CN106278827A - A kind of method and device of extract and separate phenolic compound from coal derived oils - Google Patents
A kind of method and device of extract and separate phenolic compound from coal derived oils Download PDFInfo
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- CN106278827A CN106278827A CN201610586679.6A CN201610586679A CN106278827A CN 106278827 A CN106278827 A CN 106278827A CN 201610586679 A CN201610586679 A CN 201610586679A CN 106278827 A CN106278827 A CN 106278827A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/005—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from products, waste products or side-products of processes, not directed to the production of phenols, by conversion or working-up
- C07C37/007—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from products, waste products or side-products of processes, not directed to the production of phenols, by conversion or working-up from the tar industry
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/005—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from products, waste products or side-products of processes, not directed to the production of phenols, by conversion or working-up
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
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Abstract
The invention discloses a kind of method and device of extract and separate phenolic compound from coal derived oils, wherein said method comprise the steps: rich in phenol fraction distillation cutting: coal derived oils is carried out distillation fraction cutting, cut a certain temperature section rich in phenol fraction；Solvent Centrifugical extraction separates: will be enriched in phenol fraction, extractant and auxiliary agent and is centrifuged separating, obtain is light phase for dephenolize oil assistant solution, heavy phase is the liquid phase containing extractant of enrichment phenolic compound, the wherein said extractant at least one or at least one aqueous solution in following butanone, Hexalin, dihydroxylic alcohols and glacial acetic acid；Centrifugal back extraction separates；Auxiliary agent reclaims；Strippant reclaims；Crude phenols purify: the crude phenols raw material containing a small amount of extractant is carried out azeotropic distillation separation, is extracted agent and crude phenols product.
Description
Technical field
The present invention relates to Coal Chemical Industry, petrochemicals separation technology field, extract from coal derived oils particularly to one
Take the method and device of separating phenols compounds.
Background technology
Coal can produce a large amount of coal derived oils rich in phenolic compound in the conversion processes such as pyrolysis, coking, gasification, as
Coking by-product high temperature tar phenol content 1～2.5% (mass fraction, lower same), in coal direct liquefaction oil, phenol content is 10～20%,
Phenol content in middle coalite tar is up to 15%～30%.The technology of current existing separation and Extraction phenolic compound, industrial
Main employing soda acid elution method, utilizes the acidity of aldehydes matter, uses sodium hydrate aqueous solution to neutralize with it, the sodium phenolate of generation
It is transferred to aqueous phase insoluble in oil phase, re-uses carbon dioxide or sulphuric acid makes sodium phenolate be reduced to aldehydes matter, practice have shown that,
Soda acid is washed due to needs substantial amounts of use strong acid and strong alkali aqueous solution, there is problems in that (1) substantial amounts of strong acid and strong base is perishable
Process equipment, the equipment that affects normally uses；(2) substantial amounts of strong acid and strong alkali aqueous solution can cause producing in separation process substantial amounts of
Phenol wastewater, easily causes environmental pollution, and in waste water, substantial amounts of K, Na ion subsequent biochemical is difficult；(3) soda acid elution method separates
In the crude phenols product extracted, water content is relatively big (correlation standard 10%), increases subsequent treatment difficulty and processing cost；(4) acid
Alkaline Elution technical process is loaded down with trivial details, uses conventional hybrid defecator or turntable extracting tower, and floor space is big, and energy consumption is high.
Having many documents or patent report at present uses other method (such as ionic liquid, solvent extraction, pressure partial crystallization
Deng) research of separation and Extraction phenolic compound from coal tar or liquefied coal coil.One of which is
Extractant separates coal tar, and ionic liquid forms ionic liquid phase (lower phase) with phenolic compound thus realizes oil phenol and separate；
Ionic liquid is used ether compound or nitrogen air stripping back extraction mutually with phenol mixture, ionic liquid is separated with phenol, real
Existing ionic liquid cycling and reutilization.The method extraction carries that phenol efficiency is low, neutral oil is carried secretly greatly, has a strong impact on subsequent fine phenolic product matter
Amount, ionic liquid production cost is high, remains in the laboratory research stage at present, and industrialization difficulty is big.
Another is to react with the raw material containing phenol with ammonia spirit, forms the ammonium salt in heavy being soluble in the aqueous phase, and aqueous phase is again
With dihydro carbon (CO2) reaction generation ammonium hydrogen carbonate, and the crude phenols that dissociate, heat ammonium bicarbonate aqueous solution, be decomposed into ammonia and two
Carbonoxide, ammonia is soluble in the aqueous phase and forms ammonia spirit and CO2Recycle.This method the most unavoidably produces a large amount of phenol wastewater, work
Skill process is complex, and energy consumption is big, and big to equipment corrosion.
Also having one is to be less than 230 DEG C using glycerin solution or diethanolamine aqueous solution as extractant, separation and Extraction
Rich in phenol fraction, after extract and separate, phenolic compound is enriched in the aqueous phase containing extractant, using toluene class, ethers as back extraction
Agent, by multistage back extraction, obtains back washing agent-phenol solution and extractant, and back washing agent and extractant are reclaimed in rectification, recycle, water
Steam removes the neutral oil that phenolic compound is carried secretly, it is thus achieved that crude phenols product, utilizes rectification to refine further.The multistage back extraction of this process
Carrying that phenol efficiency is low, neutral oil is carried secretly greatly, affect phenols purity, steam is except impurity such as neutral oils, and energy consumption is bigger.
Summary of the invention
In view of this, the embodiment of the present invention provides method and the dress of a kind of extract and separate phenolic compound from coal derived oils
Putting, main purpose is
For reaching above-mentioned purpose, present invention generally provides following technical scheme:
On the one hand, embodiments provide a kind of method of extract and separate phenolic compound from coal derived oils, bag
Include following steps:
Rich in phenol fraction distillation cutting: coal derived oils is carried out distillation fraction cutting, cut a certain temperature section rich in phenol
Fraction；
Solvent Centrifugical extraction separate: will be enriched in phenol fraction, extractant and auxiliary agent be centrifuged separate, obtain light phase be de-
Carbolic oil-compounding agent solution, heavy phase is the liquid phase containing extractant of enrichment phenolic compound, and wherein said extractant is selected from following fourth
At least one or at least one aqueous solution in ketone, Hexalin, dihydroxylic alcohols and glacial acetic acid；
Centrifugal back extraction separates: strippant and extract and separate are obtained be enriched with phenolic compound containing extractant
Liquid phase is centrifuged separating, and obtain is light phase for strippant-phenol solution, wherein containing a small amount of extractant；Heavy phase is enrichment
Extractant；
Auxiliary agent reclaims: reclaimed by the auxiliary agent in dephenolize oil-compounding agent solution；
Strippant reclaims: by strippant-phenol solution rectification, obtains strippant and the crude phenols containing a small amount of extractant are former
Material；
Crude phenols purify: the crude phenols raw material containing a small amount of extractant is carried out azeotropic distillation separation, be extracted agent and crude phenols produce
Product.
As preferably, it is C that azeotropic distillation separates the entrainer used5-C10N-alkane, entrainer with containing a small amount of extractant
The mass ratio of crude phenols raw material be 1:(1-10).
As preferably, described entrainer is C7-C9N-alkane.
As preferably, described entrainer is 1:(1-2 with the mass ratio of the crude phenols raw material containing a small amount of extractant).
As preferably, extractant and coarse powder that centrifugal back extraction obtains purify after the extractant obtained reclaims for solvent
Centrifugical extraction separating step, it is achieved extractant recycles.
As preferably, also include extractant regeneration step: the extractant of recycling is carried out rectification regeneration, after regeneration
Extractant recycles.
As preferably, described extractant is the aqueous solution of glacial acetic acid and dihydroxylic alcohols.
As preferably, described auxiliary agent is selected from least in following solvents oil, low carbon chain hydrocarbon solvent, kerosene and petroleum ether
Kind.
As preferably, described auxiliary agent is the mixed liquor of low carbon chain hydrocarbon solvent and petroleum ether.
As preferably, the mass ratio of low carbon chain hydrocarbon solvent and petroleum ether is 1:(0.5-5).Preferably mass ratio is 1:
(1-2)。
As preferably, described extractant with rich in phenol fraction by 1:(1-10) mass ratio be centrifuged extract and separate.
As preferably, described extractant with rich in phenol fraction by 1:(2-4) mass ratio be centrifuged extract and separate.
As preferably, described auxiliary agent with rich in phenol fraction by 1:(0.2-5) mass ratio be centrifuged extract and separate.
As preferably, described carry out supergravity multistage extraction rich in phenol fraction, use adverse current or cross-current flow, use cross-flow
It is 2-8 level during extraction mode, preferably 2-4 level；It is 2-12 level during employing counter-current extraction mode, preferably 2-6 level.
As preferably, extraction temperature is 20～120 DEG C, preferably 30～60 DEG C.
As preferably, described strippant is selected from following dimethyl sulfoxide, oxolane, butyl ether, ethyl acetate and diisopropyl ether
In at least one.
As preferably, described strippant is butyl ether or diisopropyl ether.
As preferably, the liquid phase containing extractant of described strippant and enrichment phenolic compound is with (0.1-3): 1
Mass ratio is centrifuged back extraction.
As preferably, described strippant with the mass ratio of the liquid phase containing extractant of enrichment phenolic compound is
(0.5-1):1。
As preferably, described back extraction is multitple extraction, and described back extraction uses adverse current or cross-current flow, uses mistake
It is 2-8 level during stream extraction mode, preferably 2-4 level；It is 2-12 level during employing counter-current extraction mode, preferably 2-6 level.
As preferably, the temperature of described back extraction is 20～120 DEG C, preferably 30～60 DEG C.
On the other hand, embodiments provide a kind of device of extract and separate phenolic compound from coal derived oils,
Including:
Rich in phenol fraction distillation column, coal derived oils normal pressure or vacuum distillation tower are carried out fraction cutting, cuts a certain temperature
Duan Fuhan phenol fraction；
On-line continuous blender, is connected with rich in phenol fraction distillation column, mixes cut with auxiliary agent rich in phenol fraction
To homogeneous rich in phenol fraction liquid phase；
Supergravity multistage extraction equipment, heavy liquid inlet is connected with on-line continuous blender, the richness that will enter from heavy liquid inlet
Containing phenol fraction liquid phase and the quick hybrid separation of extractant entered from light phase inlet, it is light phase for dephenolize that light phase export exports
Oil-compounding agent solution, the liquid phase containing extractant that heavy phase is enrichment phenolic compound of heavy out output；
Supergravity multistage back extraction device, its heavy liquid inlet is connected with the heavy out of supergravity multistage extraction equipment,
By the liquid phase containing extractant of heavy phase enrichment phenolic compound entered from heavy liquid inlet and the back extraction from light phase inlet entrance
Taking the quick hybrid separation of agent, the light phase of light phase export output is the strippant-phenol solution containing a small amount of extractant；Heavy out is defeated
The heavy phase gone out is the extractant of enrichment；
Strippant recovery tower, is connected with the light phase export of supergravity multistage back extraction device, by strippant-phenol solution
In strippant carry out rectification recovery, tower top output strippant, recycle；The output crude phenols containing a small amount of extractant at the bottom of tower
Raw material；
Auxiliary agent recovery tower, is connected with the light phase export of supergravity multistage extraction equipment, by helping in dephenolize oil-compounding agent solution
Agent carries out rectification recycling use, and tower top is auxiliary agent；
Extractant recovery tower, is connected at the bottom of the tower of strippant recovery tower, is carried out by the crude phenols raw material containing a small amount of extractant
Azeotropic distillation, isolated extractant and crude phenols product.
As preferably, also include that the heavy phase of multistage back extraction device is gone out by extractant regeneration tower, described extractant regeneration tower
The extractant of mouth and the output of extractant Distillation recovery tower carries out rectification regeneration.
As preferably, also include de-solid preprocessor, be connected with the charging aperture rich in phenol fraction distillation column, described de-solid pre-
Processor carries out de-solid process to coal derived oils raw material, obtains coal derived oils.
As preferably, described de-solid preprocessor is horizontal screw centrifuge.
As preferably, described is normal pressure or vacuum distillation tower rich in phenol fraction distillation column.
As preferably, also include that extractant blender, described extractant blender are described supergravity multistage extraction equipment
Extractant is provided, the extractant of the heavy out of supergravity multistage back extraction device and the output of extractant Distillation recovery tower directly or
Described extractant blender is inputted after extractant regeneration tower rectification regenerates.
As preferably, also including entrainer storage tank, described entrainer storage tank provides entrainer for described extractant recovery tower.
As preferably, also include that strippant blender, described strippant blender fill with described multistage back extraction
Putting connection, described strippant blender provides strippant to described multistage back extraction device.
Compared with prior art, the beneficial effects of the present invention is:
The method that the embodiment of the present invention provides, compared with traditional soda acid elution method, uses green high-efficient to be combined organic molten
Agent, it is high that addition is few, extraction puies forward phenol efficiency, it is to avoid strong acid and strong base uses and a large amount of high slat-containing wastewaters produce, and reduces dress
The corrosivity put.The crude phenols product quality indicator obtained is better than existing index, reduces follow-up refining of crude phenol cost.Whole process
Without waste water, waste gas discharge, substantially without waste residue, separation process use extractant, strippant equal solvent all recycle, fall
Low operation cost, is greatly improved environmental benefit.
Scheme attached explanation
The structure of the device of extract and separate phenolic compound from coal derived oils that Fig. 1 provides for the embodiment of the present invention and work
Make schematic flow sheet.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, but not as a limitation of the invention.?
In the description below, what different " embodiments " or " embodiment " referred to is not necessarily same embodiment.Additionally, one or more is implemented
Special characteristic, structure or feature in example can be combined by any suitable form.
The structure of the device of extract and separate phenolic compound from coal derived oils that Fig. 1 provides for the embodiment of the present invention and work
Make schematic flow sheet, see Fig. 1.Extract and separate phenolic compound from coal derived oils, specific as follows:
Rich in the distillation cutting of phenol fraction: with rich in phenol fraction distillation column 2, coal derived oils is carried out distillation fraction cutting, cut
A certain temperature section rich in phenol fraction, cut is delivered to on-line continuous blender 3 rich in phenol fraction；
Premix: be mixed to get homogeneous evaporating rich in phenol by cut rich in phenol fraction and auxiliary agent with online continuous mixing device 3
Divide liquid phase, be delivered to multitple extraction device 4 rich in phenol fraction liquid phase；
Solvent Centrifugical extraction separates: input multitple extraction device 4 respectively rich in phenol fraction liquid phase and extractant, through multistage
The quick hybrid separation of extraction equipment 4, it is light phase for dephenolize oil-compounding agent solution, the heavy phase of heavy out output that light phase export exports
For being enriched with the liquid phase containing extractant of phenolic compound, wherein extractant is selected from following butanone, Hexalin, dihydroxylic alcohols and ice vinegar
At least one or at least one aqueous solution in acid；
Centrifugal back extraction separates: the enrichment phenols chemical combination of the heavy out output of strippant and multitple extraction device 4
The liquid phase containing extractant of thing inputs multistage back extraction device 5 respectively, quickly mixes through multistage back extraction device 5 and divides
From, obtain is light phase for strippant-phenol solution, wherein containing a small amount of extractant；Heavy phase is the extractant of enrichment；
Auxiliary agent reclaims: the dephenolize oil of the light phase export output of multitple extraction device 4-compounding agent solution input auxiliary agent recovery tower 7,
Dephenolize oil-compounding agent solution carries out rectification in auxiliary agent recovery tower 7, and the auxiliary agent of tower top output reclaims and recycles；
Strippant reclaims: the strippant of the light phase export output of multistage back extraction device 5-phenol solution input back extraction
Agent recovery tower 6, strippant-phenol solution carries out rectification in strippant recovery tower 6, and the strippant of tower top output reclaims also
Recycle, the output crude phenols raw material containing a small amount of extractant at the bottom of tower；
Crude phenols purify: the input extractant of the crude phenols raw material containing a small amount of extractant of output at the bottom of the tower of strippant recovery tower 6
Recovery tower 8, the crude phenols raw material containing a small amount of extractant carries out azeotropic distillation, the extractant of tower top output in extractant recovery tower 8
Reclaim and recycle, at the bottom of tower, export crude phenols product.
In the method eco-friendly butanone of employing, Hexalin, dihydroxylic alcohols and glacial acetic acid that the embodiment of the present invention provides extremely
Few one or aqueous solution are as separating medium, and through multitple extraction, phenolic compound is enriched in lower floor's liquid phase containing extractant
In, by reverse multitple extraction, extractant and phenolic compound are separated, obtains back washing agent-phenol solution and extractant, through rectification
Realize respectively reclaiming back washing agent and extractant, recycle, purify, by coarse powder, the neutral oil carried secretly in removing coarse powder raw material miscellaneous
Matter, it is thus achieved that crude phenols product.Embodiment of the present invention technique is simple, separation costs is low, good to environment.Whole process is strong without strong acid
Alkali, produces without waste water and gas, has certain reality and environment protection significance.
Crude phenols purify and the method such as azeotropic distillation or vapor distillation can be used to realize.As above-described embodiment one
Preferably, crude phenols purification step uses azeotropic distillation method, and it is C that azeotropic distillation separates the entrainer used5-C10N-alkane, azeotropic
Agent is 1:(1-10 with the mass ratio of the crude phenols raw material containing a small amount of extractant).The present embodiment can be by a small amount of extraction in crude phenols raw material
Agent separates, thus carries out recycling use, and makes the quality of crude phenols product obtained higher.Entrainer is preferably C7-C9Positive structure
Alkane.Entrainer is preferably 1:(1-2 with the mass ratio of the crude phenols raw material containing a small amount of extractant).May further ensure that extractant
Recovery and the quality of crude phenols product.
Auxiliary agent in the embodiment of the present invention can improve the organic solvent (extractant) solvability to phenols, and reduces neutrality
Oily carries secretly and disturbs.Preferred as above-described embodiment, auxiliary agent is selected from following solvents oil, low carbon chain hydrocarbon solvent, kerosene and stone
At least one in oil ether.In the present embodiment, auxiliary agent can be the one in above-mentioned substance, it is also possible to be two or more
Any mixing, the auxiliary agent of the present embodiment can dissolve each other with coal derived oils, and insoluble with extractant, improves molten to phenols of extractant
Solution ability, and reduce the impurity such as neutral oil be mixed into enrichment phenolic compound the liquid phase (weight of extract and separate containing extractant
Phase).Wherein, auxiliary agent is preferably the mixed liquor of low carbon chain hydrocarbon solvent and petroleum ether.Low carbon chain hydrocarbon solvent and the preferred matter of petroleum ether
Amount ratio is 1:(0.5-5).Low carbon chain hydrocarbon solvent and the further preferred mass ratio of petroleum ether are 1:(1-2).
Preferred as above-described embodiment, for ensureing back extraction effect, the preferred strippant that the present embodiment is given is selected from
At least one in following dimethyl sulfoxide, oxolane, butyl ether, ethyl acetate and diisopropyl ether.Wherein, strippant is preferably fourth
Ether or diisopropyl ether.The liquid phase containing extractant of strippant and enrichment phenolic compound is with (0.1-3): the mass ratio of 1 is carried out
Centrifugal back extraction.Strippant is preferably (0.5-1) with the mass ratio of the liquid phase containing extractant of enrichment phenolic compound:
1。
Preferred as above-described embodiment, back extraction is supergravity multistage extraction, and back extraction uses adverse current or cross-flow
Mode, is 2-8 level during employing cross current solvent extraction mode, preferably 2-4 level；It is 2-12 level during employing counter-current extraction mode, preferably
2-6 level.
Preferred as above-described embodiment, the extraction temperature of back extraction is 20～120 DEG C, preferably 30～60 DEG C.This
In bright embodiment, back extraction can be carried out at a lower temperature, saves operating cost, and has preferable back extraction effect
Really.
Preferred as above-described embodiment, extractant that back extraction obtains and coarse powder purify after the extractant obtained reclaims
For solvent Centrifugical extraction separating step, it is achieved extractant recycles.The present embodiment achieves the recycling of extractant, both
It is beneficial to reduce cost, the most beneficially environmental conservation.Due to extractant meeting accumulated impurity during recycling, for ensureing extractant
Normal use, after extractant recycles a period of time, can be to extractant regeneration, the extractant that specifically can recycle
Carrying out rectification regeneration, the extractant after regeneration recycles.
Preferred as above-described embodiment, extractant is the aqueous solution of glacial acetic acid and dihydroxylic alcohols.Use above two material
Mixed aqueous solution can further improve effect of extracting as extractant.
Preferred as above-described embodiment, extractant with rich in phenol fraction by 1:(1-10) mass ratio be centrifuged extracting
Separate.Extractant with rich in phenol fraction preferably by 1:(2-4) mass ratio be centrifuged extract and separate.
Preferred as above-described embodiment, carries out supergravity multistage extraction rich in phenol fraction, uses adverse current or cross-current flow,
It is generally 2-8 level, preferably 2-4 level when using cross current solvent extraction mode；It is generally 2-12 level when using counter-current extraction mode, excellent
Select 2-6 level.
In the embodiment of the present invention, extraction and back extraction all preferably employ supergravity multistage extraction, and concrete mode can be adverse current
Or cross-flow.
Preferred as above-described embodiment, extraction temperature is 20～120 DEG C, preferably 30～60 DEG C.The embodiment of the present invention
Extraction can be carried out at a lower temperature.
By above-described embodiment, the method for the embodiment of the present invention can be by (but being not limited to) embodiment of the present invention
Device realizes.
In conjunction with Fig. 1, preferred as above-described embodiment, the device of the embodiment of the present invention also includes extractant regeneration tower 9, extraction
Take agent regenerator 9 and the heavy out of multistage back extraction device and the extractant of extractant Distillation recovery tower output are carried out rectification again
Raw.The heavy out of multistage back extraction device and the tower top of extractant Distillation recovery tower connect extractant regeneration tower by pipeline,
So that the extractant recycling a period of time is regenerated.
Preferred as above-described embodiment, also includes in the present embodiment that extractant blender 10, extractant blender 10 are
Multitple extraction device 4 provides extractant.Each material inputs extractant blender of composition extractant can be mixed, then
It is supplied to multitple extraction device.At running, heavy out and the extractant Distillation recovery tower 8 of multistage back extraction device 5 are defeated
The extractant gone out can be directly inputted in extractant blender 10, it is achieved the recycling of extractant.Above-mentioned, there is extractant
On the basis of the embodiment of regenerator, the heavy out of multistage back extraction device 5 and extractant Distillation recovery tower 8 are except directly connecting
Connecing outside extractant blender 10, be also connected with extractant regeneration tower 9, extractant regeneration tower 9 connects extractant blender 10, the most logical
Crossing Valve controlling, can to realize the extractant of the heavy out of multistage back extraction device 5 and the output of extractant Distillation recovery tower 8 direct
It is input in extractant blender 10 or after extractant regeneration tower 9 rectification regenerates, inputs extractant blender 10.This enforcement
The extractant recycling a period of time can be regenerated by example, to remove the impurity of accumulation in cyclic process, it is ensured that extraction
Effect.
Preferred as above-described embodiment, also includes de-solid preprocessor 1 in the present embodiment, de-solid preprocessor 1 is with rich
Charging aperture containing phenol fraction distillation column 2 connects, and coal derived oils raw material is carried out taking off solid process by de-solid preprocessor 1, obtains coal and spreads out
Oil generation, then inputs and cuts rich in phenol fraction distillation column 2.De-solid preprocessor 1 can use horizontal screw centrifuge.Evaporate rich in phenol
Dividing distillation column 2 is normal pressure or vacuum distillation tower.
Preferred as above-described embodiment, also includes entrainer storage tank 12 in the present embodiment, entrainer storage tank 12 is extraction
Agent recovery tower 8 provides entrainer.
Preferred as above-described embodiment, also includes strippant blender 11, strippant blender in the present embodiment
11 are connected 5 with multistage back extraction device, and strippant blender 11 provides strippant to multistage back extraction device 5.
Multitple extraction device and multistage back extraction device in the embodiment of the present invention use supergravity multistage extract and separate
Device, supergravity multistage extraction separation device collection mixes and is located away from one, compact conformation, and floor space is little, and unit volume is raw
Production capacity power is big, deposits flow little, and mass transfer effect is good, and start-stop car is convenient, it is easy to automatically control, energy consumption low.Spread out with different coals below
As a example by oil generation, feasibility and effect to the present invention are verified.Embodiment 1: middle coalite tar extract and separate phenols chemical combination
Thing
Choose a kind of northern Shensi typically in coalite tar as the present embodiment raw material, feedstock property is shown in Table 1, through sleeping spiral shell from
After the de-solid pretreatment of scheming, input and carry out, rich in the distillation cutting of phenol fraction, obtaining after distillation cutting rich in phenol fraction distillation column
170～230 DEG C rich in phenol fraction, its character such as table 2.
Coalite tar full fraction property analysis result in table 1
Rich in phenol fraction character after coalite tar pretreatment in table 2
De-solid through de-solid preprocessor 1 and rich in obtain after the distillation cutting of phenol fraction distillation column 2 rich in phenol fraction, and help
Agent is after on-line continuous blender 3 uniformly mixes, then respectively enters multistage extraction with from the extractant in extractant blender 10
Fetching puts 4 bottom of (using supergravity multistage extraction equipments) is light, heavy liquid inlet, and after sharp separation, top extracts light phase discharging
Entering auxiliary agent recovery tower 7, the recovered overhead auxiliary agent of auxiliary agent recovery tower 7 also recycles, and is dephenolize oil at the bottom of the tower of auxiliary agent recovery tower 7
Directly output；The extraction heavy phase discharging of multitple extraction device 4 top is as one charging of multistage back extraction device 5, and another stock enters
Expect the back washing agent from back washing agent blender 11, after multistage back extraction device 5 sharp separation, multistage back extraction device 5 upper strata
Light phase discharging enters back washing agent recovery tower 6, and the recovered overhead back washing agent of back washing agent recovery tower 6 recycles, back washing agent recovery tower 6
Materials at bottom of tower enter extractant recovery tower 8 carry out extractant azeotropic distillation recovery, from entrainer storage tank 12 entrainer from
Top enters extractant recovery tower 8, and extractant and entrainer are reclaimed in the tower top discharging of extractant recovery tower 8 after stratification,
Discharging at the bottom of the tower of extractant recovery tower 8 is crude phenols product, directly exports.The heavy phase discharging of multistage back extraction device 5 upper strata enters extraction
Take agent regenerator 9, the recovered overhead extractant of extractant regeneration tower 9, it is returned directly to extractant blender 10 and recycles.Extraction
Taking, the operating condition of back extraction and each recovery tower is shown in Table 3.
The operating condition of coalite tar extract and separate phenolic compound in table 3
Product yield and the associated loss rate of this example gained are shown in Table 4.
Table 4 product yield associated loss rate and wastewater flow rate
| Project | Numerical value, wt% |
| Put forward phenol rate | 82.59 |
| Extractant loss rate | 1.45 |
| Auxiliary agent loss rate | 2.09 |
| Back washing agent loss rate | 4.25 |
| Entrainer loss rate | 0.25 |
| Wastewater flow rate | 2kg/h |
The loss rate such as extractant, auxiliary agent is relatively low, the crude phenols product that the quality of product is extracted apparently higher than alkali wash, refers to table
5.Meanwhile, the wastewater flow rate of generation is few, significantly compared with alkali wash (alkali wash wastewater flow rate under identical scale reaches 6-8t/h)
Reduce the cost that waste water processes.
The product characteristics of this example gained is shown in Table 5.
Table 5 crude phenols product property
| Index name | Standard | Test oneself index |
| Phenol and congener content | > 83% | 85.84% |
| Boiling range < 210 DEG C | > 60% | 86.81% |
| Neutral oil content | < 0.8% | Up to standard |
| Pyridine base content | < 0.5% | Up to standard |
| Ignition residue | < 0.4% | 0.01% |
| Moisture | < 10% | 0 |
| PH value | 5-6 | 5-6 |
Crude phenols product that is visible, that extract after extraction back extraction, indices all reaches industry standard, and wherein moisture content index is remote
Being much better than industry standard, in the crude phenols product that current industrial application alkali wash extracts, moisture is about 10%, can increase
The cost that following process is refined, and the crude phenols moisture that this process is extracted seldom makes the place during follow-up refining
Reason cost is substantially reduced.
Embodiment 2: coal direct liquefaction oil extract and separate phenolic compound
Take from the low point of oil that a kind of typical bituminous coal operates on 0.1t/d DCL/Direct coal liquefaction long run test device, low point
Oil nature is shown in Table 6, and as the present embodiment raw material, after the de-solid pretreatment of horizontal screw centrifuge, inputs and distills rich in phenol fraction
Tower carry out rich in phenol fraction distillation cutting, through distillation cutting after obtain 170～275 DEG C rich in phenol fraction, rich in phenol fraction character
Such as table 7.
Low point of oil nature analysis result of table 6 DCL/Direct coal liquefaction
The distillation cutting of table 7 coal direct liquefaction oil is rich in phenol fraction character
Owing to the phenol content in coal direct liquefaction oil is less, the chaff interference such as naphthalene and naphthane is more, therefore carries for guarantee
Phenol rate and neutral oil entrainment rate meet requirement, need to increase the consumption of extractant and auxiliary agent, increase the progression of extraction simultaneously.Tool
Body operating condition such as table 8.
The operating condition of table 8 coal direct liquefaction oil extract and separate phenolic compound
Product yield and the associated loss rate of this example gained are shown in Table 9.
Table 9 product yield and associated loss rate
| Project | Numerical value, wt% |
| Put forward phenol rate | 79.97 |
| Extractant loss rate | 1.60 |
| Auxiliary agent loss rate | 2.52 |
| Back washing agent loss rate | 5.50 |
| Entrainer loss rate | 0.30 |
The product characteristics of this example gained is shown in Table 10.
Table 10 gained crude phenols product property
Visible, owing in coal direct liquefaction oil, phenol content is relatively low, therefore the phenol rate that carries after extraction back extraction decreases, but
Indices still reaches industry standard.Can be applicable to the extraction of phenolic compound in coal direct liquefaction oil in this approach.
The above, the only detailed description of the invention of the present invention, but protection scope of the present invention is not limited thereto, and any
Those familiar with the art, in the technical scope that the invention discloses, can readily occur in change or replace, should contain
Cover within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with described scope of the claims.
Claims (12)
1. the method for extract and separate phenolic compound from coal derived oils, it is characterised in that comprise the steps:
Rich in phenol fraction distillation cutting: coal derived oils is carried out distillation fraction cutting, cut a certain temperature section rich in phenol fraction；
Solvent Centrifugical extraction separates: will be enriched in phenol fraction, extractant and auxiliary agent and be centrifuged separating, obtain is light phase for dephenolize
Oil-compounding agent solution, heavy phase is the liquid phase containing extractant of enrichment phenolic compound, and wherein said extractant is selected from following fourth
At least one or at least one aqueous solution in ketone, Hexalin, dihydroxylic alcohols and glacial acetic acid；
Centrifugal back extraction separates: the liquid containing extractant of enrichment phenolic compound strippant and extract and separate obtained
Being centrifuged mutually separating, obtain is light phase for strippant-phenol solution, wherein containing a small amount of extractant；Heavy phase is the extraction of enrichment
Agent；
Auxiliary agent reclaims: reclaimed by the auxiliary agent in dephenolize oil-compounding agent solution；
Strippant reclaims: by strippant-phenol solution rectification, obtains strippant and the crude phenols raw material containing a small amount of extractant；
Crude phenols purify: the crude phenols raw material containing a small amount of extractant is carried out azeotropic distillation separation, is extracted agent and crude phenols product.
The method of extract and separate phenolic compound from coal derived oils the most according to claim 1, it is characterised in that azeotropic
The entrainer that separated uses is C5-C10N-alkane, preferably C7-C9N-alkane, entrainer with containing a small amount of extractant
The mass ratio of crude phenols raw material is 1:(1-10), preferably 1:(1-2).
The method of extract and separate phenolic compound from coal derived oils the most according to claim 1, it is characterised in that centrifugal
Extractant and crude phenols that back extraction obtains purify after the extractant obtained reclaims for solvent Centrifugical extraction separating step, it is achieved
Extractant recycles；Being preferably, the extractant of recycling is carried out rectification regeneration, the extractant after regeneration recycles.
The method of extract and separate phenolic compound from coal derived oils the most according to claim 1, it is characterised in that described
Extractant is the aqueous solution of glacial acetic acid and dihydroxylic alcohols；Described auxiliary agent is selected from following solvents oil, low carbon chain hydrocarbon solvent, kerosene and oil
At least one in ether.
The method of extract and separate phenolic compound from coal derived oils the most according to claim 4, it is characterised in that described
Auxiliary agent is the mixed liquor of low carbon chain hydrocarbon solvent and petroleum ether, and the mass ratio of low carbon chain hydrocarbon solvent and petroleum ether is 1:(0.5-5).
The method of extract and separate phenolic compound from coal derived oils the most according to claim 1, it is characterised in that described
Extractant with rich in phenol fraction by 1:(1-10) mass ratio be centrifuged extract and separate, it is preferable that described extractant and rich in
Phenol fraction is by 1:(2-4) mass ratio be centrifuged extract and separate；Described auxiliary agent with press 1:(0.2-5 rich in phenol fraction) quality
Ratio is centrifuged extract and separate；Described carry out supergravity multistage extraction rich in phenol fraction, use adverse current or cross-current flow, use mistake
It is 2-8 level during stream extraction mode, is 2-12 level during employing counter-current extraction mode；Extraction temperature is 20～120 DEG C.
The method of extract and separate phenolic compound from coal derived oils the most according to claim 1, it is characterised in that described
At least one in following dimethyl sulfoxide, oxolane, butyl ether, ethyl acetate and diisopropyl ether of strippant；Described back extraction
Take the agent liquid phase containing extractant with enrichment phenolic compound with (0.1-3): the mass ratio of 1 is centrifuged back extraction, excellent
Selection of land, described strippant is (0.5-1) with the mass ratio of the liquid phase containing extractant of enrichment phenolic compound: 1.
The method of extract and separate phenolic compound from coal derived oils the most according to claim 1, it is characterised in that described
Back extraction is multitple extraction, and described back extraction uses adverse current or cross-current flow, is 2-8 level during employing cross current solvent extraction mode,
It is 2-12 level during employing counter-current extraction mode；The temperature of described back extraction is 20～120 DEG C, preferably 30～60 DEG C.
9. the device of extract and separate phenolic compound from coal derived oils, for running the method described in claim 1, described dress
Put and include:
Rich in phenol fraction distillation column, coal derived oils normal pressure or vacuum distillation tower are carried out fraction cutting, cut a certain temperature section rich
Containing phenol fraction；
On-line continuous blender, is connected with rich in phenol fraction distillation column, is mixed to get cut all rich in phenol fraction and auxiliary agent
One rich in phenol fraction liquid phase；
Supergravity multistage extraction equipment, heavy liquid inlet is connected with on-line continuous blender, by enter from heavy liquid inlet rich in phenol
Fraction liquid phase with from light phase inlet enter the quick hybrid separation of extractant, light phase export output light phase for dephenolize oil-help
Agent solution, the liquid phase containing extractant that heavy phase is enrichment phenolic compound of heavy out output；
Supergravity multistage back extraction device, its heavy liquid inlet is connected with the heavy out of supergravity multistage extraction equipment, will be from
The liquid phase containing extractant of the heavy phase enrichment phenolic compound that heavy liquid inlet enters and the strippant entered from light phase inlet
Quickly hybrid separation, the light phase of light phase export output is the strippant-phenol solution containing a small amount of extractant；Heavy out output
Heavy phase is the extractant of enrichment；
Strippant recovery tower, is connected with the light phase export of supergravity multistage back extraction device, by strippant-phenol solution
Strippant carries out rectification recovery, tower top output strippant, recycles；At the bottom of tower, the output crude phenols containing a small amount of extractant are former
Material；
Auxiliary agent recovery tower, is connected with the light phase export of multitple extraction device, and the auxiliary agent in dephenolize oil-compounding agent solution is carried out rectification
Recycling use, tower top is auxiliary agent；
Extractant recovery tower, is connected at the bottom of the tower of strippant recovery tower, and the crude phenols raw material containing a small amount of extractant is carried out azeotropic
Distillation, isolated extractant and crude phenols product.
The device of extract and separate phenolic compound from coal derived oils the most according to claim 9, it is characterised in that also
Including extractant regeneration tower, described extractant regeneration tower is by the heavy out of multistage back extraction device and extractant Distillation recovery tower
The extractant of output carries out rectification regeneration.
11. devices of extract and separate phenolic compound from coal derived oils according to claim 9, it is characterised in that also
Including de-solid preprocessor, being connected with the charging aperture rich in phenol fraction distillation column, described de-solid preprocessor is former to coal derived oils
Material carries out de-solid process, obtains coal derived oils, and described de-solid preprocessor is horizontal screw centrifuge.
12. devices of extract and separate phenolic compound from coal derived oils according to claim 10, it is characterised in that also
Including extractant blender, described extractant blender provides extractant, multistage back extraction device for described multitple extraction device
Heavy out and extractant Distillation recovery tower output extractant directly or through extractant regeneration tower rectification regenerate after input
Described extractant blender.
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| CN106629961A (en) * | 2017-02-14 | 2017-05-10 | 煤炭科学技术研究院有限公司 | Method for extracting high-concentration phenol-containing wastewater by super-gravity |
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| CN112569633A (en) * | 2019-09-30 | 2021-03-30 | 青岛海德利纳米科技有限公司 | Method for separating, enriching or producing phenolic compounds, and method and equipment for processing oil products |
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