CN110257101A - A kind of coal tar fraction reaction-separation-reaction prepares the device and method of chemicals - Google Patents
A kind of coal tar fraction reaction-separation-reaction prepares the device and method of chemicals Download PDFInfo
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- CN110257101A CN110257101A CN201910596238.8A CN201910596238A CN110257101A CN 110257101 A CN110257101 A CN 110257101A CN 201910596238 A CN201910596238 A CN 201910596238A CN 110257101 A CN110257101 A CN 110257101A
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- aromatic hydrocarbon
- polycyclic aromatic
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract
A kind of coal tar fraction reaction-separation-reaction prepares the device and method of chemicals, using polycyclic aromatic hydrocarbon in coal tar (two rings, tricyclic, Fourth Ring) one-component as core, dead oil after fraction is cut rich in polycyclic aromatic hydrocarbon is using de- alkyl normalized, it effectively is enriched the component that polycyclic aromatic hydrocarbon is more single in coal tar, significantly reduces the energy consumption of separating difficulty and centrifugal station.Using biggish freezing point difference between polycyclic aromatic hydrocarbon (two rings, tricyclic, Fourth Ring), it is isolated by constant-temperature condensation, centrifugal filtration.Centrifugal station energy consumption is effectively reduced in separation process normal pressure, lower temperature.To improve in coal tar for the purpose of polycyclic aromatic hydrocarbon high value added utilization, the polycyclic aromatic hydrocarbon partial hydrogenation chemicals of more high added value will further can be processed by hydrogenation reaction through the resulting high-purity fraction of polycyclic aromatic hydrocarbon separator.
Description
Technical field
The invention belongs to energy deep process technology fields, are related to a kind of coal tar polycyclic aromatic hydrocarbon fraction reaction-separation-reaction
Prepare the device and method of chemicals.
Background technique
Rich coal resources in China, a large amount of byproducts --- the coal tar of association in coal chemical industry production process are valuable
Industrial chemicals, can therefrom extract the chemical products of a variety of high added values.The research and classification sub-prime benefit of coal tar composed structure
With for being had great significance to greatest extent using coal resources, promotion China's economic development.Coal tar composition is extremely multiple
It is miscellaneous, it include aromatic hydrocarbon, aliphatic hydrocarbon, oxygen-containing, nitrogenous compound and heteroatomic compound in race's composition.Currently, how coal is realized
The high value added utilization of polycyclic aromatic hydrocarbon is the difficult point in industrial production in tar.Polycyclic aromatic hydrocarbon is the most basic chemical industry of organic chemical industry
Raw material can be used for producing a variety of fine chemical products.For example, biphenyl is used as the thermophore of chemical process, naphthalene is used to manufacture dye
Material and plasticizer, phenanthrene are used for dyestuff, synthetic resin, disperse dyes and engineering plastics for producing dyestuff and synthetic drug, pyrene,
Also it is used to insecticide processed, plasticizer etc..Not only added value height itself is widely used for polycyclic aromatic hydrocarbon, and its many downstream product produces
Measure less, added value is higher.Such as: naphthane belongs to naphthalene plus hydrogen intermediate is a kind of important hydrogen supply dissolvent；It is widely applied
In the technical study that DCL/Direct coal liquefaction, coal tar pitch add hydrogen and biomass liquefying etc..With naphthalene (500g, 180 yuan), decahydronaphthalene
The price of (250mL, 69.6 yuan) is compared, and naphthane (250mL, 695 yuan) obviously belongs to high-value product.It is more for phenanthrene, pyrene etc.
Cycloaromatics is similar, and partial hydrogenation, which prepares corresponding intermediate (such as dihydro phenanthrene, hexahydro pyrene), can promote the value of product.Coal tar
It is one of the main source of arene compound, however aromatic hydrocarbon is containing there are many side chain derivative, derivatives in existing coal tar
Many kinds of, content is small and distribution is not concentrated, thus cause its separation difficult, it can not be to existing effect processing and utilization in fact.With naphthalene
For, content is more than that 1% two cycle compounds mainly have: naphthalene (8-12%), 1- methyl naphthalene (0.8-1.2%), 2- in coal tar
Methyl naphthalene (1.0-1.8%).Therefore, at present coal tar processing method due to separation method limitation and process it is simple
Change, so that the inefficient utilization of coal tar high value component, waste of resource simultaneously pollutes environment.
Summary of the invention
The purpose of the present invention is to provide polycyclic aromatic hydrocarbon fraction reaction-separation-reactions in a kind of coal tar to prepare chemicals
Device and method.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of coal tar fraction reaction-separation-reaction prepares the device of chemicals, including fraction seperation tower, distillate delay
Rush tank, dealkylation device, level-one polycyclic aromatic hydrocarbon separator, second level polycyclic aromatic hydrocarbon separator, the first deep processing reactor, second
Deep processing reactor and third deep processing reactor；
Wherein, fraction seperation tower is connected with distillate surge tank, and distillate surge tank is connected with dealkylation device, takes off alkane
Base reactor is connected with level-one polycyclic aromatic hydrocarbon separator inlet, and level-one polycyclic aromatic hydrocarbon separator outlet is divided into two-way, all the way with two
Grade polycyclic aromatic hydrocarbon separator inlet is connected, and another way is connected with the first deep processing reactor inlet, second level polycyclic aromatic hydrocarbon separator
Outlet is divided into two-way, is connected all the way with the second deep processing reactor inlet, another way is connected with third deep processing reactor inlet.
A further improvement of the present invention lies in that fraction seperation tower is also connected with coal tar storage tank.
A further improvement of the present invention lies in that the first deep processing reactor, the second deep processing reactor and third add deeply
Work reactor inlet is connected with gas reservoir；
First deep processing reactor outlet is connected with the first afterproduct treating column, the second deep processing reactor and the two or two
Secondary product purification tower is connected；Third deep processing reactor is connected with third afterproduct treating column.
A further improvement of the present invention lies in that the first afterproduct treating column is connected with the first afterproduct storage tank, second
Afterproduct treating column is connected with second secondary product storage tank, third afterproduct treating column and third afterproduct storage tank phase
Even.
A further improvement of the present invention lies in that polycyclic aromatic hydrocarbon separator includes separator body, feed inlet, agitating paddle, folder
Set, insulating box, concentrator bowl, filter membrane and separation controller；Wherein, insulating box and concentrator bowl are provided in collet；In insulating box
It is provided with agitating paddle, feed inlet is provided at the top of insulating box, insulating box is arranged on concentrator bowl, and concentrator bowl includes inner cylinder and outer
Cylinder, inner cylinder are set in outer cylinder, and filter membrane is provided between inner barrel and outer barrel；Concentrator bowl and insulating box with separate controller phase
Even.
A further improvement of the present invention lies in that the aperture of filter membrane is 4-5 μm；Inner cylinder bottom is provided with solid phase discharge port, outside
Cylinder bottom is provided with liquid phase discharge port.
A kind of chemical processes that prepare based on above-mentioned device, coal tar are delivered into fraction seperation tower, are distilled
To 210-360 DEG C of mixed fraction oil；Or coal tar is delivered into fraction seperation tower, is obtained through distillation lateral line discharging single
Distillate, respectively naphtalene oil, naphtalene oil or carbolineum；
Single distillate or mixed fraction oil are delivered in the dealkylation device for being filled with dealkylation catalyst, de-
It is delivered to level-one polycyclic aromatic hydrocarbon separator after being reacted in alkylation reaction device (5), solid is precipitated at 145-148 DEG C, then
It is separated by filtration, obtained solid is pyrene；Gained liquid phase enters in second level polycyclic aromatic hydrocarbon separator, and solid is precipitated at 98-100 DEG C,
Centrifugal filtration, obtained solid are phenanthrene；Gained liquid phase, which enters, to be filled in the third deep processing reactor of selective hydrocatalyst,
After being reacted in third deep processing reactor, naphthane is obtained；
Pyrene is added in the first deep processing reactor for being filled with selective hydrocatalyst, is reacted in the first deep processing
It is reacted in device, obtains hexahydro pyrene；
Phenanthrene is added to the second deep processing reactor for being filled with selective hydrocatalyst, in the second deep processing reactor
In reacted, obtain dihydro phenanthrene.
A further improvement of the present invention lies in that the condition reacted in dealkylation device are as follows: mass space velocity ratio is
2-3WHSV·h-1, it is 400-520 DEG C in temperature, reaction first pressing is 1-4MPa, reacts 2-8h；
It is reacted in the first deep processing reactor, reaction is carried out in the second deep processing reactor and is added deeply in third
The condition reacted in work reactor is equal are as follows: mass space velocity ratio is 2-3WHSVh-1, it is 160-240 DEG C in temperature, reaction is just
Pressure is 4-8MPa, reacts 4-8h.
A further improvement of the present invention lies in that dealkylation catalyst is made by following procedure: using equi-volume impregnating
Active component, auxiliary agent are supported on carrier, 4-6h is stood, roasts 4-6h after then drying at 450-550 DEG C, obtains de- alkane
Base catalyst；Wherein, based on mass fraction, the load capacity of active component is 3-9%, and the load capacity of auxiliary agent is 0.07-0.5%；
Selective catalytic hydrogenation catalyst is made by following procedure: being supported on active component using equi-volume impregnating
In catalyst carrier, through ultrasound, stands, roast 4-6h at 450-550 DEG C after then drying, obtain selective catalytic hydrogenation and urge
Agent；Wherein, based on mass fraction, the load capacity of active component is 12%-36%.
A further improvement of the present invention lies in that when prepared by dealkylation catalyst, in active component Ni, Mo, Co, W one
Kind is a variety of；Auxiliary agent is lanthanum；Carrier is the mixture of one or more of ZSM-5, Beta, HY；
When selective catalytic hydrogenation catalyst preparation, carrier SiO2、TiO2、Al2O3, one of HY, HZSM-5 or several
The mixture of kind；Active component is one or more of Co, Mo, Ni, W.
Compared with prior art, the beneficial effects of the present invention are:
The present invention passes through setting fraction seperation tower, distillate surge tank, dealkylation device, the separation of level-one polycyclic aromatic hydrocarbon
Device, second level polycyclic aromatic hydrocarbon separator, the first deep processing reactor, the second deep processing reactor and third deep processing reactor；
Fraction seperation tower is connected with distillate surge tank, and distillate surge tank is connected with dealkylation device, dealkylation device and one
Grade polycyclic aromatic hydrocarbon separator inlet is connected, and level-one polycyclic aromatic hydrocarbon separator outlet is divided into two-way, divides all the way with second level polycyclic aromatic hydrocarbon
It is connected from device entrance, another way is connected with the first deep processing reactor inlet, and second level polycyclic aromatic hydrocarbon separator outlet is divided into two-way,
It is connected all the way with the second deep processing reactor inlet, another way is connected with third deep processing reactor inlet.It is provided by the invention
Device, which can be realized, adds the high-purity high purity dicyclo (naphthalene) after separating-purifying/tricyclic (phenanthrene)/Fourth Ring (pyrene) using selectivity
Hydrogen deep processing becomes the chemicals of more high added value.And the selective hydrogenation catalysis that method therefor is prepared in the present invention
Agent effectively raises the conversion ratio (95.62%) and selectivity (99.75%) of selective hydrogenation, effectively increases mesh
Mark the yield of product.
Further, traditional equipment is compared, separator is mainly by insulating box, concentrator bowl two parts and agitating paddle, folder
The accessories such as set, separation controller；Insulating box realizes that material constant temperature, condensation process, concentrator bowl are realized material filtering, were centrifuged
Journey；Concentrator bowl is located at concentrator bowl lower end, and two parts have external jacket to provide required temperature, and separation controller in insulating box to stirring
The temperature for mixing heat medium in the revolving speed, concentrator bowl revolving speed and collet of paddle is controlled；Material inlet is one, material outlet
Be two, material can continuous feed, solid-liquid product discharges respectively.
The present invention maximumlly separates the polycyclic aromatic hydrocarbon being utilized in coal tar, while improving its added value, improves
The efficiency that coal tar classification sub-prime utilizes while improving economy, reduces it and pollutes environment.It is cut compared to traditional fraction
To the pre-separation workshop section of coal tar, this method is not only suitable for the difference processing and utilization of three naphtalene oil, washing oil, carbolineum fractions, simultaneously
It is also applied for naphthalene, washes, the utilization of the mixed fraction overall processing of carbolineum.Due to different coal tar composition and nature difference compared with
Greatly, thus this method applicability is extensive.Remaining light oil distillate can be used for mentioning phenol, production gasoline, and the mink cell focus of tower bottom is available
In production pitch plus hydrogen lighting processing etc..Compared to traditional distillate separating-purifying workshop section, this method is taken off before separation
Alkylation reaction, the distillate that will be enriched in polycyclic aromatic hydrocarbon take off alkyl normalized, can largely be enriched in polycyclic aromatic hydrocarbon more single
A component.And the hydrodealkylation catalyst that method therefor is prepared in invention, effectively raise dealkylation
Conversion ratio (81.23%) and selectivity (64.22%).Polycyclic aromatic hydrocarbon after dealkylation, effectively reduces coal tar
In number of components while improve the contents of target components, and avoid its a variety of derivative and its separation process done
It disturbs, that is, reduces the separating difficulty of polycyclic aromatic hydrocarbon in coal tar, shorten separation process, centrifugal station energy consumption will be significantly reduced.
Compared to traditional separating-purifying workshop section, the separation of the polycyclic aromatic hydrocarbon after dealkylation uses polycyclic aromatic hydrocarbon separator, polycyclic
Aromatic hydrocarbons mixture is through multistage constant temperature, and-condensation-is centrifuged-is separated by filtration, and obtains polycyclic aromatic hydrocarbon one pack system.Compared to other points such as rectifying
From mode, separation process is (to be lower than 150 DEG C) under normal pressure and lower temperature to carry out, and equipment operation is simple, and consumption can be effectively reduced
Energy and operating cost.Compared to traditional coal tar processing, further by the high-purity high purity dicyclo after separating-purifying
(naphthalene)/tricyclic (phenanthrene)/Fourth Ring (pyrene) becomes the chemicals of more high added value using selective hydrogenation deep processing.And the present invention
The selective hydrocatalyst that middle method therefor is prepared effectively raises the conversion ratio of selective hydrogenation
(95.62%) and it is selective (99.75%), effectively increase the yield of target product.This method first evaporates coal tar aromatic hydrocarbons
Divide normalization, isolated polycyclic aromatic hydrocarbon one-component after enrichment, the polycyclic aromatic hydrocarbon of one-component can be used as high added value production
Chemical products are sold, while can be using deep processing as high valuable chemicals.This method can effectively be enriched with polycyclic aromatic hydrocarbon one-component
Content, and be isolated in a manner of low power consuming, while the high valuable chemicals that deep processing obtains have higher economy
Property.This method effectively increases the yield of polycyclic aromatic hydrocarbon one-component in coal tar, and the high added value that deep processing obtains
Product value it is higher, component concentration effect is low during overcoming existing coal tar processing, high added value substance processing difficulties and
The technical problems such as utilization rate is low.
Detailed description of the invention
Fig. 1 is the process for the method that polycyclic aromatic hydrocarbon fraction reaction-separation-reaction prepares chemicals in coal tar of the invention
Schematic diagram；
Fig. 2 is the structure for the device that polycyclic aromatic hydrocarbon fraction reaction-separation-reaction prepares chemicals in coal tar of the invention
Schematic diagram；
Fig. 3 is the structural schematic diagram of polycyclic aromatic hydrocarbon separator；
Fig. 4 is the effect picture of hydro-dealkylation catalysis；
Fig. 5 is the effect picture (A:SiO of selective hydrogenation catalysis2、B:TiO2、C:Al2O3、D:HY、E:HZSM-5)。
In figure, 1, coal tar storage tank, 2, gas reservoir, 3, fraction seperation tower, 4, distillate surge tank, 5, de- alkyl
Reactor, 6, polycyclic aromatic hydrocarbon separator, 7, second level polycyclic aromatic hydrocarbon separator, the 8, first polycyclic aromatic hydrocarbon storage tank, the 9, second polycyclic virtue
Hydrocarbon storage tank, 10, third polycyclic aromatic hydrocarbon storage tank, the 11, first deep processing reactor, the 12, second deep processing reactor, 13, third depth
Processing reactor, the 14, first afterproduct treating column, 15, second secondary product purification tower, 16, third afterproduct treating column,
17, the first afterproduct storage tank, 18, second secondary product storage tank 19, third afterproduct storage tank, 20, mixed material entrance,
21, agitating paddle, 22, collet, 23, insulating box, 24, concentrator bowl, 25, filter membrane, 26, liquid phase discharge port, 27, solid phase discharge port, 28,
Separator controller.
Specific embodiment
By specific embodiment, the present invention is described in detail with reference to the accompanying drawing.
Referring to Fig. 1 and Fig. 2, polycyclic aromatic hydrocarbon fraction reaction-separation-reaction prepares the device of chemicals in a kind of coal tar,
It is more including coal tar storage tank 1, gas reservoir 2, fraction seperation tower 3, distillate surge tank 4, dealkylation device 5, level-one
Cycloaromatics separator 6, second level polycyclic aromatic hydrocarbon separator 7, the first polycyclic aromatic hydrocarbon storage tank 8, the second polycyclic aromatic hydrocarbon storage tank 9, third is more
Cycloaromatics storage tank 10, the first deep processing reactor 11, the second deep processing reactor 12, third deep processing reactor the 13, the 1st
Secondary product purification tower 14, second secondary product purification tower 15, third afterproduct treating column 16, the first afterproduct storage tank 17,
Second secondary product storage tank 18 and third afterproduct storage tank 19.
Wherein, coal tar storage tank 1 is connected with fraction seperation tower 3, and fraction seperation tower 3 is connected with distillate surge tank 4,
Distillate surge tank 4 is connected with dealkylation device 5, and dealkylation device 5 is connected with 6 entrance of level-one polycyclic aromatic hydrocarbon separator,
The outlet of level-one polycyclic aromatic hydrocarbon separator 6 is divided into two-way, is connected all the way with 7 entrance of second level polycyclic aromatic hydrocarbon separator, another way and the
One polycyclic aromatic hydrocarbon storage tank 8 be connected, second level polycyclic aromatic hydrocarbon separator 7 outlet is divided into two-way, all the way with 9 phase of the second polycyclic aromatic hydrocarbon storage tank
Even, another way and third polycyclic aromatic hydrocarbon storage tank 10；First polycyclic aromatic hydrocarbon storage tank 8 is connected with 11 entrance of the first deep processing reactor,
Second polycyclic aromatic hydrocarbon storage tank 9 is connected with 12 entrance of the second deep processing reactor, third polycyclic aromatic hydrocarbon storage tank 10 and third deep processing
13 entrance of reactor is connected, gas reservoir 2 and the first deep processing reactor 11, the second deep processing reactor 12, third deep processing
13 entrance of reactor is connected, and the outlet of the first deep processing reactor 11 is connected with the first afterproduct treating column 14, and first is secondary
Product purification tower 14 is connected with the first afterproduct storage tank 17；Second deep processing reactor 12 and second secondary product purification tower 15
It is connected, second secondary product purification tower 15 is connected with second secondary product storage tank 18；Third deep processing reactor 13 and the 3rd 2
Secondary product purification tower 16 is connected, and third afterproduct treating column 16 is connected with third afterproduct storage tank 19.
Referring to Fig. 3, polycyclic aromatic hydrocarbon separator 6 includes separator body, feed inlet 20, agitating paddle 21, collet 22, insulating box
23, concentrator bowl 24, filter membrane 25 (aperture is 4-5 μm on filter membrane), liquid phase discharge port 26, solid phase discharging 27 and separation controller
28。
Wherein, insulating box 23 and concentrator bowl 24 are provided in collet 22；Agitating paddle 21, insulating box are provided in insulating box 23
23 tops are provided with feed inlet 20, and insulating box 23 is arranged on concentrator bowl 24, and concentrator bowl 24 includes inner barrel and outer barrel, and inner cylinder is arranged
Filter membrane 25 is provided in outer cylinder, between inner barrel and outer barrel, inner cylinder bottom is provided with solid phase discharge port 27, and outer cylinder bottom is provided with
Liquid phase discharge port 26；Concentrator bowl 24 and insulating box 23 with separate controller 28 and be connected.
Specifically, agitating paddle 21 is located at 23 center of insulating box, guarantee that the heat transfer of thermostatic process material is uniform.The heating of collet 22 is situated between
Matter provides separation process required temperature.It is concentrator bowl 24 below insulating box 23, structure is double layer sleeve barrel, and inner cylinder is used for polycyclic
Aromatic hydrocarbons solidliquid mixture receive and is separated by centrifugal filtration, and solid phase is stranded in inner cylinder and liquid phase is outer through the entrance of filter membrane 25
Cylinder.Feed inlet 20 is located at 23 top of insulating box, and liquid phase discharge port 26 is located at 24 outer cylinder lower end of concentrator bowl, and solid phase discharge port 27 is located at
24 inner cylinder lower end of concentrator bowl.Separating controller 28 has temperature, revolution speed control system, temperature and concentrator bowl 24 to insulating box
Revolving speed controlled.
Referring to Fig. 1, polycyclic aromatic hydrocarbon reaction-separation-reaction prepares chemicals in the coal tar based on above-mentioned apparatus method
Are as follows: the coal tar of coal tar storage tank 1 is delivered into fraction seperation tower 3, and it is oily (210-360 DEG C) that distillation obtains mixed fraction
After be delivered to distillate surge tank 4.Can also the coal tar of coal tar storage tank 1 delivered into fraction seperation tower 3, through distilling
Lateral line discharging obtains single distillate, respectively naphtalene oil (210-230 DEG C), naphtalene oil (230-280 DEG C) and carbolineum (280-360
DEG C), every kind of single distillate is then delivered to corresponding distillate surge tank (three) respectively.Single distillate or mixing evaporate
Divide oil to be then delivered to the dealkylation device 5 for being filled with dealkylation catalyst, comes into full contact with (quality sky with dealkylation catalyst
Speed ratio is 2-3WHSVh-1), it is 400-520 DEG C in temperature, reaction first pressing is 1-4MPa, reacts 2-8h.By dealkylation
The normalized distillate of dealkylation is delivered to level-one polycyclic aromatic hydrocarbon separator 6 in device 5, using freezing point multi-stage separation, one
The temperature of 6 inside holding case of grade polycyclic aromatic hydrocarbon separator is controlled by collet at 145-148 DEG C, and four cycloaromatics-pyrene is precipitated first at this time,
Mixed material enters in concentrator bowl (2000-3000rmin-1) be separated by filtration, pyrene by level-one polycyclic aromatic hydrocarbon separator 6 solid phase
Discharge port is sent out, into the first polycyclic aromatic hydrocarbon storage tank 8.Liquid phase mixture is sent out by liquid phase discharge port, into second level polycyclic aromatic hydrocarbon
Separator 7, using freezing point multi-stage separation, the temperature of incubator is controlled by collet at 98-100 DEG C, at this time thrcylic aromatic hydrocarbon-phenanthrene analysis
Out, it is sent out after centrifugal filtration by the solid phase discharge port of second level polycyclic aromatic hydrocarbon separator 7, into the second polycyclic aromatic hydrocarbon storage tank 9.Liquid
Phase-naphthalene is then sent out by liquid phase discharge port, into third polycyclic aromatic hydrocarbon storage tank 10.
The further reacting processing of primary production (pyrene, phenanthrene, naphthalene) is separated into the chemicals of more high added value.First polycyclic aromatic hydrocarbon
Storage tank 8, the second polycyclic aromatic hydrocarbon storage tank 9, the primary production in third polycyclic aromatic hydrocarbon storage tank 10 respectively enter load it is selective plus
Hydrogen catalyst (12%-36%-Ni/Mo-Al2O3/ HY/HZSM-5) the first deep processing reactor 11, the second deep processing reactor
12, third deep processing reactor 13, with selective hydrocatalyst come into full contact with (mass space velocity ratio be 2-3WHSVh-1),
Temperature is 160-240 DEG C, and reaction first pressing is 4-8MPa, reacts 4-8h；
Wherein, reaction obtains hexahydro pyrene in the first deep processing reactor 11, reacts and obtains in the second deep processing reactor 12
Dihydro phenanthrene；Reaction obtains naphthane in third deep processing reactor 13.
Deep processing is carried out using selective hydrogenation, reaction product (i.e. hexahydro pyrene, dihydro phenanthrene, naphthane) respectively enters first
Afterproduct treating column 14, second secondary product purification tower 15, third afterproduct treating column 16 carry out separation decontamination, obtain
Chemicals (naphthane, dihydro phenanthrene, hexahydro pyrene) enters the first afterproduct storage tank 17, second secondary product storage tank the 18, the 3rd 2
Secondary product storage tank 19.
H needed for reacting2Enter the first deep processing reactor 11, the second deep processing reactor 12 and third from gas reservoir 2
Deep processing reactor 13 is equipped with shut-off valve control gas switch.
Wherein, dealkylation catalyst includes carrier, active component, co-catalyst, and the carrier is in ZSM-5, Beta, HY
One or more of mixtures；The active component is one of Ni, Mo, Co, W or a variety of；The oxide of active component
Load capacity be 3-9% (based on mass fraction)；Auxiliary agent is the lanthanum of load capacity 0.07-0.5%；It will be lived using equi-volume impregnating
Property component, auxiliary agent load on a catalyst support, stand 4-6h, then 450-550 DEG C of roasting 4-6h after 120 DEG C of dry 4-6h,
It can get dealkylation catalyst, as (0.07-0.5%La-3-9%Ni/Mo/Co/W-HYZSM-5/Beta/HY).
Selective catalytic hydrogenation catalyst includes carrier and active component, and the carrier is SiO2、TiO2、Al2O3、HY、
The mixture of one or more of HZSM-5；The active component is one or more of Co, Mo, Ni, W metal；Activity
The load capacity of the oxide of component is 12%-36%.Active component is loaded on a catalyst support using equi-volume impregnating,
It through ultrasound, stands, roasts 4-6h at 450-550 DEG C after then drying, obtain selective catalytic hydrogenation catalyst.
Polycyclic aromatic hydrocarbon material after taking off alkyl normalization enters polycyclic aromatic hydrocarbon separator 6 by feed inlet 20, first in perseverance
The cooling polycyclic aromatic hydrocarbon one pack system for starting that high-solidification point is precipitated, is uniformly mixed and enters under the action of agitating paddle 21 in incubator 23
(the revolving speed 2000-3000rmin of concentrator bowl 24-1), the filter membrane 25 that centrifugation barrel is.Solids product is stopped with inner cylinder and by solid phase
Discharge port 27, which is sent out, enters product storage tank.Liquid phase passes through filter membrane and enters outer cylinder and sent out by liquid phase discharge port 26 polycyclic into second level
Aromatics seperation device.Such multi-stage separation obtains each single-component product of polycyclic aromatic hydrocarbon.
Coal tar is coalite tar, middle coalite tar, medium temperature coal tar or high temperature coal-tar in the present invention.
This method process strong applicability, coal tar oil tank are followed by fraction seperation tower.Fraction seperation part be suitable for naphthalene, wash,
Carbolineum mixed fraction is oily (210-360 DEG C), while being suitable for naphtalene oil (210-230 DEG C), washing oil (230-280 DEG C), carbolineum (280-
360 DEG C) single distillate.Fraction seperation tower is one, and lateral line discharging can realize single fraction discharging.
Distillate surge tank 4 is followed by dealkylation device.Dealkylation device 5 is 1, interior to be equipped with catalyst bed.
Bicyclic (naphthalene)/tricyclic (phenanthrene)/Fourth Ring (pyrene) separation uses polycyclic aromatic hydrocarbon separator 6.Polycyclic aromatic hydrocarbon separator 6 is two
A, using multistage constant temperature ,-condensation-is centrifuged-is separated by filtration.Polycyclic aromatic hydrocarbon storage tank is followed by the first deep processing reactor 11, and second is deep
Processing reactor 12, third deep processing reactor 13.High purity dicyclo (naphthalene)/tricyclic (phenanthrene)/Fourth Ring (pyrene), continues to adopt after separation
Become the chemicals (naphthane, dihydro phenanthrene, hexahydro pyrene) of more high added value with selective hydrogenation deep processing.Deep processing reactor
It is 3, it is interior to be equipped with catalyst bed.
Embodiment 1
Using the coal tar of northern Shensi coke-oven plant as raw material, the results are shown in Table 1 with elemental analysis for fundamental property.It is steamed
It evaporates and obtains each fraction of naphtalene oil, washing oil, carbolineum and its mixed fraction (for the mixture of 3 kinds of single fractions).Gained yield such as 2 institute of table
Show.Obtained mixed fraction is tested to analyze using gas chromatography combined with mass spectrometry.
The fundamental property of coal tar used and elemental analysis are shown in Table 1 in embodiment 1.
The fundamental property of 1 coal tar of table and elemental analysis
Each yield of 2 coal tar of table
Embodiment 2
Using the coal tar of northern Shensi coke-oven plant as raw material, wherein naphthalene, phenanthrene, pyrene content be respectively 11.84%, 4.67%,
1.52%.Obtain that mixed fraction is oily (210-360 DEG C) through distillation, be then delivered to be filled with dealkylation catalyst de- alkyl it is anti-
Answer device 5, with dealkylation catalyst come into full contact with (mass space velocity ratio be 2-3WHSVh-1), it is 480 DEG C in temperature, reacts first pressing
To react 4h under the conditions of 2MPa.Naphthalene in reaction product, phenanthrene, pyrene content distribution improve to 14.09%, 6.12%, 2.48%.Through
It crosses the normalized distillate of dealkylation and is delivered to multistage polycyclic aromatic hydrocarbon separator and separated, the naphthalene, phenanthrene, pyrene in material
Yield is respectively 13.81%, 5.94%, 2.36%.It the results are shown in Table 3, hydro-dealkylation reaction effectively raises in coal tar
The content of polycyclic aromatic hydrocarbon one pack system, the polycyclic aromatic hydrocarbon one pack system yield after separator separates is still compared with material content height.Polycyclic virtue
Hydrocarbon one pack system isolates and purifies after chosen property hydrogenation reaction to obtain chemicals naphthane, dihydro phenanthrene, hexahydro pyrene, yield point respectively
Not Wei 13.53%, 5.69%, 2.10%, content of the chemicals yield still compared with naphthalene in raw material, phenanthrene, pyrene is high.It the results are shown in Table 4.
Polycyclic aromatic hydrocarbon yield in each workshop section's material of table 3
4 chemicals yield of table
Embodiment 3
Hydro-dealkylation workshop section in the present embodiment is to alkyl polycyclic aromatic compounds (alkylnaphthalene, alkyl phenanthrene, the alkyl in crude oil
Pyrene) carry out hydro-dealkylation.With 2- methyl naphthalene (model compound) for raw material, hydrodealkylation catalyst is to alkane in investigation method
Quito cycloaromatics hydro-dealkylation is converted into the effect of polycyclic aromatic hydrocarbon.Hydrodealkylation catalyst in the present embodiment includes carrying
Body, active component, co-catalyst, the carrier are the mixture of one or more of ZSM-5, Beta, HY；The active group
It is divided into one of Ni, Mo, Co, W or a variety of；The load capacity of the oxide of active component is 3-9% (based on mass fraction)；It helps
Agent is the lanthanum of load capacity 0.07-0.5%；Active component, auxiliary agent are loaded on a catalyst support using equi-volume impregnating, it is quiet
4-6h is set, then 450-550 DEG C of roasting 4-6h after 120 DEG C of dry 4-6h, can get hydrodealkylation catalyst.The catalyst is answered
The reaction temperature of used time is 480 DEG C, and reaction first pressing is 2MPa, has reacted 4h.Reaction effect is shown in Fig. 4, what this method was prepared
Hydrodealkylation catalyst effectively removes the side chain of alkylnaphthalene.For the selectivity of naphthalene up to being 64.22%, conversion ratio is can
Up to 81.23%.By conversion ratio and selectivity this it appears that improving the yield of naphthalene, alkylnaphthalene is effectively transformed into
Naphthalene, the effective content for improving naphthalene in raw material coal tar.
Embodiment 4
Selective hydrogenation workshop section in the present embodiment carries out selective hydrogenation to the polycyclic aromatic hydrocarbon (naphthalene, phenanthrene, pyrene) in crude oil,
With naphthalene (model compound) for raw material, catalyst is investigated to polycyclic aromatic hydrocarbon selective hydrogenation effect.Selectivity in the present embodiment
Catalytic hydrogenation catalyst includes carrier and active component, and the carrier is Al2O3, one or more of HY, HZSM-5 mixing
Object；The load capacity of the oxide of active component is 12%-36%, and nickel molybdenum ratio is 1:5.Using equi-volume impregnating by active component
Load stands 12h on a catalyst support, through ultrasonic 0.5-1h, then 450-550 DEG C of roasting 4-6h after 120 DEG C of dry 4-6h,
It can get selective hydrocatalyst.Catalyst reaction temperature in application is 200 DEG C, reaction time 8h, initial H2 pressure
Power is 6MPa.As a result as shown in figure 5, the conversion ratio of naphthalene is up to 95.62%, and the selectivity of naphthane is up to 99.75%.By
Conversion ratio and selectivity are this it appears that improve the yield of naphthane.
The present invention, as core, fraction is cut using polycyclic aromatic hydrocarbon in coal tar coal tar (two rings, tricyclic, Fourth Ring) one-component
Dead oil after cutting rich in polycyclic aromatic hydrocarbon is effectively enriched polycyclic aromatic hydrocarbon in coal tar using de- alkyl normalized
More single component significantly reduces the energy consumption of separating difficulty and centrifugal station.Utilize polycyclic aromatic hydrocarbon (two rings, tricyclic, four
Ring) between biggish freezing point difference, be isolated by constant-temperature condensation, centrifugal filtration.Separation process normal pressure, lower temperature, have
Effect reduces centrifugal station energy consumption.To improve in coal tar for the purpose of polycyclic aromatic hydrocarbon high value added utilization, will be separated through polycyclic aromatic hydrocarbon
The resulting high-purity fraction of device can further be processed into the polycyclic aromatic hydrocarbon partial hydrogenation of more high added value by hydrogenation reaction
Chemicals.Present method solves the separation problem of component in existing coal tar, it is enriched valuable one-component in coal tar
Content, and to the deep processing and utilization of polycyclic aromatic hydrocarbon compounds in coal tar, effectively improve the utility value of coal tar.
Claims (10)
1. the device that a kind of coal tar fraction reaction-separation-reaction prepares chemicals, which is characterized in that including fraction seperation tower
(3), distillate surge tank (4), dealkylation device (5), level-one polycyclic aromatic hydrocarbon separator (6), second level polycyclic aromatic hydrocarbon separator
(7), the first deep processing reactor (11), the second deep processing reactor (12) and third deep processing reactor (13)；
Wherein, fraction seperation tower (3) is connected with distillate surge tank (4), distillate surge tank (4) and dealkylation device (5)
It is connected, dealkylation device (5) is connected with level-one polycyclic aromatic hydrocarbon separator (6) entrance, level-one polycyclic aromatic hydrocarbon separator (6) outlet
It is divided into two-way, is connected all the way with second level polycyclic aromatic hydrocarbon separator (7) entrance, another way and first deep processing reactor (11) entrance
It is connected, second level polycyclic aromatic hydrocarbon separator (7) outlet is divided into two-way, is connected all the way with second deep processing reactor (12) entrance, separately
It is connected all the way with third deep processing reactor (13) entrance.
2. a kind of coal tar fraction reaction-separation-reaction according to claim 1 prepares the device of chemicals, feature
It is, fraction seperation tower (3) is also connected with coal tar storage tank (1).
3. a kind of coal tar fraction reaction-separation-reaction according to claim 1 prepares the device of chemicals, feature
It is, the first deep processing reactor (11), the second deep processing reactor (12) and third deep processing reactor (13) entrance are equal
It is connected with gas reservoir (2)；
The outlet of first deep processing reactor (11) is connected with the first afterproduct treating column (14), the second deep processing reactor (12)
It is connected with second secondary product purification tower (15)；Third deep processing reactor (13) and third afterproduct treating column (16) phase
Even.
4. a kind of coal tar fraction reaction-separation-reaction according to claim 4 prepares the device of chemicals, feature
It is, the first afterproduct treating column (14) is connected with the first afterproduct storage tank (17), second secondary product purification tower (15)
It is connected with second secondary product storage tank (18), third afterproduct treating column (16) is connected with third afterproduct storage tank (19).
5. a kind of coal tar fraction reaction-separation-reaction according to claim 1 prepares the device of chemicals, feature
It is, polycyclic aromatic hydrocarbon separator (6) includes separator body, feed inlet (20), agitating paddle (21), collet (22), insulating box
(23), concentrator bowl (24), filter membrane (25) and separation controller (28)；Wherein, be provided in collet (22) insulating box (23) and
Concentrator bowl (24)；It is provided with agitating paddle (21) in insulating box (23), is provided with feed inlet (20), insulating box at the top of insulating box (23)
(23) be arranged on concentrator bowl (24), concentrator bowl (24) includes inner barrel and outer barrel, and inner cylinder is set in outer cylinder, inner barrel and outer barrel it
Between be provided with filter membrane (25)；Concentrator bowl (24) and insulating box (23) with separate controller (28) and be connected.
6. a kind of coal tar fraction reaction-separation-reaction according to claim 5 prepares the device of chemicals, feature
It is, the aperture of filter membrane (25) is 4-5 μm；Inner cylinder bottom is provided with solid phase discharge port (27), and outer cylinder bottom is provided with liquid phase and goes out
Material mouth (26).
7. a kind of prepare chemical processes based on device described in any one of claim 1-6, which is characterized in that coal tar
Oil is delivered into fraction seperation tower (3), and distillation obtains 210-360 DEG C of mixed fraction oil；Or coal tar is through delivering into
Fraction seperation tower (3) is distilled lateral line discharging and obtains single distillate, respectively naphtalene oil, naphtalene oil or carbolineum；
Single distillate or mixed fraction oil are delivered in the dealkylation device (5) for being filled with dealkylation catalyst, de-
It is delivered to level-one polycyclic aromatic hydrocarbon separator (6) after being reacted in alkylation reaction device (5), solid is precipitated at 145-148 DEG C, so
After be separated by filtration, obtained solid is pyrene；Gained liquid phase enters in second level polycyclic aromatic hydrocarbon separator (7), is precipitated at 98-100 DEG C
Solid, centrifugal filtration, obtained solid are phenanthrene；Gained liquid phase enters the third deep processing reaction for being filled with selective hydrocatalyst
In device (13), after being reacted in third deep processing reactor (13), naphthane is obtained；
Pyrene is added in the first deep processing reactor (11) for being filled with selective hydrocatalyst, is reacted in the first deep processing
Device is reacted in (11), obtains hexahydro pyrene；
Phenanthrene is added to the second deep processing reactor (12) for being filled with selective hydrocatalyst, in the second deep processing reactor
(12) it is reacted in, obtains dihydro phenanthrene.
8. according to claim 7 prepare chemical processes, which is characterized in that carried out in dealkylation device (5) anti-
The condition answered are as follows: mass space velocity ratio is 2-3WHSVh-1, it is 400-520 DEG C in temperature, reaction first pressing is 1-4MPa, reacts 2-
8h；
It reacted in the first deep processing reactor (11), carry out reaction in the second deep processing reactor (12) and in third
The condition reacted in deep processing reactor (13) is equal are as follows: mass space velocity ratio is 2-3WHSVh-1, it is 160-240 in temperature
DEG C, reaction first pressing is 4-8MPa, reacts 4-8h.
9. according to claim 7 prepare chemical processes, which is characterized in that
Dealkylation catalyst is made by following procedure: active component, auxiliary agent is supported on carrier using equi-volume impregnating,
4-6h is stood, roasts 4-6h after then drying at 450-550 DEG C, obtains dealkylation catalyst；Wherein, based on mass fraction,
The load capacity of active component is 3-9%, and the load capacity of auxiliary agent is 0.07-0.5%；
Selective catalytic hydrogenation catalyst is made by following procedure: active component being supported on catalysis using equi-volume impregnating
It on agent carrier, through ultrasound, stands, roasts 4-6h at 450-550 DEG C after then drying, obtain selective catalytic hydrogenation catalysis
Agent；Wherein, based on mass fraction, the load capacity of active component is 12%-36%.
10. according to claim 9 prepare chemical processes, which is characterized in that when prepared by dealkylation catalyst, active group
It is divided into one of Ni, Mo, Co, W or a variety of；Auxiliary agent is lanthanum；Carrier is the mixing of one or more of ZSM-5, Beta, HY
Object；
When selective catalytic hydrogenation catalyst preparation, carrier SiO2、TiO2、Al2O3, one or more of HY, HZSM-5
Mixture；Active component is one or more of Co, Mo, Ni, W.
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| CN111584012A (en) * | 2020-04-17 | 2020-08-25 | 中国神华煤制油化工有限公司 | Modeling method and control device for raw material reaction dynamics model |
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| EP1165473B1 (en) * | 1999-04-08 | 2004-06-23 | Kabushiki Kaisha Kobe Seiko Sho | Process for preparing 2,6-dialkylnaphtalene |
| CN103773489A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrogenation method for treating high-nitrogen high-aromatic hydrocarbon inferior diesel oil raw materials |
| CN208865285U (en) * | 2018-09-12 | 2019-05-17 | 大闽食品（漳州）有限公司 | One kind standing clarified separation system for concentrate refrigeration |
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| EP1165473B1 (en) * | 1999-04-08 | 2004-06-23 | Kabushiki Kaisha Kobe Seiko Sho | Process for preparing 2,6-dialkylnaphtalene |
| CN103773489A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrogenation method for treating high-nitrogen high-aromatic hydrocarbon inferior diesel oil raw materials |
| CN208865285U (en) * | 2018-09-12 | 2019-05-17 | 大闽食品（漳州）有限公司 | One kind standing clarified separation system for concentrate refrigeration |
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| CN111584012A (en) * | 2020-04-17 | 2020-08-25 | 中国神华煤制油化工有限公司 | Modeling method and control device for raw material reaction dynamics model |
| CN111584012B (en) * | 2020-04-17 | 2023-10-03 | 中国神华煤制油化工有限公司 | Modeling method and control device for raw material reaction kinetic model |
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