxiliary agent (solvent oil) according to a mass ratio of 3:1 as a raw material liquid. According to the extraction operation requirement, a sieve plate extraction tower is used, raw material liquid and a solvent I (a mixed solution of 90% of furfural and 10% of butanone) are fed to two ends of the tower respectively, and the parameters of the extraction tower are set as follows: the temperature is 90 ℃, the pressure is 0.3Mpa, the feeding agent-oil ratio is 2:1, obtaining an extract phase I through multistage continuous countercurrent extraction, and separating the solvent I to obtain the phenolic compound with the yield not lower than 98.6%.

Example 24:

according to the extraction operation requirements, a filler extraction tower is used, the two ends of the tower are respectively fed with fractions of high-temperature coal tar below 300 ℃ and a solvent I (85% ethylene glycol aqueous solution) for extraction, the set temperature is 180 ℃, the extraction pressure is 0.5Mpa, and the solvent-oil ratio is 5:1, extracting by multiple stages to obtain an extract phase I. Then using a sieve plate extraction tower, respectively feeding the extraction phase I and the solvent II (p-xylene) at two ends of the tower, and setting the parameters of the sieve plate extraction tower: the temperature is 80 ℃, the pressure is 0.1Mpa, the ratio of agent to oil is 2:1, obtaining raffinate phase II through continuous multi-stage countercurrent extraction. After the solvent I and the solvent II are separated from the raffinate phase II, the phenolic compound with high yield is obtained, and the purity of the phenol is more than 98.6 percent.

Example 25:

according to the extraction operation requirements, a filler extraction tower is used, medium-temperature coal tar neutralizing solvent I (mixed solution of 85% dimethyl sulfoxide and 15% propionic acid) is fed into two ends of the tower respectively for extraction, the temperature is set to be 170 ℃, the extraction pressure is 0.7Mpa, and the solvent-oil ratio is 0.35: 1, obtaining an extract phase I through multistage continuous cross-flow extraction. And then using a filler extraction tower, respectively feeding the extraction phase I and the neutralizing solvent II (methyl cyclopentane) at two ends of the tower, and setting the parameters of the filler extraction tower: the temperature is 30 ℃, the agent-oil ratio is 5:1, the pressure is 0.7Mpa, and the raffinate phase II is obtained by continuous multi-stage countercurrent extraction. And separating the solvent I and the solvent II from the raffinate phase II to obtain the phenolic compound with the purity higher than 98 percent.

Example 26:

according to the extraction operation requirements, a filler extraction tower is used, the distillate of low-temperature coal tar with the temperature of more than 210 ℃ and a solvent I (60% acetone aqueous solution) are respectively fed into two ends of the tower for extraction, the set temperature is 110 ℃, the extraction pressure is 0.8Mpa, and the solvent-oil ratio is 4:1, obtaining an extract phase I through multi-stage continuous countercurrent extraction. And then using a filler extraction tower, wherein the extraction phase I and a solvent II (80% methylcyclohexane and 20% toluene) are respectively fed into two ends of the tower, the temperature of the extraction tower is 40 ℃, the solvent-oil ratio is 6:1, the pressure is 0.8Mpa, and the raffinate phase II is obtained by continuous multi-stage countercurrent extraction. Separating the solvents I and II to obtain the phenolic compound with the purity of not less than 98.7 percent.

While the invention has been described in detail by way of the general description and the specific embodiments, it will be apparent to those skilled in the art that certain modifications or improvements may be made in the invention and any combination may be made as required. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims

1. A method of separating, enriching or producing phenolic compounds or a method of processing oils comprising:

adding an auxiliary agent into an oil product;

the solvent I is a polar solvent and contains at least one organic solvent.

2. A method of separating, enriching or producing phenolic compounds or a method of processing oils comprising:

the solvent I is a polar solvent and contains at least one organic solvent;

the solvent II is a weak polar or non-polar solvent.

3. The method of claim 2, further comprising: adding an auxiliary agent to the oil product before extraction with the solvent I, wherein the auxiliary agent is selected from a weakly polar solvent and a non-polar solvent;

optionally, the adjuvant is the same or different from the solvent II;

optionally, the extraction phase I is subjected to extraction with a solvent ii after separation or recovery of the solvent and/or auxiliary agent therefrom.

4. The method of any one of claims 1 to 3,

the extraction temperature is 0-200 ℃, 20-150 ℃, 25-120 ℃ or 25-100 ℃ in the extraction process using the solvent I and/or the extraction process using the solvent II; and/or

In the extraction process using the solvent I, the extraction pressure is 0.01MPa to 15MPa, 0.05MPa to 5MPa, or 0.1MPa to 0.5MPa in absolute pressure; and/or

In the extraction process using the solvent II, the extraction pressure is 0.01MPa to 15MPa, 0.05MPa to 5MPa, or 0.1MPa to 1MPa in absolute pressure; and/or

The ratio of extracted liquid to corresponding extraction solvent in the extraction process using solvent I and/or in the extraction process using solvent II is 0.02-50:1, 0.1-10:1, 0.2-5:1, or 0.25-4: 1; and/or

The ratio of the raw oil product to the auxiliary agent is 0.02-50:1, 0.1-10:1, 0.2-5:1, or 0.25-4: 1; and/or

The extraction device used is selected from a mixer-settler, an extraction column, a centrifugal extractor and a combination thereof; wherein optionally, the extraction column comprises a packed extraction column, a sieve plate extraction column, a rotating disc extraction column, a vibrating sieve plate column, and combinations thereof; and/or

The method further comprises the step of removing or recovering solvents and/or auxiliary agents from the extract phase I and/or the raffinate phase II enriched in phenolic compounds; optionally, the step of removing or recovering the solvent and/or adjuvant comprises a step selected from the group consisting of extraction, distillation, and combinations thereof; optionally, the removed or recovered auxiliary, solvent I and/or solvent II are returned to the extraction process for recycling.

5. An apparatus for separating, enriching or producing phenolic compounds or for processing oils comprising:

a raw oil product tank, an auxiliary agent tank, a solvent I tank and an extraction device I; wherein

optionally, a discharge port of the phenol-containing extract phase I is arranged on the extraction device I;

optionally, the discharge port of the phenol-containing extract phase I is arranged on the side wall, the upper part or the bottom of the extraction device I;

optionally, the equipment further comprises a desolventizing and/or auxiliary agent device I, and the discharge port is connected to the desolventizing and/or auxiliary agent device I, so that the phenol-containing extract phase I enters the desolventizing and/or auxiliary agent device I after being discharged from the discharge port;

optionally, the solvent removal and/or auxiliary agent device I is connected with the solvent I tank and/or the auxiliary agent tank, so that the removed solvent I and/or auxiliary agent are respectively recycled to the solvent I tank and/or the auxiliary agent tank or returned to the extraction process for recycling;

optionally, the desolventizing and/or adjunct apparatus I is selected from the group consisting of an extraction apparatus, a distillation apparatus, and combinations thereof;

optionally, the apparatus further comprises a valve to control the flow of fluid.

6. An apparatus for separating, enriching or producing phenolic compounds or for processing oils comprising: a raw oil product tank, a solvent I tank, a solvent II tank, an extraction device I and an extraction device II; wherein:

the solvent II tank is connected with the extraction device II;

a discharge port of the phenol-containing extract phase I is formed in the extraction device I, and the phenol-containing extract phase I is discharged from the discharge port of the phenol-containing extract phase I and then enters the extraction device II;

optionally, the extract phase I is discharged from a discharge port of the phenol-containing extract phase I and then directly enters the extraction device II;

optionally, the equipment further comprises an auxiliary agent tank, wherein the auxiliary agent tank is connected with the extraction device I and is filled with an auxiliary agent selected from a non-polar solvent and a weak-polar solvent;

optionally, the adjuvant is the same or different from the solvent II;

optionally, when the auxiliary agent is the same as the solvent II, an auxiliary agent tank does not need to be additionally arranged, and the solvent II tank is simultaneously used as an auxiliary agent tank; and in this case the solvent II tank is also connected to the extraction unit I, so that solvent II is also fed as an auxiliary agent to the extraction unit I;

optionally, the equipment further comprises a desolventizing and/or auxiliary agent device I, and the discharge port of the phenol-containing extract phase I is connected to the desolventizing and/or auxiliary agent device I, so that the phenol-containing extract phase I enters the desolventizing and/or auxiliary agent device I after being discharged from the discharge port of the phenol-containing extract phase I; and the desolventizing and/or auxiliary agent device I is connected to the extraction device II, so that the crude phenol subjected to desolventizing and/or auxiliary agent removal enters the extraction device II;

optionally, a feed inlet of the phenol-containing extract phase I or the crude phenol subjected to solvent and/or auxiliary agent removal into the extraction device II is formed in the upper side wall or the upper part of the extraction device II;

optionally, a phenol-containing raffinate phase II discharge hole is formed in the extraction device II;

optionally, the discharge hole of the phenol-containing raffinate phase II is arranged on the lower side wall or the bottom of the extraction device II;

optionally, the equipment further comprises a desolventizing and/or auxiliary agent device II, and the discharge port of the phenol-containing raffinate phase II is connected to the desolventizing and/or auxiliary agent device II, so that the phenol-containing raffinate phase II enters the desolventizing and/or auxiliary agent device II after being discharged from the discharge port of the phenol-containing raffinate phase II;

optionally, the solvent removal and/or auxiliary agent device II is connected with the solvent I tank, the solvent II tank and/or the auxiliary agent tank, so that the removed solvent I, solvent II and/or auxiliary agent are respectively recycled to the solvent I tank, the solvent II tank and/or the auxiliary agent tank or returned to the extraction process for recycling;

optionally, the desolventizing and/or adjunct apparatus I and the desolventizing and/or adjunct apparatus II are selected from the group consisting of an extraction apparatus, a distillation apparatus, and combinations thereof;

7. The method of any one of claims 1 to 4 or the apparatus of claim 5 or 6, wherein:

the coal tar is selected from low temperature coal tar, medium temperature coal tar, high temperature coal tar and their combination;

dielectric constant of solvent I at 20 DEG C>2.5 and dipole moment>2×10^-30C.m；

Dielectric constant of solvent II at 20 DEG C<2.3 or dipole moment<1.5×10^-30C.m；

Dielectric constant of the assistant at 20 DEG C<2.3 or dipole moment<1.5×10^-30C.m。

8. The method of claim 7 or the apparatus of claim 7, wherein:

the low-temperature coal tar is coal tar obtained by pyrolyzing coal at 450-650 ℃, the medium-temperature coal tar is coal tar obtained by pyrolyzing coal at 650-800 ℃, and the high-temperature coal tar is coal tar obtained by pyrolyzing coal at 800-1200 ℃;

optionally, the oil as a starting material is selected from untreated low temperature coal tar, untreated medium temperature coal tar, untreated high temperature coal tar, untreated biomass pyrolysis liquid or their rectified or extracted fractions, and any combination thereof;

wherein optionally, the fraction of the oil that is rectified is selected from: the low-temperature coal tar distillate at 170-400 ℃, the medium-temperature coal tar distillate at 170-400 ℃, the high-temperature coal tar distillate at 170-360 ℃, the biomass pyrolysis liquid distillate at 170-400 ℃ and any combination thereof;

optionally, the auxiliary agent is selected from benzene, toluene, xylene, C₉～C₂₀Aromatic hydrocarbon, C₉～C₂₀Aromatic ether, C₁～C₂₀Halogenated alkanes, C₃～C₂₀Alkane, C₅～C₂₀Cycloalkanes, C₂～C₂₀Fatty ethers, C₁～C₂₀Esters of fatty acids, mineral spirits, and combinations thereof;

optionally, the solvent I is selected from the group consisting of nitrogen-containing compounds, sulfur-containing compounds, alcohols, ketones, ethers, carboxylic acids, esters, aromatic hydrocarbons, aldehydes, water, and combinations thereof;

optionally, the solvent II is selected from the group consisting of aromatic hydrocarbons, alkanes, haloalkanes, ethers, carboxylic acids, esters, mineral spirits, and combinations thereof.

9. The method of claim 8 or the apparatus of claim 8, wherein:

the nitrogen-containing compound solvent in solvent I is selected from acetonitrile, butyronitrile, succinonitrile, formamide, acetamide, benzamide, N-methylformamide, N-dimethylformamide, N-ethylformamide, N-diethylformamide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidone, and a combination thereof; and/or

The sulfur compound-based solvent in solvent I is selected from the group consisting of dimethyl sulfoxide, sulfolane, dimethyl sulfone, and combinations thereof; and/or

The alcoholic solvent in solvent I is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, pentanol, isopentanol, fusel oil, hexanol, heptanol, octanol, isooctanol, phenethyl alcohol, cyclohexanol, methylcyclohexanol, ethylene glycol, glycerol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, furfuryl alcohol, tetrahydrofurfuryl alcohol, and combinations thereof; and/or

The ketone solvent in solvent I is selected from the group consisting of acetone, methyl acetone, butanone, methyl isobutyl ketone, 2-pentanone, 3-pentanone, isophorone, cyclopentanone, cyclohexanone, methylcyclohexanone, acetophenone, and combinations thereof; and/or

The ether solvent in the solvent I is selected from hydroxyl-containing ether; optionally, the hydroxyl-containing ether is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-tertiary-butyl ether, ethylene glycol isopentyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, and combinations thereof; and/or

The carboxylic acid-based solvent in solvent I is selected from the group consisting of acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, heptanoic acid, and combinations thereof; and/or

The ester-based solvent in solvent I is selected from the group consisting of methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, hexyl acetate, dimethyl carbonate, tributyl phosphate, tricresyl phosphate, di (2-ethylhexyl) phosphate, tri (2-ethylhexyl) phosphate, diisobutyl phthalate, dibutyl phthalate, diethyl phthalate and combinations thereof; and/or

The aromatic hydrocarbon solvent in the solvent I is selected fromBenzene, toluene, xylene, C₉～C₂₀Aromatic hydrocarbons and combinations thereof; and/or

The aldehyde solvent in the solvent I is selected from furfural.

10. The method of claim 8 or 9 or the apparatus of claim 8 or 9, wherein:

the aromatic hydrocarbon solvent in the solvent II is selected from benzene, toluene, xylene and C₉～C₂₀Aromatic hydrocarbons, pyridine, picoline, furan, methylfuran, thiophene, methylthiophene, and combinations thereof; and/or

The alkane solvent in the solvent II is selected from C₃～C₂₀Alkane, C₅～C₂₀Cycloalkanes and combinations thereof; and/or

The haloalkanes in solvent II are selected from the group consisting of methyl chloride, ethyl chloride, methylene chloride, ethylene dichloride, chlorobutane, and combinations thereof; and/or

The ether solvent in the solvent II is selected from diethyl ether, propyl ether and C₆～C₂₀Aliphatic ethers and combinations thereof; and/or

The carboxylic acid-based solvent in solvent II is selected from the group consisting of octanoic acid, 2-ethylhexanoic acid, tetradecanoic acid, oleic acid, and combinations thereof; and/or

The ester solvent in solvent II is selected from the group consisting of methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, hexyl acetate and combinations thereof.