CN106867556B - A kind of coal tar fraction separating technology and device - Google Patents

A kind of coal tar fraction separating technology and device Download PDF

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Publication number
CN106867556B
CN106867556B CN201710118555.XA CN201710118555A CN106867556B CN 106867556 B CN106867556 B CN 106867556B CN 201710118555 A CN201710118555 A CN 201710118555A CN 106867556 B CN106867556 B CN 106867556B
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solvent
tower
knockout tower
neutral oil
crude phenols
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CN106867556A (en
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孙鸣
杨叶伟
钟姣姣
苏小平
马晓迅
张丹
徐龙
郝青青
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Northwest University
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Northwest University
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10CWORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C1/00Working-up tar
    • C10C1/18Working-up tar by extraction with selective solvents
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10CWORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C1/00Working-up tar
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10CWORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C1/00Working-up tar
    • C10C1/04Working-up tar by distillation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10CWORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C1/00Working-up tar
    • C10C1/04Working-up tar by distillation
    • C10C1/08Winning of aromatic fractions

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

A kind of coal tar fraction separating technology and device, including the first paste state bed reactor and the first vacuum filter, it is connected at the top of first paste state bed reactor top and the first vacuum filter, first vacuum filter motor spindle is divided into two-way, the remaining part storage tank of absorption is extracted with solvent A all the way to be connected, it is connected at the top of another way and third paste state bed reactor, is connected at the top of third paste state bed reactor top and third vacuum filter, third vacuum filter motor spindle is connected with solvent B elution fraction storage tank;Solvent B elution fraction storage tank is connected with crude phenols knockout tower, and solvent A extraction adsorbs remaining part storage tank and is connected with neutral oil knockout tower.The present invention is green separation technique, does not generate waste water, waste residue and exhaust gas, and solvent can recycle, and the operating condition of technique is mild, easy, technique and the advantages that equipment manufacturing cost is low, less investment.

Description

A kind of coal tar fraction separating technology and device
Technical field
The invention belongs to technical field of coal chemical industry, it is related to a kind of coal tar fraction separating technology and device.
Background technique
Coal tar is one of staple product of coking industry, and yield accounts for about the 3%~4% of furnace coal, and composition is extremely Complexity is used after exclusively carrying out separation, purification by coal-tar industry in most cases.Coal tar is according to chemical composition master It to include neutral compound (mainly including aromatic hydrocarbon and aliphatic compound) and acid compound.Neutral compound is also known as Neutral oil, the high added values such as naphthalene, anthracene, phenanthrene and pyrene that compound fragrant hydrocarbon has petrochemical industry that cannot obtain or be not directly available Fine chemicals;Aliphatic compound is the important component of the fuel oil such as gasoline, diesel oil, is plus hydrogen produces high hexadecane It is worth the good raw material of diesel oil.Acid compound is primarily referred to as the phenolic compound in coal tar, being important of phenolic compound Work raw material and high value added product can manufacture pesticide, medicine, resin, dyestuff etc..Therefore, isolated from coal tar content compared with High neutral compound and acid compound is very necessary.
Coal tar isolation technics includes distillation and rectifying, crystallization, absorption, UF membrane and solvent extraction etc., wherein distillation All be method each component separated using boiling point difference with rectifying, but its energy consumption is high, temperature is excessively high also to be will cause in coal tar Certain decomposition of components;Crystallization technique is close for some boiling points, and the separating effect that crystalline temperature differs biggish object system is obvious but right It is restricted in the separating capacity of this polynary complex component of coal tar;Absorption and membrane separation technique are according to filler in knockout tower The difference of absorption property separates certain component in mobile phase from mixed system, due to coal tar poor fluidity, leads to this Method low separation efficiency;Solvent extraction is a kind of different separation methods using different material solubility in selected solvent, But this method solvent usage is larger, easily causes to corrode to equipment.
Chinese patent CN105368473A the method is a kind of coal tar fraction separator and separating technology, with silica gel Extraction and separation are carried out for the chromatographic column method of filler, elution point is carried out to the coal tar fraction for removing asphalt component using two kinds of solvents From, then through distillation column distillation processing, respectively obtain neutral oil ingredient and crude phenols component.Silica gel can not move in the invention chromatographic column It is dynamic, make to remain coal tar fraction in silica gel, leads to the reduction of coal tar fraction separative efficiency.
A kind of separator of coal tar is described in Chinese patent CN204958816U, which leads to from top to down Heating tube heat supply is crossed to separate the fraction of different flash-points, each fraction upper end is communicated with accumulator tank and temperature reducing unit, but should Device cannot be sufficiently by the fraction seperation of different flash-points, and is difficult to control temperature, is unfavorable for being sufficiently separated for coal tar.
Chinese patent CN105419837A describes a kind of coal carbonaceous residues extraction separating method, which passes through ultrasonic wave Auxiliary extraction, melt cinder separation, organic matter is enriched with and the recycling step of extractant carries out extraction and separation to coal carbonaceous residues, in room temperature It is reacted under normal pressure using carbon dioxide, water, extractant and realizes and extract organic matter in coal carbonaceous residues, the life is destroyed after heating At system finally produce waste water to realize separation, but ultrasonic extraction low efficiency, pollute environment.
Chinese patent CN103111088A describes in a kind of extraction separation and Extraction the complete of phenols in coalite tar Equipment, the equipment are made of five kettles, four tanks and three groups of condensers, obtain refining crude using solvent extraction extraction and separation Phenol, but should the device is complicated, to realize industrialization also require further improvement.
In conclusion during traditional coal tar processing, not only energy consumption is high, low separation efficiency, and can generate a large amount of Phenol wastewater, the problems such as causing environmental pollution.So finding low energy consumption, no pollution, a kind of efficient skill for separating coal tar Art tool has very important significance.
Summary of the invention
To overcome the problems in currently available technology, the object of the present invention is to provide a kind of coal tar fraction separating technology and Device, the separating technology can realize the low energy consumption of coal tar fraction, no pollution, high efficiency, be easily industrialized.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of coal tar fraction separator, including the first paste state bed reactor and the first vacuum filter, the first slurry It is connected at the top of bed reactor top and the first vacuum filter, the first vacuum filter motor spindle is divided into two-way, extracts all the way with solvent A Take the remaining part storage tank of absorption to be connected, be connected at the top of another way and the second paste state bed reactor, the second paste state bed reactor bottom and Third paste state bed reactor is connected;It is connected at the top of third paste state bed reactor top and third vacuum filter, third vacuum mistake Filter bottom is divided into two-way, is connected all the way with solvent B elution fraction storage tank, is connected at the top of another way and the 4th paste state bed reactor; Solvent B elution fraction storage tank is connected with crude phenols knockout tower, and solvent A extraction adsorbs remaining part storage tank and is connected with neutral oil knockout tower.
A further improvement of the present invention lies in that the first vacuum filter motor spindle another way is through the second paste state bed reactor and Two vacuum filters are connected, and the second vacuum filter motor spindle is divided into two-way, extract with solvent A adsorb remaining part storage tank phase all the way Even, it is connected at the top of another way and third paste state bed reactor.
A further improvement of the present invention lies in that third vacuum filter motor spindle also with the 4th paste state bed reactor at the top of phase Even, the 4th paste state bed reactor top is connected with the 4th vacuum filter;4th vacuum filter motor spindle is divided into two-way, all the way with Solvent B elution fraction storage tank is connected, and is connected at the top of another way and the first paste state bed reactor.
It is connected at the top of column overhead and crude phenols knockout tower overhead condenser a further improvement of the present invention lies in that crude phenols separate, Crude phenols knockout tower overhead condenser bottom is connected with crude phenols knockout tower overhead reflux tank top, crude phenols knockout tower overhead reflux tank bottom Portion is connected with crude phenols knockout tower overhead reflux pump intake, and crude phenols knockout tower overhead reflux pump discharge is divided into two-way, all the way with crude phenols It separates column overhead to be connected, another way is connected with solvent B storage tank.
A further improvement of the present invention lies in that crude phenols knockout tower tower bottom is divided into two-way, all the way again through crude phenols knockout tower tower bottom Boiling device is connected with crude phenols knockout tower tower bottom, and another way is connected with crude phenols component discharging condenser inlet, the discharging condensation of crude phenols component Device outlet is connected with crude phenols component discharging pump intake, and crude phenols component discharging pump discharge is connected with crude phenols storage tank.
A further improvement of the present invention lies in that neutral oil separation column and phase at the top of neutral oil knockout tower overhead condenser Even, neutral oil knockout tower overhead condenser bottom is connected with neutral oil knockout tower overhead reflux tank top;Neutral oil knockout tower tower Top reflux pot bottom is connected with neutral oil knockout tower overhead reflux pump intake, and neutral oil knockout tower overhead reflux pump discharge is divided into two Road is connected with neutral oil separation column all the way, and another way is connected with solvent A storage tank.
A further improvement of the present invention lies in that neutral oil knockout tower tower bottom is divided into two-way, all the way through neutral oil knockout tower tower Bottom reboiler is connected with neutral oil knockout tower tower bottom, and another way is connected with neutral oil ingredient discharging condenser inlet;Neutral oil group It separates material condensator outlet to be connected with neutral oil ingredient discharging pump entrance, neutral oil ingredient discharging pump outlet and neutral oil tank phase Even.
A kind of coal tar fraction separating technology, comprising the following steps:
Coal tar fraction, solvent A and silica gel are added in the first paste state bed reactor, in the first paste state bed reactor After heating, extraction, solvent A is separated with coal tar fraction mixed liquor through the first vacuum filter, obtain silica gel phenol and removes phenol The solvent A extraction absorption residue of class component;Silica gel phenol is added in the second paste state bed reactor after solvent A washs, is passed through Remaining part is adsorbed in the isolated silica gel phenol of second vacuum filter and solvent A extraction;
The isolated silica gel phenol of second vacuum filter is added in third paste state bed reactor, is eluted through solvent B Afterwards, it is separated by third vacuum filter, obtains eluting silica gel and solvent B elution fraction;
It will be added to progress rectifying separation in crude phenols knockout tower after the preheating of solvent B elution fraction, obtains crude phenols and solvent B;
The solvent A for removing phenolic component is extracted after absorption residue extracts the remaining part preheating of absorption with solvent A and is added to Rectifying separation is carried out in neutral oil knockout tower, obtains neutral oil ingredient and solvent A.
A further improvement of the present invention lies in that eluting silica gel is added in the 4th paste state bed reactor, carried out through solvent B After elution, is separated by the 4th vacuum filter, obtain silica gel and solvent B elution fraction;
Crude phenols separate column overhead output solvent B steam, and solvent B steam is all condensed into through crude phenols knockout tower overhead condenser Liquid phase, the solvent B of Quan Ninghou enter crude phenols knockout tower return tank of top of the tower, then return through crude phenols knockout tower tower top return pump a part It is flow to crude phenols separation column overhead, another part returns in solvent B storage tank, obtains solvent B;
Neutral oil separates column overhead output solvent A steam, and solvent A steam is all cold through neutral oil separation column overhead complete condenser It coagulates for liquid phase, the solvent A of Quan Ninghou enters in neutral oil knockout tower return tank of top of the tower, then through neutral oil knockout tower overhead reflux By being back in neutral oil separation column overhead, another part returns in solvent A storage tank pump a part, obtains solvent A.
A further improvement of the present invention lies in that the temperature of heating, preheating is 60~100 DEG C;
The volume ratio of coal tar fraction and solvent A, silica gel is 1:1:1~1:20:20;Solvent A is in the alkane of C5~C8 Single alkane or several single alkane mixture, wherein the alkane of C5~C8 be n-alkane or branched paraffin;
Solvent B is the mixture of one or more of ethyl acetate, toluene, ethyl alcohol, methanol;
Silica gel partial size is 75~250 μm.
Compared with prior art, the invention has the benefit that the present invention by setting the first paste state bed reactor with First vacuum filter is extracted in the first paste state bed reactor using solvent A and coal tar fraction, silica gel, passes through One vacuum filter is separated, and then rectifying separates in neutral oil knockout tower, available neutrality oil ingredient;Pass through setting Third paste state bed reactor, third vacuum filter and crude phenols knockout tower elute the crude phenols of silica gel absorption by solvent B, It is separated by third vacuum filter, rectifying separates in through crude phenols knockout tower, to obtain crude phenols component.Present apparatus knot Structure is simple, at low cost, can be realized the separation of coal tar fraction.
Further, by the way that the second paste state bed reactor is arranged, silica gel phenol can further be washed using solvent A It washs.
Further, by the way that the 4th paste state bed reactor is arranged, eluting silica gel can be eluted using solvent B, is obtained To the silica gel that can be reused.
Further, it is separated by setting crude phenols knockout tower overhead condenser, crude phenols knockout tower return tank of top of the tower and crude phenols Column overhead reflux pump can obtain reusable solvent B.
Further, by setting neutral oil knockout tower overhead condenser, neutral oil knockout tower return tank of top of the tower and in Property oil separate column overhead reflux pump, reusable solvent A can be obtained.
Further, through the second paste state bed reactor in conjunction with the second vacuum filter, pass through the second slurry reactor Device and the second vacuum filter combine so that the washing of silica gel phenol is abundant.
Coal tar fraction, solvent A and silica gel are added in the first paste state bed reactor by the present invention, anti-in the first slurry bed system Answer in device heat, extract after, solvent A is separated with coal tar fraction mixed liquor through the first vacuum filter, obtain silica gel phenol and Remove the solvent A extraction absorption residue of phenolic component;Silica gel phenol is added in the second paste state bed reactor and is washed through solvent A Afterwards, remaining part is adsorbed by the isolated silica gel phenol of the second vacuum filter and solvent A extraction;
The isolated silica gel phenol of second vacuum filter is added in third paste state bed reactor, is eluted through solvent B Afterwards, it is separated by third vacuum filter, obtains eluting silica gel and solvent B elution fraction;It will add after the preheating of solvent B elution fraction Enter into crude phenols knockout tower and carry out rectifying separation, obtains crude phenols and solvent B;The solvent A extraction absorption for removing phenolic component is surplus Excess is added to progress rectifying in neutral oil knockout tower after extracting the remaining part preheating of absorption with solvent A and separates, and obtains neutral oil group Point and solvent A.The present invention solve during existing coal tar processing it is existing energy consumption is high, multi-process handling and complicated, product Each component separation and the problem of utilization efficiency is lower, environmental pollution is serious.The present invention is green separation technique, do not generate waste water, Waste residue and exhaust gas, extractant are recycled, and the operating condition of technique is mild, easy, and technique and equipment manufacturing cost are low, put into It is few.
Further, silica gel phenol is added in the 4th paste state bed reactor after solvent B elution, passes through the 4th vacuum filter The isolated eluting silica gel of machine and solvent B elution fraction.
Detailed description of the invention
Fig. 1 is that coal tar fraction of the invention separates solvent A extraction absorbing process process;
Fig. 2 is that coal tar fraction of the invention separates solvent B elution processes process;
Fig. 3 is that remaining part and elution fraction concentration technology process are adsorbed in coal tar fraction separation of the invention;
Fig. 4 is the total ion chromatogram of neutral oil ingredient;
Fig. 5 is the total ion chromatogram of crude phenols component;
Fig. 6 is the influence that solvent A elutes that number remains phenol content to neutral oil;
Fig. 7 is that solvent B elutes influence of the number to phenol content in crude phenols;
In figure, 1, silica gel batcher;2, coal tar fraction storage tank;3, solvent A storage tank;4, the first valve;5, the second valve; 6, solvent A feed pump;7, the first paste state bed reactor;8, third valve;9, the 4th valve;10, the first vacuum filter;11, First silica gel phenol batcher;12, the second paste state bed reactor;13, the 5th valve;14, the second vacuum filter;15, the second silicon Glue phenol batcher;16, solvent B storage tank;17, the 6th valve;18, solvent B feed pump;19, the 7th valve;20, third slurry bed system Reactor;21, the 8th valve;22, third vacuum filter;23, third silica gel phenol batcher;24, the 9th valve;25, the 4th Paste state bed reactor;26, the 4th vacuum filter;27, solvent B elution fraction storage tank;28, solvent B elution fraction feed pump;29, thick Phenol knockout tower;30, crude phenols knockout tower overhead condenser;31, crude phenols knockout tower return tank of top of the tower;32, crude phenols separation column overhead is returned Stream pump;33, crude phenols knockout tower tower bottom reboiler;34, crude phenols component discharging condenser;35, crude phenols component discharging pump;36, crude phenols Storage tank;37, remaining part storage tank is adsorbed in solvent A extraction;38, remaining part feed pump is adsorbed in solvent A extraction;39, neutral oil knockout tower; 40, neutral oil knockout tower overhead condenser;41, neutral oil separates return tank of top of the tower;42, neutral oil knockout tower tower top return pump; 43, neutral oil knockout tower tower bottom reboiler;44, neutral oil ingredient discharging condenser;45, neutral oil ingredient discharging pump;46, neutral Oil tank.
Specific embodiment
Below in conjunction with attached drawing, by embodiment, present invention is further described in detail.
Heretofore described all raw materials, intermediate products and storage tank all has Liquid level;First slurry bed system Reactor 7, the second paste state bed reactor 12, third paste state bed reactor 20, the 4th paste state bed reactor 25 band heating mantle;Institute The solvent A storage tank 3 and solvent B storage tank 16 stated are with heating mantle;First paste state bed reactor 7, the second slurry reactor Device 12, third paste state bed reactor 20, the 4th paste state bed reactor 25 and the first vacuum filter 10, the second vacuum filter 14, third vacuum filter 22, the 4th vacuum filter 26, silica gel batcher 1, the second silica gel phenol batcher 15 are tandem junctions Structure.
Coal tar fraction is coalite tar, medium temperature coal tar or high temperature coal-tar depitching matter gained coal tar in the present invention Oil;
Silica gel phenol of the invention is the abbreviation in silica gel absorption coal tar fraction after phenolic substances.
Referring to figure 1, figure 2 and figure 3, a kind of coal tar fraction continuous separation device includes: that silica gel batcher 1, coal tar evaporate Divide storage tank 2, solvent A storage tank 3, solvent A feed pump 6, the first paste state bed reactor 7, the first vacuum filter 10, the second slurry bed system Reactor 12, the second vacuum filter 14, the second silica gel phenol batcher 15, solvent B storage tank 16, solvent B feed pump 18, third slurry State bed reactor 20, third vacuum filter 22, third silica gel phenol batcher 23, the 4th paste state bed reactor 25, the 4th vacuum Filter 26, solvent B elution fraction storage tank 27, solvent B elution fraction feed pump 28, crude phenols knockout tower 29, crude phenols separation column overhead are cold Condenser 30, crude phenols knockout tower return tank of top of the tower 31, crude phenols knockout tower tower top return pump 32, crude phenols knockout tower tower bottom reboiler 33, Remaining part storage tank 37, molten is adsorbed in discharge condenser 34, crude phenols component discharging pump 35, crude phenols storage tank 36, the solvent A extraction of crude phenols component Agent A extraction adsorbs remaining part and feeds 38, neutral oil knockout tower 39, neutral oil knockout tower overhead condenser 40, neutral oil knockout tower Top return tank 41, neutral oil knockout tower tower top return pump 42, neutral oil knockout tower tower bottom reboiler 43, neutral oil ingredient discharging are cold Condenser 44, neutral oil ingredient discharging pump 45 and neutral oil tank 46.
Referring to Fig. 1, silica gel batcher 1 at the top of the first valve 4 and the first paste state bed reactor 7 through being connected;Coal tar fraction Storage tank 2 at the top of the second valve 5 and the first paste state bed reactor 7 through being connected;The 4th valve 9 of first paste state bed reactor, 7 top It is connected at the top of the first vacuum filter 10;First vacuum filter, 10 bottom is divided into two-way, surplus with solvent A extraction absorption all the way Remaining part storage tank 37 is connected, and another way is connected with the first silica gel phenol batcher 11;The outlet of first silica gel phenol batcher 11 and the second slurry It is connected at the top of state bed reactor 12;3 bottom of solvent A storage tank is connected with solvent A feed pump 6;The outlet of solvent A feed pump 6 is divided into two Road is connected at the top of the first paste state bed reactor 7 all the way, and another way is through 12 top of third valve 8 and the second paste state bed reactor It is connected;The 5th valve 13 of second paste state bed reactor, 12 top is connected with the second vacuum filter 14;Second vacuum filter 14 bottoms are divided into two-way, extract the remaining part storage tank 37 of absorption with solvent A all the way and are connected, another way and the second silica gel phenol batcher 15 It is connected.
Referring to fig. 2, the second silica gel phenol batcher 15 at the top of the 6th valve 17 and third paste state bed reactor 20 through being connected;It is molten 16 bottom of agent B storage tank is connected with solvent B feed pump 18, and the outlet of solvent B feed pump 18 is divided into two-way, anti-with third slurry bed system all the way It answers and is connected at the top of device 20, another way at the top of the 7th valve 19 and the 4th paste state bed reactor 25 through being connected;Third slurry reactor It is connected at the top of the 8th valve 21 of 20 top of device and third vacuum filter 22;22 bottom of third vacuum filter is divided into two-way, It is connected all the way with solvent B elution phenol storage tank 27, another way is connected with third silica gel phenol batcher 23;Third silica gel phenol batcher 23 It exports and is connected at the top of the 4th paste state bed reactor 25;The 9th valve 24 of 4th paste state bed reactor, 25 top and the 4th vacuum Filter 26 is connected;4th vacuum filter, 26 bottom is divided into two-way, is connected all the way with solvent B elution phenol storage tank 27, another way It is connected with silica gel batcher 1.
Referring to Fig. 3, solvent B elution fraction storage tank 27 is connected with 28 entrance of solvent B elution fraction feed pump, solvent B elution fraction into 28 outlet of material pump is connected with crude phenols knockout tower 29;29 tower top of crude phenols knockout tower and 30 top phase of crude phenols knockout tower overhead condenser Even, it is connected at the top of 30 bottom of crude phenols knockout tower overhead condenser and crude phenols knockout tower return tank of top of the tower 31;Crude phenols separate column overhead 31 bottom of return tank is connected with 32 entrance of crude phenols knockout tower tower top return pump, and the outlet of crude phenols knockout tower tower top return pump 32 is divided into two Road is connected with 29 tower top of crude phenols knockout tower all the way, and another way is connected with solvent B storage tank 16;29 tower bottom of crude phenols knockout tower is divided into two Road is connected through crude phenols knockout tower tower bottom reboiler 33 with 29 tower bottom of crude phenols knockout tower, i.e. crude phenols knockout tower tower bottom reboiler all the way 33 entrances are connected with 29 tower bottom of crude phenols knockout tower, and another way is connected with crude phenols component discharging 34 entrance of condenser;Crude phenols group It separates the outlet of material condenser 34 to be connected with 35 entrance of crude phenols component discharging pump, the outlet of crude phenols component discharging pump 35 and crude phenols storage tank 36 It is connected;Solvent A extraction adsorbs remaining part storage tank 37 and is connected with remaining 38 entrance of part feed pump of solvent A extraction absorption, solvent A extraction Remaining 38 outlet of part feed pump is adsorbed to be connected with neutral oil knockout tower 39;39 top of neutral oil knockout tower and neutral oil knockout tower tower It pushes up and is connected at the top of condenser 40,41 top of 40 bottom of neutral oil knockout tower overhead condenser and neutral oil knockout tower return tank of top of the tower It is connected;41 bottom of neutral oil knockout tower return tank of top of the tower is connected with 42 entrance of neutral oil knockout tower tower top return pump, neutral oil It is divided into two-way from the outlet of column overhead reflux pump 42, is connected all the way at the top of neutral oil knockout tower 39, another way and solvent A storage tank 3 It is connected;39 tower bottom of neutral oil knockout tower is divided into two-way, all the way through neutral oil knockout tower tower bottom reboiler 43 and neutral oil knockout tower 39 tower bottom are connected, i.e., 43 entrance of neutral oil knockout tower tower bottom reboiler is connected with 39 tower bottom of neutral oil knockout tower, another way It is connected with neutral oil ingredient discharging 44 entrance of condenser;Neutral oil ingredient discharging condenser 44 outlet and neutral oil ingredient discharging pump 45 entrances are connected, and the neutral outlet of oil ingredient discharging pump 45 is connected with neutral oil tank 46.
Coal tar fraction separating technology of the invention the following steps are included:
One, solvent A extraction absorption and solvent B elution processes process
(1) solvent A extraction and absorbing process process
Referring to Fig. 1, coal tar fraction raw material is continuously stored up in coal tar fraction storage tank 2 by certain flow, then by coal tar Oil distillate raw material injects the first paste state bed reactor 7.Solvent A is heated to after 60~100 DEG C by solvent A storage tank 3 through solvent A simultaneously Feed pump 6 is pumped into the first paste state bed reactor 7 after being pressurised into 0.2~0.5MPa.A certain amount of silica gel is by silica gel batcher 1 simultaneously It is added in the first paste state bed reactor 7,7 bottom of the first paste state bed reactor, which is passed through air, makes solvent A, coal tar fraction raw material Be uniformly mixed with silica gel, control 7 temperature of the first paste state bed reactor be 60~100 DEG C, extraction after a certain period of time, by solvent A with Coal tar fraction raw material mixed liquor is separated through the first vacuum filter 10, and silica gel phenol is adopted through 10 outlet at bottom of the first vacuum filter Out, it is added in the second paste state bed reactor 12 by the first silica gel phenol batcher 11, and solvent A extraction adsorbs remaining part by the Another outlet at bottom outflow of one vacuum filter 10, flows to solvent A extraction and adsorbs in remaining part storage tank 37.It is added to the second slurry The solvent A that the silica gel phenol of bed reactor 12 flows into the second paste state bed reactor 12 through solvent A feed pump 6 is washed.Gained Mixed liquor is separated through the second vacuum filter 14, and outlet gained solvent A extraction absorption in 14 bottom one of the second vacuum filter is remaining Part flows to solvent A extraction and adsorbs remaining part storage tank 37, and another silica obtained phenol in outlet in 14 bottom of the second vacuum filter is through second Silica gel phenol batcher 15 carries out solvent B elution processes process.Wherein, the volume ratio of coal tar fraction and solvent A, silica gel is 1:1: 1~1:20:20;Solvent A is the mixture (alkane of C5~C8 of the single alkane or several single alkane in the alkane of C5~C8 For n-alkane or branched paraffin).
(2) solvent B elution processes process
Referring to fig. 2, a certain amount of silica gel phenol is added in third paste state bed reactor 20 by the second silica gel phenol batcher 15, molten Agent B flows into after solvent B storage tank 16 is preheated to 20~60 DEG C after solvent B feed pump 18 is forced into 0.2MPa~0.5MPa The silica gel phenol being added in third paste state bed reactor 20 is eluted in three paste state bed reactors 20, by third slurry reactor 20 gained mixture of device is separated through third vacuum filter 22, and gained eluting silica gel is through 22 bottom one of third vacuum filter Outlet extraction, solvent B elution fraction are flowed out by another outlet in 22 bottom of third vacuum filter, flow to solvent B elution fraction storage tank 27. Gained eluting silica gel is added in the 4th paste state bed reactor 25 by third silica gel phenol batcher 23, and solvent B is fed through solvent B Pump 18, which is pumped into the 4th paste state bed reactor 25, further elutes eluting silica gel, and gained mixture passes through the 4th vacuum mistake Filter 26 separates, 26 bottom one of the 4th vacuum filter export it is silica obtained recycled through silica gel batcher 1, the 4th is true Solvent B elution fraction obtained by the empty another outlet in 26 bottom of filter flows in solvent B elution fraction storage tank 27.
The solvent B is the mixture of one or more of ethyl acetate, toluene, ethyl alcohol, methanol.
Two, remaining part and solvent B elution fraction rectification process process are adsorbed in solvent A extraction
(1) rectifying of solvent B elution fraction (crude phenols production) process flow
Referring to Fig. 3, the solvent B elution fraction from solvent B elution fraction storage tank 27 is eluted after being preheating to 20~60 DEG C by solvent B Part feed pump 28 enters the progress rectifying separation of crude phenols knockout tower 29 after being forced into 0.2~0.5MPa.29 tower top of crude phenols knockout tower produces Solvent B steam out, solvent B steam are all condensed into liquid phase through crude phenols knockout tower overhead condenser 30, and the solvent B of Quan Ninghou enters Then crude phenols knockout tower return tank of top of the tower 31 is back to through 32 a part of crude phenols knockout tower tower top return pump by certain reflux ratio 29 tower top of crude phenols knockout tower, another part return to solvent B storage tank 16.
Crude phenols a part of 29 outputs of crude phenols knockout tower is back to after the heating vaporization of crude phenols knockout tower tower bottom reboiler 33 In crude phenols knockout tower 29, another part is as tower reactor product output.The crude phenols of output are cooling through crude phenols component discharging condenser 34, Crude phenols after cooling enter in crude phenols storage tank 36 through the pump of crude phenols component discharging pump 35 as product.
(2) remaining part rectifying (neutral oil production) technique is adsorbed in solvent A extraction
Referring to Fig. 3, extracted from solvent A adsorb remaining part storage tank 37 solvent A extraction adsorb remaining part be preheating to 60~ It is extracted after 100 DEG C by solvent A to adsorb remaining part feed pump 38 and be pressurized to after 0.2~10MPa and is pumped into neutral oil knockout tower 39 and carries out Rectifying separation.39 tower top output solvent A steam of neutral oil knockout tower, solvent A steam separate column overhead complete condenser 40 through neutral oil It all is condensed into liquid phase, the solvent A of Quan Ninghou enters in neutral oil knockout tower return tank of top of the tower 41, then through neutral oil knockout tower 42 a part of tower top return pump is back to 39 tower top of neutral oil knockout tower by certain reflux ratio, and another part returns to solvent A It is recycled in storage tank 3.
Neutral oil a part of 39 outputs of neutral oil knockout tower is heated through neutral oil knockout tower tower bottom reboiler 43 and is vaporized After be back in neutral oil knockout tower 39, another part is as tower reactor product output.The neutral oil ingredient of output is through the condenser that discharges 44 is cooling, and neutral oil after cooling is pumped out through neutral oil ingredient discharging pump 45, enters neutral oil tank 46 as product and stores.
Heretofore described solvent A is the mixture of the single alkane or several single alkane in the alkane of C5~C8 (alkane of C5~C8 is n-alkane or branched paraffin).
The silica gel partial size is 75~250 μm, and silica gel is adsorbent.4th vacuum filter, 26 bottom one outlet gained silicon Glue can be recycled through silica gel batcher 1.
The present invention can be realized the continuous separation of coal tar, obtain neutral oil ingredient and crude phenols component, neutral oil ingredient, Crude phenols component is product.
Solvent A enters in neutral oil knockout tower return tank of top of the tower 41, then through neutral oil knockout tower tower top return pump 42 1 Part is back to 39 tower top of neutral oil knockout tower by certain reflux ratio, and another part, which returns to circulation in solvent A storage tank 3, to be made With.
Solvent B enters in crude phenols knockout tower return tank of top of the tower 31, then through 32 a part of crude phenols knockout tower tower top return pump It is back to 29 tower top of crude phenols knockout tower by certain reflux ratio, another part returns to solvent B storage tank 16.As it can be seen that the present invention obtains To solvent A and solvent B can be recycled.
The solvent A feed pump moulding pressure range is 0.2~0.5MPa, and feed temperature range is 60~100 DEG C.
The solvent B feed pump moulding pressure range is 0.2~0.5MPa, and feed temperature range is 20~60 DEG C.
The remaining 38 moulding pressure range of part feed pump of solvent A extraction absorption is 0.2~10MPa, temperature is 60~100 ℃;
The 28 moulding pressure range of solvent B elution fraction feed pump is 0.2~0.5MPa, and feed temperature range is 20~60 ℃。
In order to illustrate effect of the invention, following embodiment is using coalite tar in the progress of coal tar fraction separating technology Fraction seperation test is carried out in order to accurate Analyze & separate product using composition of the gas chromatograph-mass spectrometer (GC-MS) to product Detection.It is now to be derived from the coal tar (heavy oil) of semi-coke factory, northern Shensi Shenmu County to be separated as experimental subjects using experimental raw, Heavy oil (tar clarifying basin subsurface layer oil) is shown in Table 1 by the fundamental property that national standard measures.
The fundamental property of 1 coal tar heavy oil of table
Note: * minusing
Using coal tar fraction continuous separation technology of the present invention, select respectively solvent A (the specially linear paraffin of C7) and Solvent B (specially polar solvent ethyl acetate) be eluant, eluent, silica gel is adsorbent, separate coal tar in neutral oil ingredient, Crude phenols component.
It takes a certain amount of coal tar to be tested according to foregoing schemes, is obtained after the test and respectively to from products pot Neutral oil ingredient and each 1mL of crude phenols component, then dissolved with the methylene chloride of 2mL, then carry out GC-MS analysis, analyze result See Fig. 4, Fig. 5 and table 2 and table 3.
50g coal tar fraction is taken to mix with a certain amount of silica gel, the silica gel phenol obtained in the first vacuum filter is with molten Agent A elution is every time 4L using the amount of solvent A, and elution number is respectively 1 time, 2 times, 3 times, 4 times, the neutrality obtained after elution Oil is detected by GC-MS, and analysis result is as shown in Figure 6.Can be obtained by Fig. 6, with elution number increase neutral oil in phenol content by Decrescence few, when eluting number is 3 times, phenol content is basically reached at least in neutral oil, and elution number elutes effect when being more than 3 times It is unobvious, and increase cost, comprehensively consider, elution number is advisable for 3 times.Phenol silica obtained in second vacuum filter is passed through Solvent B elution, each solvent B elution amount is also 4L, and elution number is respectively 1 time, 2 times, 3 times, 4 times, and what is obtained after elution is thick Phenol is detected by GC-MS, and analysis result is as shown in Figure 7.It can be obtained by Fig. 7, as increase of the solvent B to silica gel phenol washing steps is thick Phenol content also gradually increases in phenol, and when washing steps are 3 times, phenol content basically reaches maximum in crude phenols, when washing steps are super When crossing 3 times, elution effect is unobvious, and increases cost, comprehensively considers, and washing steps are 3 Shi Weiyi.
Coalite tar neutral oil forms in table 2
Coalite tar crude phenols form in table 3
The present invention has carried out product analysis to the peak of peak 1-26 in Fig. 4, carries out in Fig. 5 to the peak that peak number is 1-26 Product analysis, the peak number in figure have all marked in table.
By the experimental studies results of Fig. 4, Fig. 5 and Fig. 6 as it can be seen that continuously separating new work using coal tar fraction of the invention Skill can efficiently separate to obtain neutral oil ingredient in coal tar, crude phenols component, be compared with the traditional method, and the present invention is a kind of The method of green continuous separation coal tar, do not generate Industrial " three Waste " and device taken up little area with respect to conventional separating apparatus, small investment, It is easily industrialized.Energy consumption is high, trivial operations, separation the present invention overcomes existing during existing coal tar processing simultaneously The problems such as low efficiency, pollution environment.

Claims (8)

1. a kind of coal tar fraction separator, which is characterized in that including the first paste state bed reactor (7) and the first vacuum filter It is connected at the top of machine (10), the first paste state bed reactor (7) top and the first vacuum filter (10), the first vacuum filter (10) Bottom is divided into two-way, extracts the remaining part storage tank (37) of absorption with solvent A all the way and is connected, another way and the second paste state bed reactor (12) top is connected, and the second paste state bed reactor (12) bottom is connected with third paste state bed reactor (20);Third slurry bed system is anti- It answers and is connected at the top of device (20) top and third vacuum filter (22), third vacuum filter (22) bottom is divided into two-way, all the way It is connected with solvent B elution fraction storage tank (27), is connected at the top of another way and the 4th paste state bed reactor (25);The storage of solvent B elution fraction Tank (27) is connected with crude phenols knockout tower (29), and solvent A extraction adsorbs remaining part storage tank (37) and is connected with neutral oil knockout tower (39);
Second paste state bed reactor (12) is connected with the second vacuum filter (14), and the second vacuum filter (14) bottom is divided into two Road extracts the remaining part storage tank (37) of absorption with solvent A all the way and is connected, phase at the top of another way and third paste state bed reactor (20) Even;
4th paste state bed reactor (25) top is connected with the 4th vacuum filter (26);4th vacuum filter (26) bottom point For two-way, it is connected all the way with solvent B elution fraction storage tank (27), is connected at the top of another way and the first paste state bed reactor (7).
2. a kind of coal tar fraction separator according to claim 1, which is characterized in that crude phenols knockout tower (29) tower top It is connected with crude phenols knockout tower overhead condenser (30) top, crude phenols knockout tower overhead condenser (30) bottom and crude phenols knockout tower tower It pushes up and is connected at the top of return tank (31), crude phenols knockout tower return tank of top of the tower (31) bottom enters with crude phenols knockout tower tower top return pump (32) Mouth is connected, and crude phenols knockout tower tower top return pump (32) outlet is divided into two-way, is connected all the way with crude phenols knockout tower (29) tower top, another Road is connected with solvent B storage tank (16).
3. a kind of coal tar fraction separator according to claim 1, which is characterized in that crude phenols knockout tower (29) tower bottom It is divided into two-way, is connected all the way through crude phenols knockout tower tower bottom reboiler (33) with crude phenols knockout tower (29) tower bottom, another way and crude phenols Component discharges, and condenser (34) entrance is connected, and crude phenols component discharging condenser (34) exports and crude phenols component discharging pump (35) entrance It is connected, crude phenols component discharging pump (35) outlet is connected with crude phenols storage tank (36).
4. a kind of coal tar fraction separator according to claim 1, which is characterized in that neutral oil knockout tower (39) top It is connected at the top of portion and neutral oil knockout tower overhead condenser (40), neutral oil knockout tower overhead condenser (40) bottom and neutral oil It is connected at the top of knockout tower return tank of top of the tower (41);Neutral oil knockout tower return tank of top of the tower (41) bottom separates column overhead with neutral oil Reflux pump (42) entrance be connected, neutral oil knockout tower tower top return pump (42) outlet is divided into two-way, all the way with neutral oil knockout tower (39) top is connected, and another way is connected with solvent A storage tank (3).
5. a kind of coal tar fraction separator according to claim 1, which is characterized in that neutral oil knockout tower (39) tower Bottom is divided into two-way, is connected all the way through neutral oil knockout tower tower bottom reboiler (43) with neutral oil knockout tower (39) tower bottom, another way It is connected with neutral oil ingredient discharging condenser (44) entrance;Neutral oil ingredient discharging condenser (44) outlet goes out with neutral oil ingredient Material pump (45) entrance is connected, and neutral oil ingredient discharging pump (45) outlet is connected with neutral oil tank (46).
6. a kind of coal tar fraction separating technology using coal tar fraction separator described in claim 1, feature exist In, comprising the following steps:
It is that 75~250 μm of silica gel is added in the first paste state bed reactor (7) by coal tar fraction, solvent A and partial size, the After being heated to 60~100 DEG C in one paste state bed reactor (7), extracting, by solvent A and coal tar fraction mixed liquor through the first vacuum Filter (10) separation obtains silica gel phenol and removes the solvent A extraction absorption residue of phenolic component;Silica gel phenol is added second In paste state bed reactor (12) after solvent A washs, extracted by the isolated silica gel phenol of the second vacuum filter (14) and solvent A Take the remaining part of absorption;
The isolated silica gel phenol of second vacuum filter (14) is added in third paste state bed reactor (20), through solvent B It after elution, is separated by third vacuum filter (22), obtains eluting silica gel and solvent B elution fraction;
Solvent B elution fraction is preheated to after 60~100 DEG C to be added in crude phenols knockout tower (29) and carries out rectifying separation, obtains crude phenols With solvent B;
After the solvent A for removing phenolic component extraction absorption residue and solvent A extraction absorption residue part are preheated to 60~100 DEG C It is added in neutral oil knockout tower (39) and carries out rectifying separation, obtain neutral oil ingredient and solvent A.
7. a kind of coal tar fraction separating technology according to claim 6, which is characterized in that
Eluting silica gel is added in the 4th paste state bed reactor (25), after solvent B is eluted, by the 4th vacuum filter Machine (26) separation, obtains silica gel and solvent B elution fraction;
Crude phenols knockout tower (29) tower top output solvent B steam, solvent B steam are all cold through crude phenols knockout tower overhead condenser (30) It coagulates for liquid phase, the solvent B of Quan Ninghou enters crude phenols knockout tower return tank of top of the tower (31), then through crude phenols knockout tower tower top return pump (32) a part is back to crude phenols knockout tower (29) tower top, and another part returns in solvent B storage tank (16), obtains solvent B;
Neutral oil knockout tower (39) tower top output solvent A steam, solvent A steam are complete through neutral oil separation column overhead complete condenser (40) Portion is condensed into liquid phase, and the solvent A of Quan Ninghou enters in neutral oil knockout tower return tank of top of the tower (41), then through neutral oil knockout tower Tower top return pump (42) a part is back in neutral oil knockout tower (39) tower top, and another part returns to solvent A storage tank (3) In, obtain solvent A.
8. a kind of coal tar fraction separating technology according to claim 6, which is characterized in that
The volume ratio of coal tar fraction and solvent A, silica gel is 1:1:1~1:20:20;Solvent A is the list in the alkane of C5~C8 The mixture of one alkane or several single alkane, wherein the alkane of C5~C8 is n-alkane or branched paraffin;
Solvent B is the mixture of one or more of ethyl acetate, toluene, ethyl alcohol, methanol.
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CN107446606B (en) * 2017-08-30 2024-01-23 西北大学 Process and device for producing modified asphalt, aliphatic hydrocarbon and aromatic hydrocarbon from coal tar
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