CN106281407A - The preprocess method of a kind of coal tar and the production method of fuel oil - Google Patents
The preprocess method of a kind of coal tar and the production method of fuel oil Download PDFInfo
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Abstract
The present invention relates to oil product manufacture field, disclose the preprocess method of a kind of coal tar and the production method of fuel oil.The preprocess method of described coal tar include mixing coal tar and fuel oil after as raw oil, carry out electro-desalting with water and demulsifier after then being mixed by described raw oil.The method using the present invention carries out pretreatment to coal tar; wherein metal impurities and the content of salt can be significantly reduced such that it is able to reduce the harm to follow-up hydrogenation processing procedure of these impurity, protect hydrogenation catalyst; reduce the speed that reactor pressure decrease increases, extend cycle of operation.
Description
Technical field
The present invention relates to preprocess method and the production method of a kind of fuel oil of a kind of coal tar.
Background technology
Along with World Economics and the fast development of China's economic, the petroleum resources as fuel are more and more tighter
?.Coal tar is the significant by-products of coking industry, Coal Chemical Industry and coal gasification, its boiling range and composition and stone
Oil is close.China has become coke the biggest in the world and coal tar manufacturing country, and coal tar yield is continuously increased.
Coal tar oil composition is based on aromatic hydrocarbon, and polycyclic aromatic hydrocarbon, metal, salt and sulfur nitrogen oxygen impurities content are high.Mesh
Before, coal tar is typically by using as inferior fuel after being in harmonious proportion, and economic worth is low, and combustion process ring
Environment pollution is serious.Therefore, by coal tar deep processing to produce fuel oil such as gasoline and diesel oil, can significantly carry
The value of high coal tar, reduces environmental pollution, has significant economic benefit, social benefit and ring
Protect benefit.
At present, the technology that coal tar produces fuel oil by hydrogenation is as follows:
CN1766058A discloses a kind of full fraction of coal tar hydroprocessing technique, this process technology utilization
Suspension bed hydrogenation process processes full fraction of coal tar, loops back suspension bed by evaporating the tail oil being a little more than 370 DEG C
Reactor is further converted to fuel oil.
CN101724461A discloses the catalystic hydrogenation of coal tar of a kind of productive, lightweight and clean fuel oil though and processes
Method, coal tar is carried out prefractionation by the method, removes the heavy constituents such as Colophonium and heavy metallic salt and solid
Impurity etc., cut the most respectively less than 300 DEG C and the fraction of 300-380 DEG C is as Hydrogenation raw oil, it
After both fractions are reacted in different reactor.But, coal tar is not carried out by the method
Fully utilized.
CN101240191A discloses a kind of method that coal tar heavy fractioning hydrogenation produces high-grade fuel oil,
The method uses hydrofinishing-hydrocracking combined process, specifically includes coal tar heavy fractioning and mixes with hydrogen
Close and enter hydrofining reaction district, after the separated system of effluent after refining, obtain Petroleum, diesel oil
And heavy distillat, wherein heavy distillat enters hydrocracking reaction district, the hydrocracking reaction effluent portion of gained
Divide or all circulation enters piece-rate system as hydrorefined charging, remainder.
CN103540351A discloses a kind of group technology processing full fraction of coal tar, and this technique is one
Plant and slurry bed system hydrotreating and fixed bed hydrogenation are processed technique combination processing full fraction of coal tar
Combined technical method, concrete steps include lightweight coal full fraction of coal tar being divided into less than or equal to 350 DEG C
Tarry distillate and more than the heavy coal tar fraction of 350 DEG C, the heavy coal tar fraction more than 350 DEG C with
The reaction of slurry bed system hydrogenation plant is entered, the partial hydrogenation tail oil circulation in product after the mixing of hydrogen, catalyst
To paste state bed reactor, 350-470 DEG C of cut fraction hydrogenation tail oil is delivered to solid after filtering and removing solid particle
Fixed bed residual hydrogenation equipment, the light tar fraction less than or equal to 350 DEG C and hydrogen pass through feed(raw material)inlet
Enter in fixed bed residual hydrogenation equipment and react.
The difficult point of coal tar hydrogenating is: (1) coal tar density is big, poor fluidity；(2) in coal tar
The impurity contents such as metal, salt, solid particle are high.These impurity can cause in follow-up hydrogenation reaction and add
Hydrogen catalyst is poisoned, and bed pressure drop increases, it is difficult to realize the long-term operation of device.Therefore, at hydrogenation
Before typically require coal tar carried out pretreatment.
Preconditioning technique before existing coal tar hydrogenating is as follows:
CN101838550A discloses the preprocess method of a kind of coal tar, and the method includes coal tar
Being mixed and heated to 50-150 DEG C with extractant A, described extractant A is diesel oil, kerosene or from coal tar
One or more in the intermediate oil of oil hydrogenation plant out hydrogenated oil, mix gained afterwards
Liquid isolates soluble substance and impure extraction insoluble matter by sedimentation type centrifuge.
CN101012385A discloses the preprocess method of a kind of coal tar, and the method includes coal tar
Mix with distillate and aromatic hydrocarbons respectively and carry out two step extractions with by the most of impurity removal in coal tar.
CN102079983A discloses a kind of coal tar pretreating process and complete set of equipments, its be main by
Coal tar raw material storage tank, three phase centrifugation seperator, automatic backwashing filter, one-level high voltage electric field separate
The integrated pretreatment system that tank, two grades of high voltage electric field knockout drums etc. collectively constitute.This system uses high pressure
The pulse power improves the treatment effect of two-stage electric field separates equipment.
Owing to coal tar density is big, impurity content is high, and prior art uses sedimentation or the mode of centrifugation
All it is difficult to effectively remove the metal in coal tar and salt, and uses the method for electric field to there is desalination electric current
Greatly, power consumption height even send situation about not powering on, bad to coal tar pretreating effect, after so causing
Continuous hydrogenation catalyst poisoning, reactor bed pressure drop increase, and cycle of operation shortens.
Summary of the invention
The invention aims to overcome and use existing method to be difficult to the gold effectively removing in coal tar
Belong to impurity and the defect of salt, and the preprocess method of a kind of new coal tar and a kind of fuel oil are provided
Production method.
Specifically, the invention provides the preprocess method of a kind of coal tar, the method includes coal tar
As raw oil after mixing with fuel oil, after then being mixed by described raw oil, carry out electricity with water and demulsifier
Desalination.
Present invention also offers the production method of a kind of fuel oil, the method includes using coal tar above-mentioned
Method carries out pretreatment, and carries out hydrogenation essence after the oil-phase product that described pretreatment obtained and hydrogen mixing
System reaction, then isolates diesel oil distillate and tail oil fraction from the product of described hydrofining reaction, connects
And carry out hydrocracking reaction after described tail oil fraction being mixed with diesel oil distillate partly and hydrogen；Described
Diesel oil distillate is boiling point fraction between 220-350 DEG C, and described tail oil fraction is that boiling point is higher than 350 DEG C
Fraction.
Owing to coal tar is of poor quality, the content of metal and salt is high, uses existing preprocess method to be difficult to reality
The now effective demetallated purpose of desalination, thus catalyst poisoning in follow-up hydrogenation processing procedure can be caused,
Bed pressure drop raises, and the situation of plant running cycle time occurs.And the present inventor is through deeply
Find after research, the preprocessing process of coal tar adds fuel oil, it is possible to be effectively improved coal tar
Character, can not only operate by continuous and stable during electro-desalting, but also can significantly reduce coal tar
Middle metal impurities and the content of salt, thus decrease the harm to follow-up hydrogenation processing procedure of these impurity,
Protect hydrogenation catalyst, reduce the speed that reactor pressure decrease increases, extend cycle of operation.
Additionally, coal tar oil composition is very different with stone oil composition, quite a lot of have for breaking petroleum emulsion
There is the demulsifier of very good effect, be but difficult to for coal tar breakdown of emulsion obtain good effect.This be probably by
In, on the one hand, containing the more solid particle based on coal dust in coal tar, these solid particles have
Amphipathic property so that Gu oil-water-three-phase intersection stability strengthens, hinder the coalescence that W/O drips,
Cause breakdown of emulsion difficulty；On the other hand, coal tar does not contain only a large amount of phenol and homologue thereof, but also
Containing more polycyclic aromatic hydrocarbon compound, these materials can affect the process of breakdown of emulsion.
And a preferred embodiment of the invention, when will be with alkyl phenolic resin and/or alkyl phenol
Polyimide resin is that the polyoxyethylene polyoxypropylene block polyether for preparing of initiator is at the preprocessing process of coal tar
Middle when using as demulsifier, owing to this demulsifier has an amphipathic property, and its amphipathic property
Size just can significantly change solid particle and aqueous phase and the contact angle of oil phase in coal tar, reduce oil-
Gu water-three-phase intersection stability, therefore there is especially significant demulsification.Additionally, this demulsifier
Have with phenol as functional group, and containing a large amount of phenol and homologue thereof in coal tar, according to similar
Mix principle, Gu described demulsifier can rapidly diffuse into oil-water two-phase interface and oil-water-three phase boundary
And adsorb on these interfaces, therefore use above-mentioned preferred demulsifier that coal tar emulsion is had breakdown of emulsion
The advantage that speed is fast, demetalization desalting effect significantly improves.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.?
In accompanying drawing:
Coal tar preprocess method and the one of the production method of fuel oil that Fig. 1 provides for the present invention are concrete
Process chart.
Description of reference numerals
1-coal tar；2-water；3-demulsifier；4-metal remover；5-static mixer；6-first order electricity takes off
Salt device；7-oil phase；8-first order electro-desalting draining；9-secondary mixer；10-second level electro-desalting dress
Put；11-oil phase；12-first order electro-desalting draining；13-hydrogen；14-hydrofining reactor；15-is raw
Become oil；16-hydrogen-rich gas；17-high-pressure separator；18-moisture；19-gas；20-fractionating column；21-
Hydrocracking reactor；22-is hydrocracked generation oil；23-gasoline fraction；24-diesel oil distillate.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The preprocess method of coal tar that the present invention provides include mixing coal tar and fuel oil after as
Raw oil, carries out electro-desalting with water and demulsifier after then being mixed by described raw oil.
The preprocess method of coal tar provided according to the present invention, although as long as pretreated at coal tar
Journey adds fuel oil and just can improve demetalization and the desalting effect of coal tar, but in order to significantly more
Reduce the content being present in the metal impurities in coal tar after pretreatment and salt, it is preferable that described former
In material oil, the weight ratio of coal tar and fuel oil is 1:0.2-2, particularly preferably 1:0.5-1.
The consumption of water used in preprocessing process and demulsifier is not particularly limited, preferably by the present invention
Ground, relative to the described raw oil of 100 weight portions, the consumption of described water is 2-10 weight portion, described
The consumption of demulsifier is 0.001-0.01 weight portion；It is highly preferred that described former relative to 100 weight portions
Material oil, the consumption of described water is 3-6 weight portion, and the consumption of described demulsifier is 0.003-0.006 weight portion.
The kind of described demulsifier can be commonly used in the art various can be in coal tar electro-desalting process
In for breakdown of emulsion to reduce the material of the content of metal therein and salt.One according to the present invention is the most real
Executing mode, described demulsifier is prepared as initiator with alkyl phenolic resin and/or alkyl phenol polyimide resin
Polyoxyethylene polyoxypropylene block polyether.Wherein, described alkyl phenolic resin refers on phenolic resin phenyl ring
Hydrogen at least partly replaced by alkyl after the product that obtains, described alkyl phenolic resin is generally of formula (1)
Shown construction unit, wherein, R is C5-C20Alkyl, preferably C8-C15Alkyl；N and m
Mol ratio be (1-5): 1, be preferably (1.5-3): 1.Described alkyl phenol polyimide resin is alkyl phenol (bag
Include the multi-ring phenol of alkyl), polyamine compounds and the condensation reaction products of formaldehyde, its structure is former along with synthesis
Expect that alkyl phenol (including the multi-ring phenol of alkyl) and the change of polyamine compounds structure change.According to one
Detailed description of the invention, described alkyl phenol polyimide resin has the construction unit shown in formula (2).
The molecular size range of described demulsifier is not particularly limited by the present invention, but in order to preferably remove
Metal impurities in coal tar and salt, it is preferable that the weight average molecular weight of described demulsifier is 3000-10000,
More preferably 4000-7000.
The present invention is to the content of each construction unit in described polyoxyethylene polyoxypropylene block polymer demulsifier
It is not particularly limited, such as, polyoxyethylene structure list in described polyoxyethylene polyoxypropylene block polyether
The content of unit can be 20-50 weight %, preferably 30-40 weight %；Polyoxypropylene construction unit
Content can be 50-80 weight %, preferably 60-70 weight %.
A preferred embodiment of the invention, the preprocess method of described coal tar is additionally included in institute
Before stating electro-desalting, metal remover is mixed together with raw oil, water and demulsifier, so can
Significantly more reduce metal impurities and the content of salt in coal tar.Described metal remover can be existing respectively
Plant the reagent that metal impurities can be removed, these those skilled in the art all can be known, do not go to live in the household of one's in-laws on getting married at this
State.Additionally, the consumption of described metal remover can select according to the content of metal impurities in coal tar,
As a rule, for the metal impurities in the described coal tar of 1mol, described metal remover
Consumption can be 2-6mol.
Additionally, the hybrid mode related in described coal tar preprocessing process typically uses static mixer
Mixing, mixing pressure reduction can be 30-150kPa.
According to a kind of detailed description of the invention of the present invention, the preprocess method of described coal tar also includes institute
State the oil phase obtained after electro-desalting and mix the step of laggard row electro-desalting the most again with water, so
The content of the metal impurities in coal tar and salt can be down to lower level.Now, described electro-desalting
Product after oil-water separation, metal impurities and salt enter aqueous phase and separate with oil-phase product, and oil phase produces
Thing carries out electro-desalting again after again mixing with the water not containing metal impurities and salt, thus removes further
Metal impurities therein and salt.Wherein, during described electro-desalting again, the consumption of water can be with for the first time
During electro-desalting, the consumption of water is same or equivalent.
Water employed in the preprocessing process of described coal tar can be purify water, it is also possible to for fresh from
Water.A preferred embodiment of the invention, when the preprocess method of described coal tar also includes
The oil phase obtained after described electro-desalting is mixed with water the step of laggard row electro-desalting the most again
Time, the water outlet that water is electro-desalting again employed in described coal tar preprocessing process, i.e. described coal
The preprocess method of tar also includes as described electro-desalting, the water outlet of described electro-desalting again is entered water
Use.
The condition of electro-desalting and electro-desalting again is not particularly limited by the present invention, and such as, described electricity takes off
The condition of salt and again electro-desalting can include that electro-desalting temperature is 80-150 DEG C independently of one another, is preferably
130-150℃；Pressure can be 0.5-2MPa, preferably 0.6-1.2MPa.In the present invention, described
Pressure refers both to gauge pressure.Additionally, the power supply of electrical desalter that described electro-desalting and again electro-desalting are used can
To be high frequency pulse power supply, it is also possible to be power of alterating and direct current, and electric field intensity can be 20-500V/cm,
It is preferably 50-200V/cm.
The production method of the fuel oil that the present invention provides includes coal tar uses said method carry out pre-place
Hydrofining reaction is carried out, then after reason, and the oil-phase product that described pretreatment obtained and hydrogen mixing
Diesel oil distillate and tail oil fraction is isolated, then by described tail oil from the product of described hydrofining reaction
Fraction carries out hydrocracking reaction after mixing with diesel oil distillate partly and hydrogen；Described diesel oil distillate is boiling
Point fraction between 220-350 DEG C, described tail oil fraction is the fraction that boiling point is higher than 350 DEG C.
The condition of described hydrofining reaction is not particularly limited by the present invention, as a rule, described in add
The condition of hydrogen refining reaction includes: average reaction temperature can be 350-420 DEG C, preferably 370-410
℃；Stagnation pressure can be 5-20MPa, preferably 10-15MPa；During liquid, volume space velocity can be 0.2-4h-1,
It is preferably 0.5-2h-1；Hydrogen to oil volume ratio can be 500-5000:1, preferably 1000-4000:1.
Described hydrofining reaction is preferably carried out in fixed bed reactors, and the catalyst of selection can be normal
The Hydrobon catalyst of rule, such as, the composition of described Hydrobon catalyst by weight percentage may be used
Thinking: molybdenum oxide 5-25%, nickel oxide 1-10%, can contain conven-tional adjuvants, remaining is containing silica
Change the carrier of the refractory oxide such as aluminum, aluminium oxide.Additionally, the pore volume of described Hydrobon catalyst is permissible
For 0.1-0.5mL/g, specific surface area can be 100-500m2/g。
In the present invention, described pore volume and specific surface area use B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature to be measured.
The consumption of diesel oil distillate during described hydrocracking reaction is not particularly limited by the present invention, example
As, relative to the described tail oil fraction of 100 weight portions, the consumption of described diesel oil distillate can be 10-40
Weight portion, preferably 20-30 weight portion.
The condition of described hydrocracking reaction is not particularly limited by the present invention, as a rule, described in add
The condition of hydrogen cracking reaction includes: average reaction temperature can be 350-420 DEG C, preferably 370-410
℃；Stagnation pressure can be 5-20MPa, preferably 10-15MPa；During liquid, volume space velocity can be 0.2-4h-1,
It is preferably 0.5-2h-1；Hydrogen to oil volume ratio can be 500-5000:1, preferably 1000-4000:1.
Described hydrocracking reaction is preferably carried out in fixed bed reactors, and the catalyst of selection can be normal
The hydrocracking catalyst of rule, such as, the composition of described hydrocracking catalyst by weight percentage may be used
Think: tungsten oxide 10-30%, nickel oxide 5-15%, a certain amount of molecular sieve (content one can be contained
As be 1-30%, such as Y type molecular sieve, beta-molecular sieve etc.), remaining is containing silicon aluminium oxide, aluminium oxide
Carrier Deng refractory oxide.Additionally, the pore volume of described hydrocracking catalyst can be
0.10-0.50mL/g, specific surface area can be 100-500m2/g。
A preferred embodiment of the invention, the production method of described fuel oil also includes described
The part obtained after hydrocracking reaction generates oil and is back to pre-treatment step as fuel oil, with coal tar
As the raw oil of pretreatment after mixing.
According to a kind of detailed description of the invention of the present invention, the production method of described fuel oil is according to shown in Fig. 1
Schematic flow sheet carry out.Specifically: by coal tar 1, be hydrocracked generation oil (fuel oil) 22,
Water 2, demulsifier 3 enter the together with optional metal remover 4 after static mixer 5 mix homogeneously
One-level electric desalting apparatus 6 carries out electro-desalting, carries out under the electric field action in first order electric desalting apparatus
Oil-water separation, salt in coal tar and metal enter aqueous phase, and aqueous phase is through first order electric desalting apparatus 6 times
Portion discharges, i.e. first order electro-desalting draining 8, and oil phase 7 is discharged from the top of first order electric desalting apparatus 6,
Being concomitantly introduced into water in secondary mixer 9 and mix, the oil-water mixture of formation enters second level electricity and takes off
Salt device 10 carries out electro-desalting again, under the electric field action of second level electric desalting apparatus 10, carries out oil
Water separates, and salt and metal enter aqueous phase, and this aqueous phase is discharged from the bottom of second level electric desalting apparatus 10,
That is, second level electro-desalting draining 12, second level electro-desalting draining 12 can drain into sewage disposal system, or
Person recycles the injection water as first order electro-desalting, and second level electric desalting apparatus 10 top is flowed out
Oil phase 11 is oil after pretreatment, and salt therein, metal and water are removed, and enters as raw material and adds
Hydrogen processing system.In hydrotreating systems, it is anti-that oil phase 11 enters hydrofinishing after mixing with hydrogen 13
Answering and carry out hydrofining reaction in device 14, reacted generation oil 15 enters high-pressure separator 17, separates
Going out hydrogen-rich gas 16, moisture 18 and liquid oil, this liquid oil then enters fractionating column 20, separates
Going out gas 19, gasoline fraction 23, diesel oil distillate 24 and tail oil fraction, described tail oil fraction is from fractionating column
Flow out bottom 20, after mixing with hydrogen 13 and part diesel oil distillate 24, enter hydrocracking reactor 21
In carry out hydrocracking reaction, the generation oil that is hydrocracked obtained after reaction 22 is back to as fuel oil
Pre-treatment step, enters pretreatment system with coal tar 2 after mixing.In the present invention, described gasoline evaporates
Be divided into boiling point fraction between initial boiling point-220 DEG C, described diesel oil distillate be boiling point 220-350 DEG C it
Between fraction, described tail oil fraction is the fraction that boiling point is higher than 350 DEG C
Hereinafter will be described the present invention by embodiment.
Embodiment 1
The preprocess method of the coal tar that this embodiment provides for the present invention is described and the production of fuel oil
Method.
Demulsifier used by this embodiment is that the polyoxyethylene prepared for initiator with alkyl phenolic resin gathers
Oxypropylene block polyethers, is produced by Research Institute of Petro-Chemical Engineering, and the trade mark is RP-yl, weight average molecular weight
Being 6000, wherein the content of polyoxyethylene construction unit is 33 weight %, polyoxypropylene construction unit
Content is 67 weight %.Metal remover is the RPD metal remover that Research Institute of Petro-Chemical Engineering develops,
Dosage is 500ppm.Hydrobon catalyst and hydrocracking catalyst are divided by Sinopec catalyst
Company's Chang Ling catalyst plant produces, and wherein, the trade mark of Hydrobon catalyst is RTC-2, is hydrocracked
The trade mark of catalyst is RCC-2.
This embodiment uses the technological process shown in Fig. 1 that coal tar is carried out pretreatment and hydrotreating.Tool
Body ground, after coal tar mixes with fuel oil, then passes through static mixer with water, demulsifier and metal remover
(wherein, being in terms of 100 weight portions by the consumption of coal tar and fuel oil, the consumption of water is 5 to mix homogeneously
Weight portion, the consumption of demulsifier is 0.004 weight portion), carry out subsequently in first order electric desalting apparatus
Electro-desalting, the oil phase obtained with water after secondary mixer mixes (relative to the oil phase of 100 weight portions,
The consumption of water is 5 weight portions) enter in second level electric desalting apparatus and carry out electro-desalting again, the oil obtained
It is mixed in hydrofining reactor with hydrogen and carries out hydrofining reaction, hydrogenation essence will be obtained afterwards
System generates oil and isolates hydrogen-rich gas, water and liquid oil in high-pressure separator, and described liquid oil exists
Fractionating column is separated into again gas, gasoline fraction, diesel oil distillate and tail oil fraction, described tail oil fraction and
After part diesel oil distillate mixes with hydrogen, (tail oil fractional distillation is 100:30 with the weight ratio of diesel oil distillate) enters
Hydrocracking reactor carries out hydrocracking reaction, afterwards the partial hydrogenation cracking obtained is generated oil and make
It is back to pre-treatment step, as raw oil after mixing with coal tar for fuel oil.This embodiment uses
Coal tar oil properties be shown in Table 1, process conditions are shown in Table 2, pretreating effect and to continuously run 4000 little
Time back end hydrogenation finishing reactor change in pressure drop data be shown in Table 3.
Embodiment 2
The preprocess method of the coal tar that this embodiment provides for the present invention is described and the production of fuel oil
Method.
The pretreatment of coal tar and the production of fuel oil is carried out according to the method for embodiment 1, except for the difference that,
The demulsifier used and process conditions are different, wherein, demulsifier be alkyl phenol polyimide resin be initiator system
(being produced by Research Institute of Petro-Chemical Engineering, the trade mark is the polyoxyethylene polyoxypropylene block polyether obtained
RP-nyl, weight average molecular weight is 8000, and wherein the content of polyoxyethylene construction unit is 25 weight %,
The content of polyoxypropylene construction unit is 75 weight %), process conditions are specifically shown in Table 2.In this embodiment
The coal tar oil properties used is shown in Table 1, pretreating effect and continuously run 4000 hours back end hydrogenations and refine
The change in pressure drop data of reactor are shown in Table 3.
Embodiment 3
The preprocess method of the coal tar that this embodiment provides for the present invention is described and the production of fuel oil
Method.
The pretreatment of coal tar and the production of fuel oil is carried out according to the method for embodiment 1, except for the difference that,
Process conditions are different, are specifically shown in Table 2.The coal tar oil properties used in this embodiment is shown in Table 1, locates in advance
Reason effect and continuously run the change in pressure drop data of 4000 hours back end hydrogenation finishing reactors and be shown in Table 3.
Embodiment 4
The preprocess method of the coal tar that this embodiment provides for the present invention is described and the production of fuel oil
Method.
The pretreatment of coal tar and the production of fuel oil is carried out according to the method for embodiment 1, except for the difference that,
In coal tar preprocessing process, coal tar be hydrocracked generate oil weight ratio be 1:0.2.This enforcement
The coal tar oil properties used in example is shown in Table 1, and process conditions are shown in Table 2, pretreating effect and transporting continuously
The change in pressure drop data turning 4000 hours back end hydrogenation finishing reactors are shown in Table 3.
Embodiment 5
The preprocess method of the coal tar that this embodiment provides for the present invention is described and the production of fuel oil
Method.
The pretreatment of coal tar and the production of fuel oil is carried out according to the method for embodiment 1, except for the difference that,
Demulsifier employed in coal tar preprocessing process is the polyoxy second with polyethylene polyamine as initiator
Alkene polyoxypropylene polyether demulsifier, the trade mark is AE1910.The coal tar oil properties used in this embodiment
Being shown in Table 1, process conditions are shown in Table 2, pretreating effect and to continuously run 4000 hours back end hydrogenations refined anti-
The change in pressure drop data answering device are shown in Table 3.
Comparative example 1
This comparative example is for illustrating preprocess method and the production method of fuel oil of the coal tar of reference.
Coal tar use simple filtration go deimpurity method to carry out pretreatment, then according to embodiment 1
Method carry out follow-up hydrotreating reaction.The coal tar oil properties used in this embodiment is shown in Table 1,
Process conditions are shown in Table 2, pretreating effect and continuously run the pressure of 4000 hours back end hydrogenation finishing reactors
Fall delta data is shown in Table 3.
Comparative example 2
This comparative example is for illustrating preprocess method and the production method of fuel oil of the coal tar of reference.
The pretreatment of coal tar and the production of fuel oil is carried out according to the method for embodiment 5, except for the difference that,
In coal tar preprocessing process, be added without fuel oil and be hydrocracked generation oil, i.e. by coal tar and water,
Electro-desalting process is carried out after demulsifier and metal remover mixing.The coal tar oil properties used in this comparative example
Being shown in Table 1, process conditions are shown in Table 2, pretreating effect and to continuously run 4000 hours back end hydrogenations refined anti-
The change in pressure drop data answering device are shown in Table 3.
Table 1 coal tar oil properties
| Project | Data |
| Density (20 DEG C), g/cm3 | 0.99 |
| Viscosity (40 DEG C), mm2/s | 73.1 |
| Viscosity (80 DEG C), mm2/s | 10.5 |
| Condensation point, DEG C | 25 |
| Tenor, μ g/g | |
| Fe | 51 |
| Ca | 198 |
| Na | 11.2 |
| Al | 10.3 |
| Salt content, mgNaCL/L | 8.5 |
Table 2 process conditions
Table 3 desalination demetalization result and change in pressure drop
As can be seen from the above results, use the method for the present invention that coal tar is carried out pretreatment, it is possible to aobvious
Write and reduce wherein metal impurities and the content of salt such that it is able to reduce these impurity and follow-up hydrogenation was processed
The harm of journey, protects hydrogenation catalyst, reduces the speed that reactor pressure decrease increases, and extends cycle of operation.
From the contrast of embodiment 1 and embodiment 4-5 it can be seen that the preprocessing process of coal tar, by coal
Tar and be hydrocracked generate oil weight ratio control the present invention preferred in the range of, or use with alkane
Base phenolic resin and/or alkyl phenol polyimide resin are initiator and prepared polyoxyethylene polyoxypropylene block gathers
Ether is as demulsifier, it is possible to the demetalization of coal tar and desalting effect are significantly improved, and more industry should
Use prospect.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (15)
1. a preprocess method for coal tar, the method is made after including mixing coal tar and fuel oil
For raw oil, after then being mixed by described raw oil, carry out electro-desalting with water and demulsifier.
Method the most according to claim 1, wherein, coal tar and fuel oil in described raw oil
Weight ratio be 1:0.2-2, preferably 1:0.5-1.
Method the most according to claim 1, wherein, relative to the described raw material of 100 weight portions
Oil, the consumption of described water is 2-10 weight portion, and the consumption of described demulsifier is 0.001-0.01 weight portion.
4. according to the method described in any one in claim 1-3, wherein, described demulsifier be with
Alkyl phenolic resin and/or alkyl phenol polyimide resin are initiator and prepared polyoxyethylene polyoxypropylene block
Polyethers.
Method the most according to claim 4, wherein, the weight average molecular weight of described demulsifier is
3000-10000。
Method the most according to claim 4, wherein, described polyoxyethylene polyoxypropylene block gathers
In ether, the content of polyoxyethylene construction unit is 20-50 weight %, and the content of polyoxypropylene construction unit is
50-80 weight %.
7. according to the method described in any one in claim 1-3, wherein, the method is additionally included in
Before described electro-desalting, metal remover is mixed together with described raw oil, water and demulsifier.
Method the most according to claim 1, wherein, the method also include by described electro-desalting it
After the oil phase that obtains mix the step of laggard row electro-desalting the most again with water.
Method the most according to claim 8, wherein, the method also includes de-for described electricity again
The water outlet of salt uses as the water that enters of described electro-desalting.
Method the most according to claim 8 or claim 9, wherein, described electro-desalting and again electro-desalting
Condition include that electro-desalting temperature is 80-150 DEG C independently of one another, pressure is 0.5-2MPa.
The production method of 11. 1 kinds of fuel oil, the method includes coal tar is used claim 1-10
Method described in middle any one carries out pretreatment, and the oil-phase product that described pretreatment obtained and hydrogen
Carry out hydrofining reaction after mixing, then from the product of described hydrofining reaction, isolate diesel oil and evaporate
Divide and tail oil fraction, add after then described tail oil fraction being mixed with diesel oil distillate partly and hydrogen
Hydrogen cracking reaction；Described diesel oil distillate is boiling point fraction between 220-350 DEG C, described tail oil fraction
For the boiling point fraction higher than 350 DEG C.
12. methods according to claim 11, wherein, the condition bag of described hydrofining reaction
Including: average reaction temperature is 350-420 DEG C, stagnation pressure is 5-20MPa, and during liquid, volume space velocity is 0.2-4h-1,
Hydrogen to oil volume ratio is 500-5000:1.
13. methods according to claim 11, wherein, during described hydrocracking reaction,
Relative to the described tail oil fraction of 100 weight portions, the consumption of described diesel oil distillate is 10-40 weight portion.
14. according to the method described in any one in claim 11-13, wherein, described in be hydrocracked
The condition of reaction includes: average reaction temperature is 350-420 DEG C, and stagnation pressure is 5-20MPa, volume during liquid
Air speed is 0.2-4h-1, hydrogen to oil volume ratio is 500-5000:1.
15. according to the method described in any one in claim 11-13, and wherein, the method also includes
The part obtained after described hydrocracking reaction is generated oil and is back to pre-treatment step as fuel oil, with
As the raw oil of pretreatment after coal tar mixing.
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