CN105316018B - A kind of coal tar deep processing preprocess method - Google Patents
A kind of coal tar deep processing preprocess method Download PDFInfo
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- CN105316018B CN105316018B CN201410384926.5A CN201410384926A CN105316018B CN 105316018 B CN105316018 B CN 105316018B CN 201410384926 A CN201410384926 A CN 201410384926A CN 105316018 B CN105316018 B CN 105316018B
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- coal tar
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- desalting
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Abstract
The present invention using centrifuge, gas back-flushing filtering, distillation, high voltage electric field carry out de- slag to coal tar, deamination water, dephenolize, desalination separation technology, it is adapted to the pretreatment of high temperature coal-tar, medium temperature coal tar and coalite tar, the ammoniacal liquor isolated can recycle, phenols directly or after refined is sold as industrial chemicals, avoid containing ammonia, phenol discharge of wastewater, the problems such as phenol hydrogenation wastes hydrogen energy source, improve the added value of coal tar.
Description
Technical field
The present invention relates to a kind of preprocess method of coal tar raw material, especially a kind of coal tar deep processing pretreatment side
Method, belong to chemical technology field.
Background technology
With the crisis of petroleum resources, seeking the approach of new oil product resource turns into focus of concern, therefore coal tar
Processing industry attracts people's attention once again.Except traditional coal tar processing product development such as naphthalene, anthracene, phenols and pitch
New purposes is gone out, the coai-tar product being processed further out by hydrotreating turns into the product of the more market competitiveness.
Coal tar hydrogenating is produced light Fuel oil tech and developed faster, reasonably processing and utilization coal tar, not only
The demand of various industrial chemicals can be provided, and petroleum resources pressure in short supply can also be alleviated, increase added value of product
Extend with product structure is expanded.
Applicant, which retrieves, to be found, the Chinese patent application of Application No. 200910045839.6 discloses a kind of coal tar coupling
Eddy flow purification method is closed, this method comprises the following steps：(a) coal tar is sufficiently mixed with trapping agent, produced coal with extraction
The salinity disperseed in tar；(b) liquid-liquid rotational flow separation is carried out to the coal tar for having extracted wherein scattered salinity, with separation
Go out salinity, obtain desalination coal tar；(c) standing sedimentation is carried out to desalination coal tar, to remove moisture therein, be dehydrated
Coal tar；(d) solid-liquid rotational flow separation is carried out to dehydrated coal tar, to remove solid particle therein, obtains being stripped of solid
The coal tar of particle；It is therein micro to remove and (e) carries out mini-hydrocyclone separation to the coal tar for being stripped of solid particle
Moisture.The problem of it is present be：The complex mixture that coal tar is made up of polar substances and apolar substance, between molecule
Existing Van der Waals force, there is also hydrogen bond, cyclonic separation can only be partially separated out non-ideal material, and phenols can also be formed with water
Hydrogen bond, therefore, the water in coal tar are difficult to be removed by cyclonic separation, and coal ash is adhered on tar in addition, and density is relatively small
Also environment containing materials such as ammonia, phenols in the water isolated in addition, can not be polluted, the present invention passes through first by cyclonic separation
Centrifuge, filters mechanical admixture is removed, 10 μm of removal efficiencies is reached 98%, secondly through being distilled off ammonia, water,
Phenols, last and then progress two level or three-level Crude Desalting System remove the salinity in coal tar, the moisture remained in coal tar
Removed by flash distillation.The Chinese patent of Application No. 200910048881.3 discloses a kind of middle coalite tar deep processing side
Method, this method will be fractionated after middle low temperature coal tar pretreatment of raw material, obtain light fraction, carbolic oil and heavy distillat, carbolic oil is taken off
Phenol processing, phenol products and dephenolize oil are obtained, dephenolize oil carries out pyrogenetic reaction jointly with step aforesaid heavy fractions, obtains each
Kind coking product, wherein at least one of coking naphtha, coker gas oil and wax tailings gently evaporate with what raw material was fractionated to obtain
Mixing is divided to carry out hydrofinishing and hydrocracking reaction, the hydrotreated naphtha for being hydrocracked to obtain carries out catalytic reforming-aromatic hydrocarbons and taken out
Carry, obtain the products such as benzene,toluene,xylene and solvent naphtha.Its shortcoming is that centrifugal filtration, electro-desalting are mentioned in coal tar pretreatment
Dehydration, centrifugal filtration only remove most of mechanical admixture, and phenols, ammonia are still present in coal tar, cause coal tar easily to emulsify
Coal tar is divided into five layers in electrical desalter body：Light oil, light oil and water emulsification layer, water layer, water and heavy oil emulsive layer, heavy oil；Make
Electro-desalting can not stable operation, electro-desalting draining enriched ammonia, phenol, pollute environment.The China of Application No. 200910224893.7
In coal tar pretreating process disclosed in patent and complete set of equipments, the process route of coal tar pretreatment is：Feed coal tar tank
Interior heat sink drop → raw oil pump conveying → ultra centrifugal separation → heat exchanger heating → filter removal of impurities → one-stage water wash electric field point
From → two level washing electric field separates → pretreatment corrected oil deep processing.The patent is similar with 200910048881.3 pretreatments, only
Only particularly point out before centrifugation and settled in hot settling tank, a part of ammoniacal liquor and a small amount of can be only deviate from settling tank
Impurity.The Chinese patent application of Application No. 201210007868.5 discloses a kind of coal tar hydrogenating combinatorial delays coking
Full cut method of comprehensive utilization, this method include coal tar pretreatment, coal tar efficiently separate, heavy end delayed coking
With four units of fixed bed hydrogenation, final products are fine chemicals, gasoline, diesel oil, the pitch cokes such as phenol, naphthalene, and operating procedure is such as
Under：
(1) enter in coal tar pretreatment unit, pending raw material full distillate oil through water removal, dedusting, desalination purified treatment
Next unit；(2) unit is efficiently separated in coal tar, pretreated coal tar enters fractionating column, fractionates out 170~210 DEG C
Carbolic oil cut and 210~230 DEG C of fraction of naphthalene oil, carbolic oil and naphtalene oil are further refining to obtain fine chemicals phenol and naphthalene, ＜
170 DEG C of light oil distillate removes fixed bed hydrogenation unit, and remaining cut removes heavy end delayed coking unit；(3) in heavy end
Delayed coking unit, delayed coking charging is 230 DEG C of ＞ coal tar fraction, and delayed coking product is light-weight fuel oil and drip
Blue or green burnt, for pitch coke as final products, light-weight fuel oil enters fixed bed hydrogenation unit；(4) in fixed bed hydrogenation unit, coal tar
Remaining cut and the mixing of delayed coking light-weight fuel oil after oily 170 DEG C of ＜ light oil distillate, carbolic oil and naphtalene oil are refined are used as and added
The raw material of hydrogen, hydrogenated products are rectifying to obtain final products gasoline and diesel oil, and it is logical first that a small amount of tail oil circulation, which is hydrogenated with the patent,
After crossing cyclonic separation dedusting, it is dehydrated subsequently into dehydrating tower, coal tar enters fractionating column after dehydration, is mentioned in the content of the invention de-
Salt treatment, the method for not having desalting processing facility and specific desalination in flow chart, dehydration and tar separation are in two towers in addition
Middle progress, the input of equipment is added, passes through coking before hydrogenation, part of coal tar is become coking, coal tar comprehensive utilization ratio
It is not high.
The content of the invention
It is an object of the invention to：It is proposed one kind and can make full use of raw material, establish ideal basic for hydrotreating, together
Shi Youxiao avoids the coal tar deep processing preprocess method of chemical pollution.
Due to containing substantial amounts of ammoniacal liquor, salt and solid impurity in coal tar, coal tar and the water capacity easily form stable emulsification
Liquid, in addition, ammonium salt can resolve into free acid and ammonia, cause pipeline and the heavy corrosion of equipment, solid impurity is mainly duff
Powder, coke powder and carbon powder etc., these solid impurities can block pipeline, therefore be needed before coal tar deep processing to coal tar
Carry out purified treatment.
Applicant is had found by studying, and after mechanical admixture is removed, should remove the ammonia in coal tar before electro-desalting first
Water, aldehydes matter, because tarry distillate can be made to be emulsified with water containing substantial amounts of ammoniacal liquor in one side coal tar, the opposing party
Face, phenolic component can form hydrogen bond with polar functional group in coal (such as water-OH), make electric desalting and dewatering effect is poor not reach
Index, and the sewage discharged contains substantial amounts of phenols, ammonia, pollutes environment, and phenols can produce water again in hydrogenation process, waste
Hydrogen.On the basis of the studies above, in order to reach object above, coal tar deep processing preprocess method of the invention, including with
Lower step：
The first step, centrifugation --- the solid impurity in coal tar is separated by centrifuge, makes solid contained therein
Grain diameter is less than 50 μm；
Second step, it is separated by filtration --- the solid impurity in coal tar is further separated by filtration by filtering material, makes it
In contained more than 15 μm solids removal rates more than 98%；
3rd step, by after centrifuging and being separated by filtration coal tar heat, distillation cut out ammoniacal liquor, light oil, carbolic oil, will
Ammoniacal liquor is further handled with carbolic oil, and carbolic oil directly or after refined be used as industrial chemicals, by the density isolated at 20 DEG C it is little
In 0.98g/cm3Light component, mixing add water, metal remover, demulsifier by static mixer mixing；Remaining restructuring
Divide and add water, metal remover, demulsifier by static mixer mixing；
4th step, light component and heavy constituent mixed liquor handled by two-stage or three-level electric desalting and dewatering respectively, removing salt,
Water and tiny mechanical admixture；
5th step, by the light component after electro-desalting, heavy constituent distinguish distillation dehydration, make its moisture content be less than 0.05%；Or
Light, heavy constituent is mixed distillation dehydration by person makes its moisture content be less than 0.05%；
6th step, light, the heavy constituent after the dehydration of the 5th step are mixed and remove hydrogenation plant.
For above method using removing mechanical admixture, distillation removes ammonia and phenols, then carries out desalting and dewatering method, reduces corruption
Erosion and environmental pollution, improve the comprehensive utilization ratio of coal tar.In the second step, filter type filters for gas back-flushing.
In 3rd step, the ammoniacal liquor for distilling to obtain is reclaimed by conventional acid wash, generates ammonium sulfate, carbolic oil is by normal
The phenols that rule acid-alkali refining obtains avoids waste hydrogen, the reluctant problem of phenol wastewater as industrial chemicals.
Light component and heavy constituent mixed liquor are handled by two-stage or three-level electric desalting and dewatering respectively in the 4th described step,
Salt, water and tiny mechanical admixture are removed, the requirement of hydrogenating materials is being reached by the 5th step；
Mainly by coal tar fractional distillation, ----electric desalting and dewatering ----hydrogenation produces light-weight fuel oil and other chemical industry to the present invention
Product.Using centrifuge, gas back-flushing filtering, distillation, high voltage electric field carry out de- slag to coal tar, deamination water, dephenolize, de-
The technology of salt separation, is adapted to the pretreatment of high temperature coal-tar, medium temperature coal tar and coalite tar, and the ammoniacal liquor isolated can return
Receive and utilize, phenols directly or after refined is sold as industrial chemicals, avoids wasting hydrogen energy source containing ammonia, phenol discharge of wastewater, phenol hydrogenation
The problems such as, improve the added value of coal tar.
Embodiment
The coal tar deep processing preprocess method of the present embodiment, comprises the following steps：
The first step, centrifugation --- the solid impurity in coal tar is separated by centrifuge, makes solid contained therein
Grain diameter is less than 50 μm；
Second step, it is separated by filtration --- the solid impurity in coal tar is further separated by filtration by filtering material, makes it
In contained more than 15 μm solids removal rates more than 98%；
3rd step, by after centrifuging and being separated by filtration coal tar heat, ammoniacal liquor, light oil, carbolic oil are distilled out, by ammoniacal liquor
Further handled with carbolic oil, dephenolize oil and heavy constituent mixing after carbolic oil is refined, add water, metal remover, demulsifier by quiet
State blender mixes；
4th step, dephenolize oil and heavy constituent mixed liquor are passed through to two-stage or the processing of three-level electric desalting and dewatering, removing salt, water
And tiny mechanical admixture；
5th step, by the blending ingredients distillation dehydration after electro-desalting, its moisture content is less than 0.05%；
6th step, the light oil that the 3rd step distills out and the 5th step are dehydrated after mixed reorganization divide and mix boiling bed hydrogenation
Device.
Example one
Coal tar is centrifuged, filtered twice, mechanical admixture particle diameter is not more than 15 μm, and coal tar is heated to
135 DEG C, injection accounts for the water of coal tar gross weight 10%, and addition accounts for the μ g/g demulsifiers of coal tar gross weight 50；The μ of metal remover 40
G/g, mixed into static mixer, mixing intensity 50KPa, the de- tank electric field intensity inside high of electricity is 800V/cm, and 40 are stopped in electric field
Minute, tar property and property after hydrogenation see the table below after three-level electricity is de-
Example two
Coal tar is centrifuged, filtered twice, mechanical admixture particle diameter is not more than 15 μm, and coal tar is heated to
130 DEG C, injection accounts for the water of coal tar gross weight 8%, and addition accounts for the μ g/g demulsifiers of coal tar gross weight 60；The μ g/ of metal remover 70
G, mixed into static mixer, mixing intensity 60KPa, the de- tank electric field intensity inside high of electricity is 100V/cm, and 35 points are stopped in electric field
Clock, tar property and property after hydrogenation see the table below after three-level electricity is de-
In addition to the implementation, the present invention can also have other embodiment.It is all to use equivalent substitution or equivalent transformation shape
Into technical scheme, all fall within the protection domains of application claims.
Claims (4)
1. a kind of coal tar deep processing preprocess method, comprises the following steps：
The first step, centrifugation --- the solid impurity in coal tar is separated by centrifuge, makes solid particle contained therein
Particle diameter is less than 50 μm；
Second step, it is separated by filtration --- the solid impurity in coal tar is further separated by filtration by filtering material, makes wherein institute
More than the 15 μm solids removal rates contained are more than 98%；
3rd step, by after centrifuging and being separated by filtration coal tar heat, distillation cut out ammoniacal liquor, light oil, carbolic oil, by ammoniacal liquor with
Carbolic oil is further handled, and carbolic oil directly or after refined is used as industrial chemicals, and the density isolated is not more than at 20 DEG C
0.98g/cm3Light component, mixing add water, metal remover, demulsifier by static mixer mixing；Remaining heavy constituent adds
Enter water, metal remover, demulsifier to mix by static mixer；
4th step, light component and heavy constituent mixed liquor handled by two-stage or three-level electric desalting and dewatering respectively, removing salt, water with
And tiny mechanical admixture；
5th step, by the light component after electro-desalting, heavy constituent distinguish distillation dehydration, make its moisture content be less than 0.05%；Or will
Gently, heavy constituent mixing distillation dehydration makes its moisture content be less than 0.05%；
6th step, light, the heavy constituent after the dehydration of the 5th step are mixed and remove hydrogenation plant.
A kind of 2. coal tar deep processing preprocess method according to claim 1, it is characterised in that in the second step, filtering
Mode filters for gas back-flushing.
A kind of 3. coal tar deep processing preprocess method according to claim 1, it is characterised in that in the 3rd step, distillation
Obtained ammoniacal liquor is reclaimed by conventional acid wash, generates ammonium sulfate, and carbolic oil passes through the phenols conductization that conventional acid-alkali refining obtains
Work raw material.
A kind of 4. coal tar deep processing preprocess method according to claim 1, it is characterised in that the light component isolated, again
Component carries out electric desalting and dewatering respectively；Light component electro-desalting electric field is arranged in desalter middle and upper part, and oil water mixture is from electro-desalting
Pot bottom enters；Heavy constituent electro-desalting electric field arranges middle and lower part, and heavy constituent oil water mixture enters from top.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106367093A (en) * | 2016-10-18 | 2017-02-01 | 北京化工大学常州先进材料研究院 | Preparation method of low-ash mesophase pitch |
| CN106929082A (en) * | 2017-04-06 | 2017-07-07 | 上海蓝科石化环保科技股份有限公司 | A kind of coal tar preprocess method and system |
| CN109097085B (en) * | 2017-06-20 | 2021-11-16 | 中国石油化工股份有限公司 | Coal tar pretreatment method |
| WO2020001205A1 (en) * | 2018-06-27 | 2020-01-02 | 河南龙成煤高效技术应用有限公司 | Method and apparatus for pretreating low temperature coal tar |
| CN110872530A (en) * | 2018-09-04 | 2020-03-10 | 武汉金中石化工程有限公司 | Coal tar pretreatment method and system |
| CN111154506B (en) * | 2018-11-08 | 2021-12-07 | 中国石油化工股份有限公司 | Method for producing white oil by hydrogenation of coal tar |
| CN110093184A (en) * | 2019-05-31 | 2019-08-06 | 武汉金中石化工程有限公司 | A kind of inferior heavy oil floating bed hydrogenation feed pretreatment technique |
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