CN107557068A - A kind of method of coal tar hydrogenating and a kind of system for coal tar hydrogenating - Google Patents
A kind of method of coal tar hydrogenating and a kind of system for coal tar hydrogenating Download PDFInfo
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- CN107557068A CN107557068A CN201610512383.XA CN201610512383A CN107557068A CN 107557068 A CN107557068 A CN 107557068A CN 201610512383 A CN201610512383 A CN 201610512383A CN 107557068 A CN107557068 A CN 107557068A
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Abstract
The present invention relates to coal tar processing field, discloses a kind of method of coal tar hydrogenating and a kind of system for coal tar hydrogenating, and this method includes：Coal tar raw material introducing pretreatment unit is removed water and/or cleaned pretreatment；The material of foregoing acquisition is introduced into the slurry bed system hydrogenation reactor of slurry bed system hydrogenation unit and carries out hydro-conversion；The material of foregoing acquisition is separated and is fractionated successively, obtains light fraction, midbarrel and heavy end；And part midbarrel and remaining heavy end are recycled back in slurry bed system hydrogenation reactor and carry out hydro-conversion；And light fraction and remaining midbarrel are introduced into the finishing reactor of the fixed bed hydrogenation unit and carry out hydrofining reaction.Method provided by the invention is realized the clean and effective utilization of tar resource, is improved liquid yield to greatest extent, improve the utilization rate and value of tar resource, and extend the service cycle of device using the combination of slurry bed system and fixed bed.
Description
Technical field
The present invention relates to coal tar processing field, in particular it relates to which a kind of method of coal tar hydrogenating and one kind are used for coal
The system of hydrogenation of tar.
Background technology
As social economy grows continuously and fast, China also increasingly increases the demand of oil product.
However, oil belongs to non-renewable energy resources, increasingly exhausted crisis is faced with.By contrast, Chinese coal reserves account
Compare it is abundant, therefore, by coal preparing liquid fuel turn into coal processing and utilization a basic orientation.
With the fast development of domestic coal chemical industry especially Modern Coal-based Chemical industry, the yield of coal tar is increasingly
Greatly, the cleaning processing of coal tar and effective utilize also become more and more important.At present, conventional coal processing method is by pre- place
Reason distillation cuts the various cuts in diversity, then various cuts are entered using the methods of acid-alkali washing, distillation, polymerization, crystallization
Row processing extraction net product；Also some coal tar is directly burnt after acid-alkali refining as low-quality fuel oil, or directly
Emulsion fuel burns are used as after connecing emulsification.The impurity such as institute's sulfur-bearing, nitrogen becomes the oxidation of sulphur and nitrogen in combustion in coal tar
Thing, which is discharged into the atmosphere, causes atmosphere pollution, and large amount of sewage can be produced during acid-alkali refining, can seriously pollute environment.Cause
This, either is intended to find an effective chemistry still from the point of view of environment comprehensive use aspects from the angle of environmental protection
Processing approach, makes coal tar obtain upgrading, to expand its own value.How effectively to utilize tar resource and make it
Meet the research direction that environmental protection requirement is always various countries.
CN1766058A discloses a kind of full fraction of coal tar hydrotreating method, and specifically discloses coal tar first
Full cut is directly entered floating bed hydrogenation device, or is carried out after being well mixed with homogeneous catalyst into suspended bed device at hydrogenation
370 DEG C of water outlet, 370 DEG C of cuts of ＜ and ＞ tail oil are cut in reason and lighting reaction, the logistics generated after reaction through distilling apparatus,
Wherein 370 DEG C of cuts of ＜ enter the hydrogenated refining reaction of fixed bed reactors, and the product after then refining cuts out 150 DEG C of ＜
Gasoline and 150-370 DEG C of diesel oil, while 370 DEG C of ＞ tail oil is recycled back to suspended-bed reactor and is further converted into light oil
Product.After 370 DEG C of light oil distillates of ＜ in the prior art refine into fixed bed hydrogenation, product diesel oil property is still poor, density
It is higher, Cetane number is relatively low, in order to further improve diesel product property, add a depth and take off arylation reaction device, this is existing
On the one hand the method for technology causes plant investment increase, flow to complicate, the de- virtue of another aspect depth needs harsh reaction bar
Part, the loss of fluid product will certainly be further resulted in, i.e. the method flow complexity of the prior art offer, liquid yield are inclined
It is low.
CN101885982A discloses a kind of hydrogenation method for coal tar suspension bed of heterogeneous catalysis, and this method includes coal
Tar stock pre-processes and separated, coal tar heavy end floating bed hydrocracking and the conventional fixed bed of light fraction oil carry
The process of matter processing.Hydrogenation reaction product separates the tail oil containing catalyst after light oil and largely direct cycles to suspension bed
Reactor, small part tail oil are recycled to suspended-bed reactor after carrying out Removal of catalyst processing, further lighting, and heavy oil is complete
Portion or maximum circulation, to realize the purpose of coal tar maximum production light oil and catalyst recycling.Hanged in the invention
The raw material of floating bed reactor is 370 DEG C of ＞ coal tar heavy end, in its suspension bed course of reaction provided, 370 DEG C of ＞
Asphalitine in heavy end is more easy to mutually polymerize generation coke through radical reaction, increases and blocks reactor inner member
Probability, it have impact on the normal operation of device.
CN103059973A discloses a kind of slurry bed system and fixed bed coupling process of full fraction of coal tar hydrogenation, main bag
Include coal tar raw material pretreatment, slurry bed system is hydrocracked, first hydrogenated products are fractionated, fixed bed hydrogenation is refined and product rectifying five
Unit.Full fraction of coal tar oil pre-processes through dehydration, dedusting etc., and enters slurry bed system after mixing preheating with hydrocracking catalyst
Reactor carries out hydrocracking reaction, and reacted just hydrogenated products are fractionated into gained light components and refined into fixed bed hydrogenation
Unit, midbarrel and catalyst are recycled back to slurry bed system hydrogenation reactor, and heavy component is removed by filtration partial catalyst and split
Coke caused by change returns to tar pretreated unit circulation hydrogenation.Light components rectifying after conventional hydrofinishing obtains petrol and diesel oil production
Product.In the method that the prior art provides, its light, neutralization heavy constituent for being provided actually are corresponded to and evaporated below 370 DEG C of diesel oil of ＜
Point, 370 DEG C of wax oil cuts of ＞ and compared with wax oil weight heavy end, it uses conventional slurry bed process, and fixed bed hydrogenation unit is only
370 DEG C of following cuts of diesel oil of ＜ are processed, and to convert 370 DEG C of cuts of ＞ then needs higher conversion level, so as to increase energy consumption.
And the slurry bed system of the prior art is hydrocracked the cracking agent used containing molecular sieve, due to nitrogen content in coal tar raw material
Height, nitride is obvious to the activity inhibition of molecular sieve type cracking agent and easily causes the inactivation of cracking agent, conventional oil base
Molecular sieve type cracking agent is not suitable for slurry bed system coal tar hydrocracking used in raw material.It is and fixed in the prior art
After bed hydroprocessing is refined, product diesel oil property is still poor, and Cetane number is relatively low.
It is above-mentioned in the prior art, slurry bed system coal tar hydrogenating mainly used for reference petroleum base heavy charge such as normal pressure slag
The thinking of the slurry bed hydroprocessing such as oil, decompression residuum, its main purpose are in the lighting and removing raw material for realize heavy charge
Impurity etc..
Structure in reactor is blocked however, generating coke using the easy coking of method of above-mentioned prior art or depositing
Part, this is also one of the main reason for current coal tar slurry bed system hydrogenation plant is unable to long period steady running.
The content of the invention
The purpose of the present invention is to prevent that slurry bed system hydrogenation reactor studies on asphaltene from depositing or coking generation coke, maximum limit
Ground improves liquid yield, improves the utilization rate and value of tar resource, and the operating of extension fixture to a certain extent
Cycle.
To achieve these goals, in a first aspect, the present invention provides a kind of method of coal tar hydrogenating, this method includes：
(1) coal tar raw material introducing pretreatment unit is removed water and/or cleaned pretreatment；
(2) in the presence of hydrogen and slurry bed catalyst, the material that will be obtained through step (1) introduces slurry bed system hydrogenation unit
Slurry bed system hydrogenation reactor in carry out hydro-conversion；
(3) material obtained through step (2) is separated and is fractionated successively, obtain light fraction, midbarrel and again
Matter cut；
(4) will be got rid of outside the heavy end of part；And heavy described in the part midbarrel and remainder is evaporated
Divide to be recycled back in the slurry bed system hydrogenation reactor and carry out hydro-conversion；And in described in the light fraction and remainder
Between cut be introduced into the finishing reactor of fixed bed hydrogenation unit and carry out hydrofining reaction；And
(5) effluent of the finishing reactor is separated and is fractionated successively, obtained naphtha cut and diesel oil evaporates
Point.
Second aspect, the present invention provide a kind of system for coal tar hydrogenating, and the system includes：
Pretreatment unit；
Slurry bed system hydrogenation unit, including slurry bed system hydrogenation reactor, the material after pretreatment unit is handled enter institute
State and hydro-conversion is carried out in slurry bed system hydrogenation reactor；
First separative element, have light fraction feed-line, the first midbarrel feed-line, the second midbarrel defeated
Pipeline, the first heavy end feed-line and the second heavy end feed-line, the material from slurry bed system hydrogenation unit is sent to exist
Separated and be fractionated successively in first separative element to obtain light fraction, midbarrel and heavy end, part institute
Heavy end is stated by being got rid of outside the first heavy end feed-line, remainder heavy end is evaporated by second heavy
Feed-line is divided to be recycled back to the slurry bed hydroprocessing by the first midbarrel feed-line with the part midbarrel
Reactor；
Fixed bed hydrogenation unit, including finishing reactor, centre described in the remainder from slurry bed system hydrogenation unit evaporate
Divide and passed through by the second midbarrel feed-line and the light fraction described in light fraction feed-line introducing
Hydrofining reaction is carried out in finishing reactor；And
Second separative element, the material from fixed bed hydrogenation unit are separated successively in second separative element
And fractionation.
The characteristics of present invention utilizes slurry bed system hydrogenation reactor adaptability to raw material strong, it is high to tenor first, mechanical miscellaneous
The high coal tar raw material inferior of matter content is converted, and realizes the lighting of coal tar raw material, and part midbarrel is circulated
Overfall state bed hydroprocessing reactor, deposition or coking generation coke are separated out to suppress asphalitine.Then subsequent fixed bed is recycled to add
The advantages of hydrogen reactor hydrogenation depth is big, good product quality, it is final to obtain cleaning high value-added product.
Slurry bed system and the efficient combination of fixed bed are realized the clean and effective of tar resource by method provided by the invention
Utilize, improve liquid yield to greatest extent, improve the utilization rate and value of tar resource, and extend device
Service cycle.
Using method provided by the invention, not only solve because metal, mechanical admixture etc. contain in full fraction of coal tar raw material
Amount is high and the problem of have a strong impact on coal tar fixed bed hydrogenation device service cycle, and by the way that part midbarrel is recycled back to
Slurry bed system hydrogenation reactor, while realizing coal tar lighting and improving liquid yield to greatest extent, moreover it is possible to effectively press down
Asphalitine in coal tar processed separates out deposition or coking generation coke, ensure that the long period steady running of device.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is a kind of process chart of coal tar hydrogenating process of the present invention.
Description of reference numerals
1st, coal tar raw material 2, pretreatment unit 3, water and mechanical admixture
4th, slurry bed catalyst 5, slurry bed system hydrogenation reactor 6, the first separative element
7th, the first hydrogen-rich gas 8, first circulation hydrogen compressor 9, new hydrogen
10th, first circulation hydrogen 11, the first separation water 12, the first fractionating column
13rd, return tank of top of the tower 14, the first tower overhead gas 15, the second separation water
16th, light fraction 17, midbarrel 18, heavy end
19th, heavy end 20, finishing reactor 21, refined effluent are got rid of outside
22nd, the second separative element 23, the 3rd separation water 24, the second liquid hydrocarbonaceous streams
25th, the second hydrogen-rich gas 26, after-fractionating tower 27, the second tower overhead gas
28th, naphtha cut 29, diesel oil distillate 30, second circulation hydrogen compressor
31st, second circulation hydrogen
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
In a first aspect, the invention provides a kind of method of coal tar hydrogenating, this method includes：
(1) coal tar raw material introducing pretreatment unit is removed water and/or cleaned pretreatment；
(2) in the presence of hydrogen and slurry bed catalyst, the material that will be obtained through step (1) introduces slurry bed system hydrogenation unit
Slurry bed system hydrogenation reactor in carry out hydro-conversion；
(3) material obtained through step (2) is separated and is fractionated successively, obtain light fraction, midbarrel and again
Matter cut；
(4) will be got rid of outside the heavy end of part；And heavy described in the part midbarrel and remainder is evaporated
Divide to be recycled back in the slurry bed system hydrogenation reactor and carry out hydro-conversion；And in described in the light fraction and remainder
Between cut be introduced into the finishing reactor of fixed bed hydrogenation unit and carry out hydrofining reaction；And
(5) effluent of the finishing reactor is separated and is fractionated successively, obtained naphtha cut and diesel oil evaporates
Point.
In the present invention, " the part heavy end " represents the part in whole heavy ends of acquisition in step (3)；
" heavy end described in remainder " represents to remove beyond " the part heavy end ", the whole obtained in step (3)
Remainder in heavy end.In other words, described " the part heavy end " and described " heavy evaporates described in remainder
Point " constitute the whole heavy ends obtained in step (3).
The method of foregoing coal tar hydrogenating provided by the invention has that liquid yield height, good product quality, technique is simple, dress
Put service cycle it is long the features such as.
The foregoing naphtha cut and diesel oil distillate of the present invention can go out device as product.
The method of the present invention pretreatment unit is removed water and/or the cleaned concrete operations mode of pretreatment does not have
It is special to limit, as long as the water in preliminary removing coal tar raw material, the purpose of mechanical admixture can be reached.Such as it can use
Sedimentation and/or the means such as centrifuge and removed water and/or cleaned pretreatment.
The method of the present invention do not required particularly the concrete operation method of the gas-liquid separation and fractionation, such as can be with
Gas-liquid separation is carried out in the gas-liquid separation device of routine, and is fractionated in such as fractionating column.
The present inventor is in research is found, the asphalitine in coal tar is the predecessor of coking, at high temperature easily
Cracking produces free radical.When colloidal dispersion has good stability, the asphalitine in coal tar raw material is in peptization state, in liquid phase
It is middle because heated and caused by free radical can be influenceed by stronger cage effect, make asphaltene free radicals often easily and surrounding
Relatively small molecule or other radical reactions and bury in oblivion, causing asphaltene free radicals, the probability that meets is smaller each other, is not easy
Further polycondensation generation coke.But during with slurry bed system hydrogenation reactor conversion level increase, the stability of colloidal dispersion is therewith
Rapid to reduce, at this moment asphalitine is separated from reacting body phase, one new liquid phase of formation, the pitch in this stylish liquid phase
Matter be easy to through radical reaction with reference to and mutually polymerize, bigger asphaltene molecules are formed, until generation coke.Therefore, to keep away
Exempt from asphalitine to separate from this body phase and mutually polymerize to form coke, it is necessary to avoid dripping during slurry reactor as far as possible
Blue or green matter mutually polymerize generation coke through radical reaction.
In order to avoid mutually polymerizeing generation coke through radical reaction in slurry reactor process studies on asphaltene, the present invention
Inventor consider around asphaltene free radicals provide hydrogen supply component because the presence of hydrogen supply component can be timely and effectively
Hydrogen is provided for asphaltene free radicals, hydrogen is reacted and is buried in oblivion with asphaltene free radicals.The present inventor passes through creativeness
Found after research, the part such as mononuclear aromatics and double ring arene with naphthenic ring hydrogenation of aromatics has good hydrogen supply performance, example
Such as indane or naphthane or naphthalenes, in consideration of it, of the invention by one in the midbarrel of this structure with more amount
Point be recycled back to slurry bed system hydrogenation reactor, as the hydrogen supply component of asphaltene free radicals, with suppress reaction conversion level it is high when
The precipitation deposition of asphalitine or coking generation coke.It was found by the inventors of the present invention that it is recycled back to the slurry bed system hydrogenation reactor
In the part midbarrel account for after step (3) 20~50 weight % of the whole midbarrel total amounts obtained, it is more excellent
When electing 25~45 weight % as, the cycle of operation of device can be obviously prolonged and realize coal tar lighting and maximum limit simultaneously
Degree improves liquid yield, and can substantially reduce the generation of coke.
Preferably, the end point of distillation of the light fraction is 150~200 DEG C；The end point of distillation of the midbarrel be 330~
400℃；It is highly preferred that the end point of distillation of the light fraction is 170~190 DEG C；The end point of distillation of the midbarrel be 360~
390℃.In the present invention, it is necessary to which special instruction, boiling range are that the cut of the end point of distillation less than or equal to the light fraction is
For the light fraction；Likewise, boiling range is the end point of distillation more than the light fraction and is less than or equal to the midbarrel
The cut of the end point of distillation is the midbarrel；Moreover, boiling range is institute for the cut of the end point of distillation more than the midbarrel
State heavy end.
The slurry bed catalyst can be that homogeneous slurry bed catalyst can also be heterogeneous slurry bed catalyst, this hair
The bright preferably slurry bed catalyst is heterogeneous slurry bed catalyst.It is highly preferred that the slurry bed catalyst is high dispersive
Heterogeneous slurry bed catalyst.The heterogeneous slurry bed catalyst of high dispersive can be selected from Fe-series catalyst, iron series compound
At least one of with iron system carbon-based loaded catalyst.The Fe-series catalyst is in troilite, bloodstone and red mud
It is at least one；The iron series compound is selected from Fe2S、Fe2O3And Fe3O4At least one of；The carbon-based supported catalyst of iron system
Agent includes carrier and load active metallic element on the carrier, the carrier be selected from coal dust, activated carbon, graphite and
The carbon-based material of at least one of carbon black, the active metallic element are selected from least one of W, Mo, Ni, Co and Fe.
Preferably, the average grain diameter of the Fe-series catalyst is 10-200 μm.
Preferably, on the basis of the gross weight of the coal tar raw material, work of the slurry bed catalyst wherein to contain
The dosage of property elemental metal is 0.1~3.5 weight %, preferably 0.15~2.5 weight %.In order to further illustrate, when
When the slurry bed catalyst is Fe-series catalyst and/or iron series compound, the dosage of the slurry bed catalyst is wherein to contain
The content meter of some ferro elements；When slurry bed catalyst loaded catalyst carbon-based for iron system, the slurry bed system catalysis
The dosage of agent is with the content meter of the active metallic element (such as W, Mo, Ni, Co and the Fe that may contain) wherein contained.
Preferably, the part heavy end got rid of outside accounts for after step (3) the 3 of the whole heavy end total amounts obtained
~16 weight %；5~10 weight % of the whole heavy end total amounts obtained are more preferably accounted for after step (3).
Preferably, the condition of hydro-conversion is carried out in the slurry bed system hydrogenation reactor to be included：Reaction temperature be 400~
460 DEG C, hydrogen dividing potential drop is 8.0~15.0MPa, and volume space velocity is 0.5~2.0h-1, hydrogen to oil volume ratio is 500~1500；It is further preferred that
Carrying out the condition of hydro-conversion includes：Reaction temperature is 410~440 DEG C, and hydrogen dividing potential drop is 8.5~12.0MPa, and volume space velocity is
0.6~1.5h-1, hydrogen to oil volume ratio is 600~1200.
Preferably, the condition that hydro-conversion is carried out in the slurry bed system hydrogenation reactor is controlled so that the fixed bed adds
The μ g/g of the weight % of solids content in the charging of the finishing reactor of hydrogen unit ≯ 0.01 and tenor ≯ 10.
Preferably, the condition of hydrofining reaction is carried out in the finishing reactor to be included：Hydrogen dividing potential drop be 8.0~
20.0MPa, more preferably 10.0~19.0MPa；Reaction temperature is 340~420 DEG C, more preferably 350~400 DEG C；Hydrogen oil body
Product is than being 600~1800；Volume space velocity is 0.1~1.5h during material liquid-1。
The hydrofining reaction can be carried out in the presence of Hydrobon catalyst.
Preferably, containing carrier and load active component on the carrier and appoint in the Hydrobon catalyst
Select the coagent contained；The metallic element of the active component is selected from vib metals element and group VIII metallic element
At least one of.The coagent optionally contained refers to that can contain coagent can also not contain coagent.
Preferably, in the Hydrobon catalyst, the carrier is silica-alumina, the vib metals
Element is molybdenum and/or tungsten, and the group VIII metallic element is cobalt and/or nickel.
According to a kind of preferred embodiment, in the Hydrobon catalyst, the carrier is silica-oxygen
Change aluminium, the group VIII metallic element loaded on the carrier is nickel and group VIII metallic element is cobalt and/or nickel, and
Contain coagent in the Hydrobon catalyst, the active element of the coagent is phosphorus；Urged with the hydrofinishing
On the basis of the gross weight of agent, the content for the nickel counted using oxide is 1-10 weight %, the content of molybdenum and tungsten in terms of oxide
Sum is that for the content for the phosphorus counted using oxide as 1-9 weight %, surplus is load to 50 weight % are less than or equal to more than 10 weight %
Body.The content sum of the molybdenum counted using oxide and tungsten extremely represents as more than 10 weight % less than or equal to 50 weight %, if together
The content sum of Shi Hanyou molybdenums and tungsten, the then molybdenum counted using oxide and tungsten is extremely less than or equal to 50 weight % as more than 10 weight %；
If only containing one kind in molybdenum and tungsten, the molybdenum counted using oxide or the content of tungsten are extremely less than or equal to 50 weights as more than 10 weight %
Measure %.
Preferably, in the carrier of the Hydrobon catalyst, the content of silica is 2-45 weight %, oxidation
The content of aluminium is 55-98 weight %.
Due to still containing a small amount of metal impurities in light fraction and the miscella of midbarrel, to avoid hydrofinishing
The activity of catalyst is influenceed by metal impurities, and prevents that the bed pressure drop rising of finishing reactor is too fast, preferably in essence
The a small amount of hydrogenation protecting catalyst of the top loading of reactor processed.It is highly preferred that the hydrogenation protecting catalyst and the hydrogenation
The admission space ratio of catalyst for refining is 0.05~0.2：1.
In the finishing reactor, the hydrogenation protecting catalyst can be a variety of guard catalyst grading loadings, excellent
Elect five kinds of hydrogenation protecting catalyst grading loadings as.The hydrogenation protecting catalyst grading mode be along reaction stream direction successively
Load hydrogenation protecting catalyst I, hydrogenation protecting catalyst II, hydrogenation protecting catalyst III, hydrogenation protecting catalyst IV and hydrogenation
Guard catalyst V；The hydrogenation protecting catalyst I, hydrogenation protecting catalyst II, hydrogenation protecting catalyst III, hydrogenation protecting are urged
Active metallic element in agent IV and hydrogenation protecting catalyst V is selected from vib metals element and/or group VIII metal member
At least one of element.
Preferably, the hydrogenation protecting catalyst I is that one kind is shaped as Round Porous column, carrier is silica or aluminum oxide
Hydrogenation protecting catalyst, its average particulate diameter is 15~17mm.Hydrogenation protecting catalyst I have higher porosity and
Especially big pore structure, solid particulate matter carried in coal tar raw material etc. can be accommodated.
Preferably, the hydrogenation protecting catalyst II be one kind be shaped as honeycomb is cylindric, average particulate diameter be 9~
11mm hydrogenation protecting catalyst.On the basis of the gross weight of the hydrogenation protecting catalyst II, the hydrogenation protecting catalyst
Contain the weight % of nickel oxide 0.05~0.2 in II, the weight % of molybdenum oxide 0.5~1.0, surplus is carrier.The hydrogenation protecting is catalyzed
Agent II has higher porosity and macroporous structure, can accommodate the particulate matter carried in coal tar raw material, metal impurities.
Preferably, the hydrogenation protecting catalyst III be one kind be shaped as Raschig ring shape, average particulate diameter be 5.6~
6.5mm hydrogenation protecting catalyst.Contain the weight % of nickel oxide 0.1~0.5, molybdenum oxide in the hydrogenation protecting catalyst III
0.5~2.5 weight %, surplus are the silica or aluminum oxide as carrier.Hydrogenation protecting catalyst III has higher hole
Gap rate and macroporous structure, the metal impurities in coal tar raw material can be accommodated, and hydrogenation saturation is carried out to alkene, alkadienes.
Preferably, the hydrogenation protecting catalyst IV be one kind be shaped as Raschig ring shape, average particulate diameter be 2.5~
3.5mm hydrogenation protecting catalyst.The hydrogenation protecting catalyst IV contains the weight % of nickel oxide 0.1~1.0, molybdenum oxide 1.0
~5.5 weight %, surplus are the silica or aluminum oxide as carrier.The hydrogenation protecting catalyst IV can remove coal tar
Metal impurities in raw material.
Preferably, the hydrogenation protecting catalyst V is that one kind is shaped as clover, average particulate diameter is 2.5~3.5mm
Hydrogenation protecting catalyst.Contain the weight % of nickel oxide 0.5~1.5, molybdenum oxide 1.5~6.5 in the hydrogenation protecting catalyst V
Weight %, surplus are the silica or aluminum oxide as carrier.The hydrogenation protecting catalyst V can remove coal tar raw material
In metal impurities.
Admission space ratio between above-mentioned a variety of hydrogenation protecting catalysts is not required particularly, those skilled in the art
Conventional admission space ratio in the art can be used to load above-mentioned a variety of hydrogenation protecting catalysts.
The coal tar refers to coal tar caused by pyrolysis of coal or coal generating gas or other processes, for example, the coal tar can
To be (including semicoke, the medium temperature coking of caused coalite tar cut or pyrolysis of coal process during coal generating gas
And high-temperature coking process) at least one of caused coalite tar, medium temperature coal tar and high temperature coal-tar.The present invention
In, the boiling range of the coalite tar can be 50-450 DEG C；The boiling range of the medium temperature coal tar can be 50-600 DEG C；It is described
The boiling range of high temperature coal-tar can be 50-650 DEG C.
Second aspect, present invention also offers a kind of system for coal tar hydrogenating, the system includes：
Pretreatment unit；
Slurry bed system hydrogenation unit, including slurry bed system hydrogenation reactor, the material after pretreatment unit is handled enter institute
State and hydro-conversion is carried out in slurry bed system hydrogenation reactor；
First separative element, have light fraction feed-line, the first midbarrel feed-line, the second midbarrel defeated
Pipeline, the first heavy end feed-line and the second heavy end feed-line, the material from slurry bed system hydrogenation unit is sent to exist
Separated and be fractionated successively in first separative element to obtain light fraction, midbarrel and heavy end, part institute
Heavy end is stated by being got rid of outside the first heavy end feed-line, remainder heavy end is evaporated by second heavy
Feed-line is divided to be recycled back to the slurry bed hydroprocessing by the first midbarrel feed-line with the part midbarrel
Reactor；
Fixed bed hydrogenation unit, including finishing reactor, centre described in the remainder from slurry bed system hydrogenation unit evaporate
Divide and passed through by the second midbarrel feed-line and the light fraction described in light fraction feed-line introducing
Hydrofining reaction is carried out in finishing reactor；And
Second separative element, the material from fixed bed hydrogenation unit are separated successively in second separative element
And fractionation.
Dehydration and/or the mechanical purifying device for settling, centrifuging can be contained in the pretreatment unit.
Preferably, include what is be sequentially connected by pipeline respectively in first separative element and second separative element
Gas-liquid separation device and fractionating column；In first separative element, the entrance of gas-liquid separation device passes through pipeline and the slurry
The outlet connection of state bed hydroprocessing unit, and the outlet of fractionating column are connected by the entrance of pipeline and the fixed bed hydrogenation unit
Connect；In second separative element, the entrance of gas-liquid separation device is connected by pipeline with the outlet of fixed bed hydrogenation unit,
And the outlet of fractionating column is led to product outside system by pipeline.
Preferably, the system further comprises recycle hydrogen unit, first separative element and second separative element
It is connected respectively by pipeline with the recycle hydrogen unit so that obtained by first separative element and second separative element
Gaseous phase materials enter the recycle hydrogen unit in.
In first separative element, described in the material from the exit of slurry bed system hydrogenation unit is introduced by pipeline
Carry out gas-liquid separation in the gas-liquid separation device of first separative element, the gaseous phase materials of acquisition enter in the recycle hydrogen unit with
Further removal of impurities is to obtain hydrogeneous logistics therein, and the liquid phase material that gas-liquid separation acquisition is carried out by gas-liquid separation device leads to
Cross pipeline into first separative element fractionating column in be fractionated, fractionation obtain the intermediate product of different boiling ranges, and
Partial intermediate is recycled back in the slurry bed system hydrogenation unit by the first midbarrel feed-line, and another part
Intermediate product is introduced into fixed bed hydrogenation unit by the second midbarrel feed-line.And by the fixed bed hydrogenation
The product that unit exit obtains, which is entered by pipeline in the gas-liquid separation device of second separative element, carries out gas-liquid separation,
The gaseous phase materials of acquisition enter further to clean to obtain hydrogeneous logistics therein in the recycle hydrogen unit, and pass through gas-liquid
The liquid phase material of separator progress gas-liquid separation acquisition is entered in the fractionating column of second separative element by pipeline to be carried out
Fractionation, fractionation obtains the product of different boiling ranges, also, the product obtained is led to outside system by pipeline.
Preferably, the recycle hydrogen unit by pipeline respectively with the slurry bed system hydrogenation unit and the fixed bed hydrogenation
Unit connection is with respectively to the slurry bed system hydrogenation unit and the hydrogeneous logistics of fixed bed hydrogenation unit supplement.
Preferably, at least one circulating hydrogen compressor is contained in the recycle hydrogen unit.Especially, first separation is single
First and described second separative element is connected by one or more of pipeline and the recycle hydrogen unit circulating hydrogen compressor respectively
Connect to obtain the hydrogeneous logistics in the gaseous phase materials obtained by first separative element and second separative element.
According to a kind of preferred embodiment, the present invention provides process route as shown in Figure 1 to carry out coal tar
It is hydrogenated with, some auxiliary equipments such as heat exchanger, preheating furnace etc. in figure do not mark, but this is known to those of ordinary skill in the art
, specific process route is as follows：
Coal tar raw material 1 introduces pretreatment unit 2 and is settled, centrifuged to remove water and mechanical admixture 3；Then will
Effluent, slurry bed catalyst 4 and first circulation hydrogen 10 in pretreatment unit 2 are concomitantly introduced into the slurry of slurry bed system hydrogenation unit
Hydro-conversion is carried out in bed hydroprocessing reactor 5；Then the effluent of slurry bed system hydrogenation reactor 5 is introduced into the first separative element 6
Gas-liquid separation device in carry out gas-liquid separation, isolated first separation water 11, the first hydrogen-rich gas 7 and the first liquid hydrocarbon thing
Stream, conduct after first hydrogen-rich gas 7 mixes after the first circulation hydrogen compressor 8 in recycle hydrogen unit is pressurized with new hydrogen 9
The first circulation hydrogen 10 of slurry bed system hydrogenation unit.Entered by first liquid hydrocarbonaceous streams obtained in first separative element 6
Enter in the first fractionating column 12 of the first separative element and carry out distillation cutting, respectively obtain gas phase light component, midbarrel 17 and again
Matter cut 18；The gas phase light component cut out enters in the return tank of top of the tower 13 of the first fractionating column 12 point for carrying out Oil, Water, Gas
From, the light fraction 16 of the second separation water 15, the first tower overhead gas 14 and oil phase is respectively obtained, wherein, the first tower top isolated
Gas 14 goes out system as fuel gas, and the part midbarrel 17, which is recycled back in the slurry bed system hydrogenation reactor 5, to be hydrogenated with
Conversion, midbarrel 17 described in remainder is together with light fraction 16 and second circulation hydrogen 31 into fixed bed hydrogenation unit
Hydrofining reaction is carried out in finishing reactor 20.A portion in the heavy end 18 cut out in first fractionating column 12
Get rid of heavy end 19 as outer and thrown away system outside, the heavy end of remainder is recycled back to slurry bed system hydrogenation reactor 5 and enters one
Step carries out hydro-conversion.Refined effluent 21 in the finishing reactor 20 of fixed bed hydrogenation unit enters the second separative element 22
Gas-liquid separation device in carry out gas-liquid separation, obtain the 3rd separation water 23, the second hydrogen-rich gas 25 and the second liquid hydrocarbonaceous streams
24；Wherein, second hydrogen-rich gas 25 mixes after the second circulation hydrogen compressor 30 in recycle hydrogen unit is pressurized with new hydrogen 9
Second circulation hydrogen 31 as fixed bed hydrogenation unit.Second liquid hydrocarbonaceous streams 24 enter second point of the second separative element
Evaporate and distillation cutting is carried out in tower 26, obtain going out as fuel gas the second tower overhead gas 27 and naphtha cut 28, diesel oil of system
Cut 29, wherein, naphtha cut 28 and diesel oil distillate 29 go out system as product.
The method of the present invention has the following advantages that：
(1) present invention realizes the lighting of coal tar using slurry bed system hydrogenation reactor, and slurry reactor product can expire
The feed needs of the subsequent fixed bed hydroprocessing unit of foot, substantially increase the utilization rate and value of tar resource；
(2) while coal tar lighting is realized using slurry bed system hydrogenation reactor, part midbarrel is recycled back to
Slurry bed system hydrogenation reactor, the precipitation deposition and coking generation coke of asphalitine are effectively inhibited, improves liquid to greatest extent
Body yield, and ensure that the long period steady running of device.
(3) combined method with fixed bed hydrogenation upgrading is hydrocracked using slurry bed system, slurry bed system raw material can be taken into account and fitted
Ying Xingqiang and fixed bed good product quality advantage, the clean and effective for realizing tar resource utilize, can be to a certain degree
It is upper to alleviate petroleum-based sources situation in short supply.
The present invention will be described in detail by way of examples below.In case of no particular description, it is used below
Various raw materials be all from it is commercially available.The property of coal tar raw material used below is shown in Table 1.
Hydrogenation protecting catalyst and Hydrobon catalyst are loaded in the finishing reactor of fixed bed hydrogenation unit, hydrogenation is protected
Catalyst packing is protected in reactor head, is five kinds of hydrogenation protecting catalyst grading loadings, is loaded successively along reaction stream direction
Hydrogenation protecting catalyst I, hydrogenation protecting catalyst II, hydrogenation protecting catalyst III, hydrogenation protecting catalyst IV and hydrogenation protecting
Catalyst V, trade names are respectively RGC-20, RGC-30E, RGC-30A, RGC-30B, RGC-1, and hydrogenation protecting catalyst I,
Hydrogenation protecting catalyst II, hydrogenation protecting catalyst III, hydrogenation protecting catalyst IV and hydrogenation protecting catalyst V filling body
Product is than being 1：2：1.5：1.5：2.
The product designation RTC-2 of Hydrobon catalyst, on the basis of the gross weight of the Hydrobon catalyst, with
The content of the nickel of oxide meter is 2.4 weight %, and the content for the molybdenum counted using oxide is 8.3 weight %, the tungsten in terms of oxide
Content be 16.7 weight %, for the content for the phosphorus counted using oxide as 2.0 weight %, surplus is Support Silica-aluminum oxide, with
On the basis of the carrier, the content of silica is 20.0 weight %, and the content of aluminum oxide is 80.0 weight %.
The heterogeneous slurry bed catalyst of high dispersive, the high score are used in the slurry bed system hydrogenation reactor of slurry bed system hydrogenation unit
It is the carbon-based loaded catalyst of high-dispersion iron to dissipate heterogeneous slurry bed catalyst, consisting of：Activated carbon is as carrier, activity
Metal component is Fe and Mo.Also, the weight of the Fe and Mo in the carbon-based loaded catalyst of high-dispersion iron in terms of element
Than for 1：0.2.
The catalyst of above-mentioned trade names is the Chang Ling catalyst plant production of Sinopec catalyst branch company.
In the following Examples and Comparative Examples, in case of no particular description, using the Hydrobon catalyst as
Benchmark, the admission space of the hydrogenation protecting catalyst are the 10% of Hydrobon catalyst.
Table 1
| Coal tar raw material | |
| Density (20 DEG C)/(g/cm3) | 1.0430 |
| Carbon residue/weight % | 6.50 |
| Nitrogen content/(μ g/g) | 6800 |
| Sulfur content/(μ g/g) | 2500 |
| C content/weight % | 81.83 |
| H content/weight % | 8.17 |
| Asphalt content/weight % | 16.0 |
| Boiling range ASTM D-1160/ DEG C | |
| IBP | 165 |
| 50% | 387 |
| 95% | 512 |
| Tenor/(μ g/g) | |
| Fe | 98.7 |
| Ni | ＜ 0.1 |
| V | 0.1 |
| Na | 25.0 |
| Ca | 100.9 |
| Al | 13.4 |
Embodiment 1
On the basis of the gross weight of coal tar raw material, use of the slurry bed catalyst in terms of the active metallic element wherein contained
Measure as 1.5 weight %.After coal tar raw material in table 1 is well mixed with the heterogeneous slurry bed catalyst of foregoing high dispersive, with
Hydrogen enters slurry bed system hydrogenation reactor and carries out hydro-conversion together, and the effluent of slurry bed system hydrogenation reactor enters the first separation
Unit carries out gas-liquid separation, and separates water outlet, and the first isolated liquid hydrocarbonaceous streams enter the first separative element, distillation cutting
For light fraction, midbarrel and heavy end.Wherein, the 7.5 of whole heavy ends that the distillation of the first separative element is cut out
Device is thrown away outside weight %, remainder heavy end is recycled back in slurry bed system hydrogenation reactor and further converted.Wherein
35 weight % of whole midbarrels that the distillation of the first separative element is cut out midbarrel is recycled back to slurry bed system hydrogenation reaction
Device is further converted.Remainder midbarrel enters fixed bed hydrogenation list after being mixed with the light fraction of whole with hydrogen
The finishing reactor of member, with Hydrobon catalyst haptoreaction, the refined effluent of finishing reactor enters the second separation list
Member carries out gas-liquid separation, and separates water outlet, and the second liquid hydrocarbon product isolated enters the second separative element, and distillation is cut into stone
Naphtha fraction, diesel oil distillate.Wherein naphtha cut and diesel oil distillate goes out device as product.
The specific reaction condition being related in above-described embodiment is shown in Table 2, and the property of the product obtained after slurry bed hydroprocessing is shown in Table
3.The naphtha product and the property of diesel product that second separative element fractionates out are shown in Table 4.
From table 3 it is observed that after slurry bed hydroprocessing, the μ g/g of tenor ＜ 10 in product, content of impurities
The weight % of ＜ 0.01, can meet subsequent fixed bed hydroprocessing device feed needs.
Moreover, part midbarrel is recycled back into slurry bed system hydrogenation reactor in the present embodiment, asphalitine is not occurred
The problem of deposition blocks reactor inner member is separated out, the cycle of oparation of slurry bed system hydrogenation plant has exceeded 5000h, and raw
Into amount of coke few 3.53 percentage points compared with comparative example 1,5.4 percentage points of respective liquid high income；And the method for comparative example 1
The cycle of oparation of middle slurry bed system hydrogenation plant is only 1080h.
This explanation can effectively be suppressed asphalitine and be separated out deposition and coking generation coke, maximum limit using the method for the present invention
Improve liquid yield and ensure that the long period steady running of device degree.
By table 4 it can also be seen that the present embodiment diesel product sulfur content be less than 10 μ g/g, condensation point be -16 DEG C, 16
Alkane value is 45.9, can be used as low-sulfur cleaning diesel oil blending component.The sulfur content of naphtha cut, which is less than 10 μ g/g, virtue is dived reaches
68.9, can be as Gao Fangqian reforming material.
Significantly improved that is, method provided by the invention can be realized on the basis of the property of diesel product is ensured
The cycle of oparation of device and the purpose for improving liquid receipts.
Embodiment 2
The present embodiment is carried out using method similar to Example 1, except that：
In the present embodiment, on the basis of the gross weight of coal tar raw material, activity gold of the slurry bed catalyst wherein to contain
The dosage for belonging to element meter is 2.0 weight %；And 5 weight % of the whole heavy ends for cutting out the distillation of the first separative element
Device is thrown away outside, remainder heavy end is recycled back in slurry bed system hydrogenation reactor and further converted.And by first
45 weight % of whole midbarrels that separative element distillation is cut out midbarrel is recycled back to slurry bed system hydrogenation reactor and entered
One step is converted, and remainder midbarrel enters fixed bed hydrogenation unit after being mixed with the light fraction of whole with hydrogen
Finishing reactor, with Hydrobon catalyst haptoreaction.
The specific reaction condition being related in above-described embodiment is shown in Table 2, and the property of the product obtained after slurry bed hydroprocessing is shown in Table
3.The naphtha product and the property of diesel product that second separative element fractionates out are shown in Table 4.
From table 3 it is observed that after slurry bed hydroprocessing, the μ g/g of tenor ＜ 10 in product, content of impurities
The weight % of ＜ 0.01, can meet subsequent fixed bed hydroprocessing device feed needs.
Moreover, part midbarrel is recycled back into slurry bed system hydrogenation reactor in the present embodiment, asphalitine is not occurred
The problem of deposition blocks reactor inner member is separated out, the cycle of oparation of slurry bed system hydrogenation plant has exceeded 5000h, and raw
Into amount of coke few 2.42 percentage points compared with comparative example 1,3.63 percentage points of respective liquid high income；And the side of comparative example 1
The cycle of oparation of slurry bed system hydrogenation plant is only 1080h in method.
This explanation can effectively be suppressed asphalitine and be separated out deposition and coking generation coke, maximum limit using the method for the present invention
Improve liquid yield and ensure that the long period steady running of device degree.
By table 4 it can also be seen that the present embodiment diesel product sulfur content be less than 10 μ g/g, condensation point be -18 DEG C, 16
Alkane value is 47.4, can be used as low-sulfur cleaning diesel oil blending component.The sulfur content of naphtha cut, which is less than 10 μ g/g, virtue is dived reaches
66.7, can be as Gao Fangqian reforming material.
Significantly improved that is, method provided by the invention can be realized on the basis of the property of diesel product is ensured
The cycle of oparation of device and the purpose for improving liquid receipts.
Embodiment 3
The present embodiment is carried out using method similar to Example 1, except that：
In the present embodiment, on the basis of the gross weight of coal tar raw material, activity gold of the slurry bed catalyst wherein to contain
The dosage for belonging to element meter is 0.5 weight %；And 10 weights of the whole heavy ends for cutting out the distillation of the first separative element
Device is thrown away outside amount %, remaining heavy end is recycled back in slurry bed system hydrogenation reactor and further converted.And by first
25 weight % of whole midbarrels that separative element distillation is cut out midbarrel is recycled back to slurry bed system hydrogenation reactor and entered
One step is converted, and remaining midbarrel enters the refined of fixed bed hydrogenation unit after being mixed with the light fraction of whole with hydrogen
Reactor, with Hydrobon catalyst haptoreaction.
The specific reaction condition being related in above-described embodiment is shown in Table 2, and the property of the product obtained after slurry bed hydroprocessing is shown in Table
3.The naphtha product and the property of diesel product that second separative element fractionates out are shown in Table 4.
From table 3 it is observed that after slurry bed hydroprocessing, the μ g/g of tenor ＜ 10 in product, content of impurities
The weight % of ＜ 0.01, can meet subsequent fixed bed hydroprocessing device feed needs.
Moreover, part midbarrel is recycled back into slurry bed system hydrogenation reactor in the present embodiment, asphalitine is not occurred
The problem of deposition blocks reactor inner member is separated out, the cycle of oparation of slurry bed system hydrogenation plant has exceeded 5000h, and raw
Into amount of coke few 3.78 percentage points compared with comparative example 1,6.12 percentage points of respective liquid high income；And the side of comparative example 1
The cycle of oparation of slurry bed system hydrogenation plant is only 1080h in method.
This explanation can effectively be suppressed asphalitine and be separated out deposition and coking generation coke, maximum limit using the method for the present invention
Improve liquid yield and ensure that the long period steady running of device degree.
By table 4 it can also be seen that the present embodiment diesel product sulfur content be less than 10 μ g/g, condensation point be -15 DEG C, 16
Alkane value is 44.1, can be used as low-sulfur cleaning diesel oil blending component.The sulfur content of naphtha cut, which is less than 10 μ g/g, virtue is dived reaches
70.1, can be as Gao Fangqian reforming material.
Significantly improved that is, method provided by the invention can be realized on the basis of the property of diesel product is ensured
The cycle of oparation of device and the purpose for improving liquid receipts.
Comparative example 1
This comparative example is carried out using method similar to Example 2, except that：
The midbarrel in slurry bed system hydrogenation reaction product is not recycled back into slurry bed system hydrogenation reactor in this comparative example to enter
One step converts.
Although this comparative example is also stripped of metal in coal tar raw material, mechanical admixture etc., coal tar raw material is realized
Lighting.But occur the precipitation deposition of asphalitine in slurry bed system hydrogenation reactor running and plug structure in reactor
Part, slurry bed system hydrogenation plant is caused not run well, its cycle of oparation is only 1080h.
Further, since midbarrel is not recycled back to slurry bed system hydrogenation reactor by this comparative example, with the progress of reaction, drip
Blue or green matter is separated from reacting body phase, through radical reaction with reference to and mutually polymerize, generate coke.
From table 3 it is observed that the coke yield of comparative example 1 is high 2.42 percentage points compared with embodiment 2, respective liquid is received
Rate is low 3.63 percentage points.
The specific reaction condition of this comparative example is shown in Table 2, and the product characteristicses after slurry bed hydroprocessing are shown in Table 3.
The naphtha product and the property of diesel product that second separative element fractionates out are shown in Table 4.
Table 2
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Slurry bed system hydrogenation reactor | ||||
| Hydrogen dividing potential drop/MPa | 9.0 | 10.5 | 8.5 | 10.5 |
| Reaction temperature/DEG C | 420 | 435 | 410 | 435 |
| Hydrogen-oil ratio/(Nm3/m3) | 800 | 1000 | 800 | 1000 |
| Volume space velocity/h-1 | 0.8 | 0.6 | 1.2 | 0.6 |
| Fixed bed hydrogenation finishing reactor | ||||
| Hydrogen dividing potential drop/MPa | 17.0 | 15.0 | 18.0 | 15.0 |
| Reaction temperature/DEG C | 360 | 370 | 380 | 370 |
| Hydrogen-oil ratio/(Nm3/m3) | 1500 | 1200 | 1800 | 1200 |
| Volume space velocity/h-1 | 0.8 | 1.2 | 0.5 | 1.2 |
Table 3
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Product distribution/weight % of slurry bed system hydrogenation unit | ||||
| Dry gas+liquefied gas | 4.20 | 5.00 | 3.42 | 6.43 |
| Coke | 3.35 | 4.46 | 3.10 | 6.88 |
| Liquid product yield/weight % | 94.03 | 92.26 | 94.75 | 88.63 |
| 180 DEG C of light fractions of ＜ | 16.76 | 20.44 | 13.19 | 19.46 |
| 180~380 DEG C of midbarrels | 47.22 | 49.03 | 44.81 | 46.44 |
| 380 DEG C of heavy ends of ＞ | 30.05 | 22.79 | 36.75 | 22.73 |
| Total metal contents in soil/(μ g/g) | 5.7 | 2.0 | 7.0 | 2.5 |
| Mechanical admixture/weight % | 0.006 | 0.002 | 0.008 | 0.002 |
| Slurry bed system cycle of oparation/h | ＞ 5000 | ＞ 5000 | ＞ 5000 | 1080 |
Table 4
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Total liquid yield/weight % | 88.45 | 85.81 | 89.74 | 83.46 |
| Fluid product distribution/weight % | ||||
| Product naphtha cut | 30.90 | 34.37 | 29.56 | 37.31 |
| Product diesel oil distillate | 69.10 | 65.63 | 70.44 | 62.69 |
| Product naphtha cut property | ||||
| Density (20 DEG C)/(g/cm3) | 0.7629 | 0.7610 | 0.7666 | 0.7574 |
| Sulfur content/(μ g/g) | 5.0 | 3.2 | 7.5 | 3.0 |
| C content/weight % | 85.35 | 85.10 | 85.60 | 85.07 |
| H content/weight % | 14.65 | 14.90 | 14.40 | 14.93 |
| Fragrant latent/% | 68.9 | 66.7 | 70.1 | 66.0 |
| Product diesel oil distillate property | ||||
| Density (20 DEG C)/(g/cm3) | 0.8513 | 0.8455 | 0.8560 | 0.8420 |
| Sulfur content/(μ g/g) | 7.5 | 4.3 | 9.6 | 2.6 |
| C content/weight % | 86.56 | 86.25 | 87.63 | 86.20 |
| H content/weight % | 13.44 | 13.75 | 12.37 | 13.80 |
| Condensation point/DEG C | -16 | -18 | -15 | -17 |
| Cetane number | 45.9 | 47.4 | 44.1 | 46.3 |
| Product diesel oil distillate boiling range (ASTMD-1160)/DEG C | ||||
| IBP | 160 | 163 | 163 | 161 |
| 50% | 266 | 257 | 268 | 253 |
| 95% | 360 | 359 | 360 | 354 |
It can be seen from the results above that method provided by the invention has device length service cycle, liquid yield height etc. excellent
Point, and can take into account that slurry bed system hydrogenation reactor adaptability to raw material is strong and the advantage of fixed bed reactors good product quality, carry
The high utilization rate and value of tar resource, a kind of effective utilization is provided for this cheap resource inferior of coal tar
Approach.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (15)
1. a kind of method of coal tar hydrogenating, this method include：
(1) coal tar raw material introducing pretreatment unit is removed water and/or cleaned pretreatment；
(2) in the presence of hydrogen and slurry bed catalyst, the material that will be obtained through step (1) introduces the slurry of slurry bed system hydrogenation unit
Hydro-conversion is carried out in state bed hydroprocessing reactor；
(3) material obtained through step (2) is separated and is fractionated successively, obtained light fraction, midbarrel and heavy and evaporate
Point；
(4) will be got rid of outside the heavy end of part；And heavy end described in the part midbarrel and remainder is followed
Hydro-conversion is carried out in slurry bed system hydrogenation reactor described in loopback；And evaporated middle described in the light fraction and remainder
Separate and hydrofining reaction is carried out in the finishing reactor of fixed bed hydrogenation unit；And
(5) effluent of the finishing reactor is separated and is fractionated successively, obtain naphtha cut and diesel oil distillate.
2. the method according to claim 11, wherein, the part centre being recycled back in the slurry bed system hydrogenation reactor
Cut accounts for after step (3) 20~50 weight % of the whole midbarrel total amounts obtained, preferably accounts for after step (3) and obtains
Whole midbarrel total amounts 25~45 weight %.
3. method according to claim 1 or 2, wherein, the end point of distillation of the light fraction is 150~200 DEG C；In described
Between cut the end point of distillation be 330~400 DEG C；Preferably
The end point of distillation of the light fraction is 170~190 DEG C；The end point of distillation of the midbarrel is 360~390 DEG C.
4. according to the method described in any one in claim 1-3, wherein, the slurry bed catalyst is heterogeneous slurry bed system
Catalyst, the heterogeneous slurry bed catalyst are selected from Fe-series catalyst, the carbon-based loaded catalyst of iron series compound and iron system
At least one of；
The Fe-series catalyst is selected from least one of troilite, bloodstone and red mud, it is preferable that the Fe-series catalyst
Average grain diameter is 10-200 μm；
The iron series compound is selected from Fe2S、Fe2O3And Fe3O4At least one of；
The carbon-based loaded catalyst of iron system includes the active metallic element of carrier and load on the carrier, the load
Body is the carbon-based material selected from least one of coal dust, activated carbon, graphite and carbon black, the active metallic element be selected from W,
At least one of Mo, Ni, Co and Fe.
5. according to the method described in any one in claim 1-4, wherein, using the gross weight of the coal tar raw material as base
Standard, the slurry bed catalyst are preferably using the dosage that the active metallic element wherein contained is counted as 0.1~3.5 weight %
0.15~2.5 weight %.
6. according to the method described in any one in claim 1-5, wherein, the part heavy end got rid of outside is accounted for through step
(3) 3~16 weight % of the whole heavy end total amounts obtained afterwards；It is preferred that the whole heavys obtained are accounted for after step (3)
5~10 weight % of cut total amount.
7. according to the method described in any one in claim 1-6, wherein, added in the slurry bed system hydrogenation reactor
The condition of hydrogen conversion includes：Reaction temperature is 400~460 DEG C, and hydrogen dividing potential drop be 8.0~15.0MPa, volume space velocity for 0.5~
2.0h-1, hydrogen to oil volume ratio is 500~1500；Preferably,
Carrying out the condition of hydro-conversion includes：Reaction temperature is 410~440 DEG C, and hydrogen dividing potential drop is 8.5~12.0MPa, volume space velocity
For 0.6~1.5h-1, hydrogen to oil volume ratio is 600~1200.
8. according to the method described in any one in claim 1-6, wherein, hydrofinishing is carried out in the finishing reactor
The condition of reaction includes：Hydrogen dividing potential drop is 8.0~20.0MPa, preferably 10.0~19.0MPa；Reaction temperature is 340~420 DEG C,
Preferably 350~400 DEG C；Hydrogen to oil volume ratio is 600~1800；Volume space velocity is 0.1~1.5h during material liquid-1。
9. according to the method described in any one in claim 1-6 and 8, wherein, the hydrofining reaction is in hydrofinishing
Carried out in the presence of catalyst；In the Hydrobon catalyst containing carrier and load active component on the carrier and
The coagent optionally contained；The metallic element of the active component is selected from vib metals element and group VIII metal member
At least one of element.
10. according to the method for claim 9, wherein, in the Hydrobon catalyst, the carrier be silica-
Aluminum oxide, the vib metals element loaded on the carrier be molybdenum and/or tungsten and group VIII metallic element be cobalt and/
Or nickel.
11. according to the method for claim 9, wherein, in the Hydrobon catalyst, the carrier be silica-
Aluminum oxide, the vib metals element loaded on the carrier is molybdenum and/or tungsten and group VIII metallic element is nickel, institute
It is phosphorus to state the active element in coagent；Preferably,
In the Hydrobon catalyst, on the basis of the gross weight of the Hydrobon catalyst, the nickel in terms of oxide
Content be 1-10 weight %, the content sum of the molybdenum counted using oxide and tungsten as more than 10 weight % to being less than or equal to 50 weights
% is measured, the content of the phosphorus counted using oxide is carrier as 1-9 weight %, surplus.
12. the method according to claim 10 or 11, wherein, in the carrier, the content of silica is 2-45 weights
% is measured, the content of aluminum oxide is 55-98 weight %.
13. according to the method described in any one in claim 9-12, wherein, the top loading of the finishing reactor, which has, to be added
The admission space ratio of hydrogen guard catalyst, the hydrogenation protecting catalyst and the Hydrobon catalyst is 0.05~0.2：1.
14. according to the method for claim 1, wherein, the coal tar raw material be selected from coalite tar, medium temperature coal tar and
At least one of high temperature coal-tar.
15. a kind of system for coal tar hydrogenating, the system includes：
Pretreatment unit；
Slurry bed system hydrogenation unit, including slurry bed system hydrogenation reactor, the material after pretreatment unit is handled enter the slurry
Hydro-conversion is carried out in state bed hydroprocessing reactor；
First separative element, there is light fraction feed-line, the first midbarrel feed-line, the second midbarrel delivery pipe
Line, the first heavy end feed-line and the second heavy end feed-line, the material from slurry bed system hydrogenation unit is described
Separated and be fractionated successively in first separative element to obtain light fraction, midbarrel and heavy end, part is described heavy
For matter cut by being got rid of outside the first heavy end feed-line, remainder heavy end is defeated by second heavy end
Pipeline is sent to be recycled back to the slurry bed system hydrogenation reaction by the first midbarrel feed-line with the part midbarrel
Device；
Fixed bed hydrogenation unit, including finishing reactor, midbarrel described in the remainder from slurry bed system hydrogenation unit are led to
Cross the second midbarrel feed-line and described refine is introduced by the light fraction feed-line with the light fraction
Hydrofining reaction is carried out in reactor；And
Second separative element, the material from fixed bed hydrogenation unit are separated and divided successively in second separative element
Evaporate.
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