CN105925304A - Coal direct liquefying and circulating solvent and preparation method thereof - Google Patents
Coal direct liquefying and circulating solvent and preparation method thereof Download PDFInfo
- Publication number
- CN105925304A CN105925304A CN201610237828.8A CN201610237828A CN105925304A CN 105925304 A CN105925304 A CN 105925304A CN 201610237828 A CN201610237828 A CN 201610237828A CN 105925304 A CN105925304 A CN 105925304A
- Authority
- CN
- China
- Prior art keywords
- temperature oil
- oil
- high temperature
- level
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/18—Solvents
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a coal direct liquefying and circulating solvent and a preparation method thereof. The preparation method comprises the following steps: step one, subjecting oil obtained by directly liquefying coal to fractionation under a pressure of 0.02 to 0.2 MPa to obtain primary low temperature oil, primary middle temperature oil, and primary high temperature oil; step two, subjecting primary high temperature oil to hydrogenation and fractionation to obtain secondary low temperature oil, secondary middle temperature oil, and secondary high temperature oil; step three, mixing all secondary high temperature oil, part of primary middle temperature oil, and part of secondary middle temperature oil according to a certain ratio to obtain the coal direct liquefying and circulating solvent; wherein the boiling ranges of the primary low temperature oil and secondary low temperature oil are under 200 DEG C; the boiling ranges of primary middle temperature oil and secondary middle temperature oil are in a range of 200 to 320 DEG C, and the boiling ranges of primary high temperature oil and secondary high temperature oil are above 320 DEG C. The provided preparation method has the advantages that the coal conversion rate and oil yield of coal direct liquefying technology can be improved, the loss of light oil products is reduced at the same time, and moreover, the discharge of slag is reduced.
Description
Technical field
The present invention relates to coal chemical technology, in particular to a kind of DCL/Direct coal liquefaction circulating solvent and preparation method thereof.
Background technology
Direct coal liquefaction process is coal dust, solvent naphtha, catalyst etc. to be made into certain density coal slurry mix with hydrogen, successively again
Enter coal slurry preheater, reactor, under certain conditions (reaction temperature 400～450 DEG C, reaction pressure 10～
30MPa) successively react, and product separated in the separator, obtain respectively gas products, liquefaction oil product,
Process with solid residue.
In existing direct coal liquefaction process, solvent is in DCL/Direct coal liquefaction course of reaction, except by the coal dust slurry of solid,
To improve outside the physical actions such as the thermal decomposition product of the transportation performance of material, macroscopic property, dissolving coal, the most also have to coal
Thermal decomposition product provides hydrogen, makes the important chemical action such as low molecule product stabilisation of pyrolysis.Coal direct liquefaction solvent not only has
There is the function of common solvent, the most also there is good hydrogen supply and the function of transmission hydrogen.Therefore, the hydrogen supply performance of solvent, to mitigation
Reaction condition, raising coal direct liquefaction oil yield have highly important relation.
During the continuously running of coal direct liquefaction device, the solvent of use be the middle matter oil that produces of DCL/Direct coal liquefaction self and
The miscella of mink cell focus, referred to as circulating solvent, it mainly comprises is aromatic hydrocarbons and the hydrogenation of aromatics of 2～4 rings.Due to its loop control
Hydrogen content relatively low, aromatic carbon rate is high, and hydrogen supply is very poor, in order to improve the hydrogen supply capacity of solvent naphtha, must adjust its aromatic carbon rate, often
Method be that circulating solvent is carried out the hydrotreating of appropriate depth.
Therefore, for being met the circulating solvent of DCL/Direct coal liquefaction hydrogen supply better performances, technical staff is made that much research for this.
Wherein, the processing characteristic of the circulating solvent of Japan's NEDOL technique is the liquefied coal coil of coal liquefaction cellular manufacture to be distilled rear portion be allocated as
For the charging of hydrogenation plant, hydrogenation plant uses Ni-Mo catalyst.(Authorization Notice No. is Shenhua of China direct coal liquefaction process
CN1257252C) processing characteristic of circulating solvent is using full cut liquefied coal coil the entering as hydrogenation plant of coal liquefaction cellular manufacture
Material, the heavy distillate that fractionation cuts out uses Ni-Mo catalyst as circulating solvent hydrogenation plant.Publication No.
The Chinese patent application of CN1844318A discloses the hydrogenation technique of a kind of brown coal directly liquefied circulating solvent, it is provided that Yi Zhongmei
Direct liquefaction full distillate oil hydroprocessing catalysts grating technology, under suitable chemical reaction condition, it is thus achieved that hydrogen supply circulating solvent.
The patent of Publication No. CN 104194830, by being first fractionated coal direct liquefaction oil, is optionally cut wherein boiling range and is more than
The heavy oil fraction of 220 DEG C, then carries out stabilized hydrogenation, thus it is straight to obtain hydrogen supply performance preferably coal the mink cell focus that cut is narrower
Connect liquefied circulating solvent.
But, there is hydrogen consumption height and the technical problem of hydrogen supply poor performance in the processing method of above-mentioned DCL/Direct coal liquefaction circulating solvent, this is
Owing to DCL/Direct coal liquefaction crude oil narrow fraction is different with boiling range, its hydrogen supply performance is the most different, so for different narrow fractions, also depositing
In the process conditions of different optimization, therefore, it is still necessary to the processing method of existing circulating solvent is improved.
Summary of the invention
It is desirable to provide a kind of DCL/Direct coal liquefaction circulating solvent and preparation method thereof, to solve DCL/Direct coal liquefaction in prior art
There is hydrogen consumption height and the technical problem of hydrogen supply poor performance in the processing method of circulating solvent.
To achieve these goals, according to an aspect of the invention, it is provided the preparation side of a kind of DCL/Direct coal liquefaction circulating solvent
Method.This preparation method comprises the following steps: S1, carries out coal direct liquefaction oil point under conditions of pressure is 0.02～0.2MPa
Evaporate, obtain one-level low-temperature oil, one-level middle temperature oil and one-level high temperature oil；S2, is hydrogenated with one-level high temperature oil and is fractionated, obtain
Two grade low-temp oil, two grades of middle temperature oil and two grades of high temperature oil；S3, by two grades of whole high temperature oil and part primary middle temperature oil and two grades
The miscella proportioning of middle temperature oil obtains DCL/Direct coal liquefaction circulating solvent, wherein, one-level low-temperature oil and two grade low-temp oil boiling ranges < 200 DEG C,
One-level middle temperature oil and the oily boiling ranges of two grades of middle temperature are 200～320 DEG C, one-level high temperature oil and two grades of high temperature oil boiling ranges > 320 DEG C.
Further, in S1, the pressure of fractionation is 0.02～0.13MPa, the cutting temperature of one-level low-temperature oil be < 200 DEG C, one
The oily cutting temperature of the middle temperature of level is 200～320 DEG C, and the cutting temperature of one-level high temperature oil is > 320 DEG C；In S2, fractionation uses
High-temperature separator, cold catch pot and fractionating column are carried out, and the separating pressure of high-temperature separator is 10～21MPa, and separation temperature is
250～400 DEG C, the operation temperature of cold catch pot is 0～20 DEG C, and the operation pressure of fractionating column is 0.02～0.2MPa, grasps at the bottom of tower
Make temperature < 320 DEG C.
Further, one-level high temperature oil is 10～21MPa at pressure, preferably 13～19MPa, and temperature is 300～420 DEG C, excellent
It is hydrogenated with under conditions of electing 340～400 DEG C as.
Further, in one-level high temperature oil hydrogenation process, hydrogen-oil ratio is 100～1500v/v, reaction volume air speed be 0.5～
2.5h-1。
Further, hydrogen-oil ratio is 300～800v/v, and reaction volume air speed is 0.7～1.5h-1。
Further, the catalyst of two grades of high temperature oil hydrogenation includes active component and carrier, and active component is by Co, Ni, Mo
With one or more in the group of the oxide composition of W and Co, Ni, Mo and W, carrier is Al2O3、Al2O3Fiber,
One or more mixtures in molecular sieve.
Further, one or more during the auxiliary agent of catalyst is the compound of Si, P or B.
Further, the mass ratio of the miscella of two grades of high temperature oil and one-level middle temperature oil and two grades of middle temperature oil is 1:5～2:4, is preferably
1:4～2:6.
According to another aspect of the present invention, it is provided that a kind of DCL/Direct coal liquefaction circulating solvent.This DCL/Direct coal liquefaction circulating solvent leads to
The preparation method crossing any of the above-described kind prepares.
Further, in DCL/Direct coal liquefaction circulating solvent, total arene content is 70～86wt%, wherein, and the content of total mononuclear aromatics
Being 45～65wt%, the content of total double ring arene is 16～28wt%；It is 20.5～26.5mg/g for hydrogen index (HI).
Application technical scheme, after coal direct liquefaction oil i.e. DCL/Direct coal liquefaction full distillate oil is by cutting, one-level low-temperature oil
Temperature oil middle with one-level is not hydrogenated with, and is only hydrogenated with one-level high temperature oil part, therefore compared with DCL/Direct coal liquefaction full distillate oil hydrogenation,
Reducing hydrogen and consume gentle productivity, it also avoid one-level middle temperature oil in hydrogenation process and one-level high temperature oil grabs hydrogen simultaneously, thus makes
Become one-level middle temperature oil excessive hydrogenation, and one-level high temperature oil is hydrogenated with not enough result.Because only to one-level high temperature oil partial hydrogenation, can
With under the conditions of keeping identical volume space velocity, reduce reactor volume；It is simultaneous for one-level high temperature oil boiling range relative narrower, richness
Feature containing polycyclic aromatic hydrocarbon, operates more stable.Because temperature oil middle to one-level is not hydrogenated with, it is ensured that S certain in one-level middle temperature oil
Concentration of element, and S is important co-catalyst during DCL/Direct coal liquefaction, when therefore can reduce configuration coal slurry, sulphur adds
Enter amount.Meanwhile, owing to one-level low-temperature oil and one-level middle temperature oil are not hydrogenated with, part oil hydrogenation can be avoided to be cracked into hydro carbons
Gas, decreases the loss of oil product.
Application technical scheme, can improve the hydrogen supply performance of DCL/Direct coal liquefaction circulating solvent, thus increase the direct liquid of coal
The productivity of carburetion product, reduces the discharge of residue simultaneously.
Accompanying drawing explanation
The Figure of description of the part constituting the application is used for providing a further understanding of the present invention, and the present invention's is schematic real
Execute example and illustrate for explaining the present invention, being not intended that inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the process flow diagram of the preparation method of DCL/Direct coal liquefaction circulating solvent according to an embodiment of the invention.
Detailed description of the invention
It should be noted that in the case of not conflicting, the embodiment in the application and the feature in embodiment can be mutually combined.
Describe the present invention below with reference to the accompanying drawings and in conjunction with the embodiments in detail.
In prior art, there is hydrogen consumption height and the technical problem of hydrogen supply poor performance, pin in the processing method of DCL/Direct coal liquefaction circulating solvent
To this technical problem, the present invention proposes techniques below scheme.
According to a kind of typical embodiment of the present invention, it is provided that the preparation method of a kind of DCL/Direct coal liquefaction circulating solvent.This preparation side
Method comprises the following steps: S1, is fractionated coal direct liquefaction oil, obtains one-level under conditions of pressure is 0.02～0.2MPa
Low-temperature oil, one-level middle temperature oil and one-level high temperature oil；S2, is hydrogenated with one-level high temperature oil and is fractionated, obtain two grade low-temps oil,
Two grades of middle temperature oil and two grades of high temperature oil；S3, by two grades of whole high temperature oil and part primary middle temperature oil and the mixing of two grades of middle temperature oil
Oil proportioning obtains DCL/Direct coal liquefaction circulating solvent, wherein, described one-level low-temperature oil and described two grade low-temp oil boiling ranges < 200 DEG C, institute
Stating the oily and described two grades of middle temperature oil boiling range of the middle temperature of one-level is 200～320 DEG C, and described one-level high temperature oil and described two grades of high temperature oil evaporate
Journey > 320 DEG C.
In the present invention, " one-level low-temperature oil, one-level middle temperature oil and one-level high temperature oil " is intended merely to " one-level high temperature in follow-up flow process
Oil " low-temperature oil being fractionated, the oily name distinguished mutually with high temperature oil of middle temperature, wherein " one-level " and " two grades " contains without special
Justice.
Application technical scheme, after coal direct liquefaction oil i.e. DCL/Direct coal liquefaction full distillate oil is by cutting, one-level low-temperature oil
Temperature oil middle with one-level is not hydrogenated with, and is only hydrogenated with one-level high temperature oil part, therefore compared with DCL/Direct coal liquefaction full distillate oil hydrogenation,
Reducing hydrogen and consume gentle productivity, it also avoid one-level middle temperature oil in hydrogenation process and one-level high temperature oil grabs hydrogen simultaneously, thus makes
Become one-level middle temperature oil excessive hydrogenation, and one-level high temperature oil is hydrogenated with not enough result, thus also improve DCL/Direct coal liquefaction circulating solvent
Hydrogen supply performance.Because only to one-level high temperature oil partial hydrogenation, reaction can be reduced under the conditions of keeping identical volume space velocity
Body amasss；It is simultaneous for one-level high temperature oil boiling range relative narrower, feature rich in polycyclic aromatic hydrocarbon, operates more stable.Because it is right
One-level middle temperature oil is not hydrogenated with, it is ensured that S concentration of element certain in one-level middle temperature oil, and S is weight during DCL/Direct coal liquefaction
The co-catalyst wanted, the addition of sulphur when therefore can reduce configuration coal slurry.
The reactor of the hydrogenation being adapted to the present invention can be fluidized bed reactor, paste state bed reactor, expanded bed reactor, consolidate
Any one in fixed bed reactor.
Preferably, in S1, the pressure of fractionation is 0.02～0.13MPa, the cutting temperature of one-level low-temperature oil be < 200 DEG C, preferably
Being 200 DEG C, the cutting temperature of one-level middle temperature oil is 200～340, is preferably, 200～320 DEG C, the cutting temperature of one-level high temperature oil
For > 320 DEG C, be preferably 340 DEG C；In S2, fractionation uses high-temperature separator, cold catch pot and fractionating column and carries out, high
The separating pressure of temperature separator is 3～21MPa, and separation temperature is 250～400 DEG C, and the operation temperature of cold catch pot is 0～20 DEG C,
The operation pressure of fractionating column is 0.02～0.2MPa, operates temperature < 320 DEG C at the bottom of tower.
According to a kind of typical embodiment of the present invention, one-level high temperature oil is 10～21MPa at pressure, preferably 13～19MPa,
Temperature is 300～420 DEG C, is hydrogenated with under conditions of preferably 340～400 DEG C.In one-level high temperature oil hydrogenation process, hydrogen oil
Ratio is 100～1500v/v, and reaction volume air speed is 0.5～2.5h-1.Preferably, hydrogen-oil ratio is 300～800v/v, reaction volume
Air speed is 0.5～1.5h-1.At this point in the reaction, in one-level high temperature oil, polycyclic aromatic hydrocarbon generation hydro carbons is saturated, converts to low PAH,
The arene content with hydrogen supply capacity increases, thus after causing hydrogenation, high temperature oil hydrogen supply capacity increases.
According to a kind of typical embodiment of the present invention, the catalyst of one-level high temperature oil hydrogenation includes active component and carrier, activity
Component is one or more in the group being made up of the oxide of Co, Ni, Mo and W and Co, Ni, Mo and W, carrier
For Al2O3、Al2O3One or more mixtures in fiber molecule sieve.Preferably, the main active ingredient of catalyst be Ni,
W, carrier is Al2O3And Al2O3The complex carrier that fiber is prepared from, the auxiliary agent of catalyst is in the compound of Si, P or B
One or more.Use this type catalyst and catalyst promoter, on the one hand ensure that catalyst has good catalysis activity
Center and acidic site, it is ensured that the hydrogenation capability of catalyst, be provided simultaneously with certain cracking activity；On the other hand the present invention is adopted
Can ensure that with carrier the macromolecular substances such as polycyclic aromatic hydrocarbon contact with the effective of catalyst activity component and react；After ensureing hydrogenation
High temperature oil has good hydrogen supply capacity.
Preferably, the mass ratio of the miscella of two grades of high temperature oil and one-level middle temperature oil and two grades of middle temperature oil is 1:5～2:4, is preferably
1:4～2:6.Middle temperature oil and the proportioning of high temperature oil, both ensure that the hydrogen supply capacity of solvent, also ensure that solvent possessed certain simultaneously
Solvability, promotes the carrying out of DCL/Direct coal liquefaction process.
According to a kind of typical embodiment of the present invention, it is provided that a kind of DCL/Direct coal liquefaction circulating solvent.This DCL/Direct coal liquefaction circulation is molten
Agent is prepared by above-mentioned preparation method.Wherein, in DCL/Direct coal liquefaction circulating solvent, total arene content is 70～86wt%, its
In, the content of total mononuclear aromatics is 45～65wt%, and the content of total double ring arene is 16～28wt%；For hydrogen index (HI) be 20.5～
26.5mg/g.This DCL/Direct coal liquefaction circulating solvent can be used for the preparation of coal slurry in coal direct liquefaction, transports and DCL/Direct coal liquefaction
The carrying out of reaction.Wherein, DCL/Direct coal liquefaction hydrogen supply dissolvent for the coal slurry conveying of direct coal liquefaction process, hydrogen supply, hydrogen transmit with
And free radical is stable, it is possible to ensure stable, the efficient output of DCL/Direct coal liquefaction oil product, also reduces hydrogen simultaneously and consume gentle productivity.
Beneficial effects of the present invention is further illustrated below in conjunction with embodiment, the operating process write the most in detail in the following example,
Parameter or reagent all can use this area conventional technique means to realize.
Embodiment 1
As it is shown in figure 1, in the present embodiment the preparation facilities of DCL/Direct coal liquefaction circulating solvent by fractionating column 10, surge tank 20, add
Hydrogen reactor 30, high-temperature separator 40, cold catch pot 50, fractionating column 60 and circulating hydrogen compressor 70 form.
The i.e. coal direct liquefaction oil of DCL/Direct coal liquefaction full distillate oil come from DCL/Direct coal liquefaction unit enters fractionating column 10, is respectively cut
Become one-level low-temperature oil, one-level middle temperature oil and three fraction section of one-level high temperature oil.Wherein, one-level high temperature oil enters surge tank 20 conduct
Follow-up hydrogenation raw material.Bottom surge tank 20, enter hydrogenation reactor 30 after two grades of high temperature oil out and hydrogen mixing add
Hydrogen reacts.It is introduced into high-temperature separator 40 from hydrogenation reactor 30 hydrogenation afterproduct out to carry out product separation top material and enter
Entering cold catch pot 50 and carry out product separation, a cold catch pot 50 top material part is after circulating air compressor 70 compresses
Mixing the raw material as hydrogenation reactor with fresh hydrogen, a part goes subsequent gases processing means as periodic off-gases；Go out bottom it
Material enters and enters fractionating column 60 with high score bottoms material and carry out product and separate, fractionating column 60 top discharge and fractionating column 10 top discharge
Mixing is as low-temperature oil product；Fractionating column 60 sidepiece discharging and fractionating column 10 side discharging mixing are as middle temperature oil product；Fractionation
Tower bottom is as two grades of high temperature oil products.By the miscella of middle to all second-order high temperature oil and part primary temperature oil and two grades of middle temperature oil (i.e.
Middle temperature oil) mixed preparing becomes DCL/Direct coal liquefaction circulating solvent.
From DCL/Direct coal liquefaction reaction full distillate oil by being fractionated in the fractionating column 10 that pressure is 0.05MPa, isolate
One-level low-temperature oil less than 220 DEG C, the one-level middle temperature oil of 220～320 DEG C, and > the one-level high temperature oil of 320 DEG C.
Above-mentioned one-level high temperature oil is hydrogenated stablize raw material surge tank 20 stable after, enter in hydrogenation reactor 30 in tungsten nickel series
Carrying out hydrogenation reaction under catalyst effect, be 19MPa at pressure, temperature is 390 DEG C, and hydrogen-oil ratio is 300v/v；Reaction sky
Speed is 1.5h-1Under conditions of carry out stabilized hydrogenation, obtain stabilized hydrogenation oil.
Drawing the stabilized hydrogenation oil obtained from hydrogenation reactor, be 19MPa at pressure, separation temperature is the hot high score of 250 DEG C
Separator 40 separates.
It is 19MPa that the light-end products at hot high score separator 40 top enter pressure, and temperature is in the cold high score separator 50 of 20 DEG C
Separating, the oil product out of the bottom after separation and Re Gao separator bottoms material enter fractionating column 60 and are fractionated, this fractionation
< 220 DEG C are mixed to get low-temperature oil (i.e. one-level low-temperature oil and two grade low-temps oil with fractionating column 10 top discharge to top of tower oil product out
Miscella), sidepiece oil product (> out 220 DEG C) and fractionating column 10 lateral line discharging be mixed to get middle temperature oil (the i.e. middle temperature of one-level
Oil and the oily miscella of two grades of middle temperature), bottom out for two grades of high temperature oil.
By all second-order high temperature oil obtained bottom fractionating column 40 and (i.e. one-level middle temperature oil and two grades of oily the mixing of middle temperature of part middle temperature oil
Close oil) become DCL/Direct coal liquefaction circulating solvent according to the proportions of 2:7.Middle temperature oil will be remained and low-temperature oil mixing can be as hydrogenation
The feedstock oil of modifying process.
The hydrogenation catalyst used in the present invention is nickel tungsten catalyst series, and carrier is modified Al2O3And Al2O3Fibre blend,
Catalyst promoter is P.
Embodiment 2
Other conditions are constant, change the reaction temperature of boiling bed hydrogenation reactor into 400 DEG C, and reaction velocity is 1h-1Under conditions of
Carry out stabilized hydrogenation, obtain stabilized hydrogenation oil.By oily for middle to obtained high temperature oil and the part temperature proportions coal-forming according to 2:7
Direct liquefaction circulating solvent.
The hydrogenation catalyst used in the present invention is with embodiment 1
Embodiment 3:
Other conditions are constant, change the reaction temperature of boiling bed hydrogenation reactor into 420 DEG C, and reaction velocity is 0.5h-1Under conditions of
Carrying out stabilized hydrogenation, hydrogen-oil ratio is 300v/v, obtains stabilized hydrogenation oil.By middle to obtained high temperature oil and part temperature oil according to 1:
The proportions of 4 becomes DCL/Direct coal liquefaction circulating solvent.
The hydrogenation catalyst used in the present invention is with embodiment 1
Embodiment 4:
Other conditions are constant, are 13MPa by the pressure of boiling bed hydrogenation reactor, and reaction temperature changes 340 DEG C into, and reaction velocity is
1.5h-1Under conditions of carry out stabilized hydrogenation, hydrogen-oil ratio is 800v/v, obtain stabilized hydrogenation oil.By obtained high temperature oil and part
Middle temperature oil becomes DCL/Direct coal liquefaction circulating solvent according to the proportions of 2:6.
The hydrogenation catalyst used in the present invention is nickel molybdenum series catalyst, and carrier is modified Al2O3。
Same above-described embodiment of step of embodiment 5～8, parameter unlike the embodiments above is as shown in table 1.
Table 1
Comparative example 1:
Choose the full distillate oil from DCL/Direct coal liquefaction, as a comparison case the DCL/Direct coal liquefaction circulating solvent of 1.
Comparative example 2:
Full distillate oil from DCL/Direct coal liquefaction reaction enters in fluidized bed reactor to enter under the catalytic action of tungsten nickel catalyst series
Row hydrogenation reaction, is 19MPa at pressure, and temperature is 390 DEG C, and hydrogen-oil ratio is 300v/v；Reaction velocity is 1.5h-1Under conditions of
Carry out stabilized hydrogenation, obtain stabilized hydrogenation oil.The stabilized hydrogenation oil obtained is drawn from fluidized bed reactor, at pressure is
19MPa, separation temperature is to separate in the hot high score separator of 400 DEG C, it is thus achieved that high temperature oil.Hot high score separator top
It is 19MPa that material enters pressure, and temperature is that the low temperature of 20 DEG C divides in separator and separates.Cold catch pot bottoms material and height
Temperature oil enters into fractionating column together and is fractionated, and controlling fractionating column pressure is 0.05MPa, isolates the low-temperature oil less than 200 DEG C,
The middle temperature oil of 200～320 DEG C, and > high temperature oil of 320 DEG C.
Whole high temperature oil temperature middle with the part oil obtained by fractionating column becomes DCL/Direct coal liquefaction circulating solvent according to the proportions of 2:7.
Middle temperature oil and the low-temperature oil mixing feedstock oil as hydrogenation modifying process will be remained.
Table 1 circulating solvent analyzes data
Then the DCL/Direct coal liquefaction circulating solvent in embodiment 1-8 and comparative example 2 has been carried out autoclave DCL/Direct coal liquefaction test.
Autoclave DCL/Direct coal liquefaction is tested:
The process conditions of autoclave DCL/Direct coal liquefaction test are as shown in table 3, use 0.5L stirred autoclave, and entering still coal amount is
28g (dry coal), circulating solvent is 1.5:1 with the mass ratio of coal, and hydrogen first pressing is 10.0MPa, and catalyst is Fe-series catalyst,
Fe addition is the 1% of dry coal mass fraction, and co-catalyst is sulphur, and n (S)/n (Fe) is 2.It is warmed up to reaction temperature 455 DEG C
After, constant temperature 60min.
Autoclave product is divided into gas-phase product and 2 parts of liquid-solid mixture, and gas-phase product uses gas chromatograph to form
Analyze；Liquid-solid phase product carries out soxhlet type with n-hexane with oxolane successively and separates.
Wherein, n-hexane DDGS is defined as oil, is preasphaltene by insoluble for n-hexane and that oxolane is solvable Material Definitions
With asphaltene (abbreviation asphaltene fraction), equal for oxolane insoluble matter is defined as unconverted coal.
Table 2 DCL/Direct coal liquefaction autoclave test condition
Table 3 DCL/Direct coal liquefaction autoclave test result
In upper table, product yield, conversion ratio and hydrogen consume with butt coal, on the basis of wt%.
The autoclave coal liquefaction result of the test of above-mentioned table 3 shows, embodiment 1,2,3 is fractionated into DCL/Direct coal liquefaction full distillate oil
After, high temperature oil is hydrogenated with the most again with middle temperature oil proportioning as circulating solvent, entirely evaporate with DCL/Direct coal liquefaction than in comparative example 2
The circulating solvent being fractionated acquisition after dividing oil hydrogenation again carries out coal blending direct liquefaction reaction, although hydrogen consumption is slightly higher, but coal conversion ratio is high,
Oil yield is high, and asphalt road material and gas yield decline, and demonstrates coal direct liquefaction oil further and is fractionated into obtaining mink cell focus,
The most hydrogenated hydrogen supply performance improving circulating solvent.
As can be seen from the above description, the above embodiments of the present invention achieve following technique effect:
1), after coal direct liquefaction oil i.e. DCL/Direct coal liquefaction full distillate oil is by cutting, one-level low-temperature oil and one-level middle temperature oil are not hydrogenated with,
Only one-level high temperature oil part is hydrogenated with, therefore compared with DCL/Direct coal liquefaction full distillate oil hydrogenation, reduces hydrogen and consume gentle productivity,
It also avoid one-level middle temperature oil in hydrogenation process and one-level high temperature oil grabs hydrogen simultaneously, thus causes one-level middle temperature oil excessive hydrogenation,
And the result that one-level high temperature oil hydrogenation is not enough, thus also improve the hydrogen supply performance of DCL/Direct coal liquefaction circulating solvent.
2) because only to one-level high temperature oil partial hydrogenation, reactor volume can be reduced under the conditions of keeping identical volume space velocity；
It is simultaneous for one-level high temperature oil boiling range relative narrower, feature rich in polycyclic aromatic hydrocarbon, operates more stable.
3) because temperature oil middle to one-level is not hydrogenated with, it is ensured that S concentration of element certain in one-level middle temperature oil, and S is at the direct liquid of coal
It is important co-catalyst during change, the addition of sulphur when therefore can reduce configuration coal slurry.
4) by the enforcement of the present invention, conversion ratio and the product oil yield of coal can be improved, reduce hydrogen consumption, minimizing discharge of materials,
Improve feed coal utilizes level, reduces the investment of solvent hydrogenation simultaneously, improves direct coal liquefaction process macroeconomic level.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for those skilled in the art
For, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, any amendment of being made, etc.
With replacement, improvement etc., should be included within the scope of the present invention.
Claims (10)
1. the preparation method of a DCL/Direct coal liquefaction circulating solvent, it is characterised in that comprise the following steps:
S1, is fractionated under conditions of pressure is 0.02～0.2MPa coal direct liquefaction oil, obtain one-level low-temperature oil,
One-level middle temperature oil and one-level high temperature oil；
S2, is hydrogenated with described one-level high temperature oil and is fractionated, and obtains two grade low-temp oil, two grades of middle temperature oil and two grades of high temperature
Oil；
S3, obtains institute by the miscella proportioning of whole described two grades of high temperature oil with part primary middle temperature oil and two grades of middle temperature oil
State DCL/Direct coal liquefaction circulating solvent,
Wherein, < 200 DEG C, the middle temperature of described one-level is oily and described two grades for described one-level low-temperature oil and described two grade low-temp oil boiling ranges
Middle temperature oil boiling range is 200～320 DEG C, described one-level high temperature oil and described two grades of high temperature oil boiling ranges > 320 DEG C.
Preparation method the most according to claim 1, it is characterised in that in described S1, the pressure of described fractionation be 0.02～
0.13MPa, the cutting temperature of described one-level low-temperature oil is that < 200 DEG C, the cutting temperature of described one-level middle temperature oil is
200～320 DEG C, the cutting temperature of described one-level high temperature oil is > 320 DEG C；In described S2, described fractionation uses high temperature
Separator, cold catch pot and fractionating column are carried out, and the separating pressure of described high-temperature separator is 10～21MPa, separation temperature
Being 250～400 DEG C, the operation temperature of described cold catch pot is 0～20 DEG C, the operation pressure of described fractionating column be 0.02～
0.2MPa, operates temperature < 320 DEG C at the bottom of tower.
Preparation method the most according to claim 1, it is characterised in that described one-level high temperature oil is 10～21MPa at pressure,
Preferably 13～19MPa, temperature is 300～420 DEG C, is hydrogenated with under conditions of preferably 340～400 DEG C.
Preparation method the most according to claim 3, it is characterised in that in described one-level high temperature oil hydrogenation process, hydrogen-oil ratio
Being 100～1500v/v, reaction volume air speed is 0.5～2.5h-1。
Preparation method the most according to claim 4, it is characterised in that described hydrogen-oil ratio is 300～800v/v, described reactant
Long-pending air speed is 0.7～1.5h-1。
Preparation method the most according to claim 1, it is characterised in that the catalyst of described two grades of high temperature oil hydrogenation includes activity
Component and carrier, described active component is to be made up of the oxide of Co, Ni, Mo and W and Co, Ni, Mo and W
Group in one or more, described carrier is Al2O3、Al2O3One or more mixtures in fiber, molecular sieve.
Preparation method the most according to claim 6, it is characterised in that the auxiliary agent of described catalyst is the chemical combination of Si, P or B
One or more in thing.
Preparation method the most according to claim 1, it is characterised in that described two grades of high temperature oil and described one-level middle temperature oil and two
The mass ratio of the miscella of level middle temperature oil is 1:5～2:4, preferably 1:4～2:6.
9. a DCL/Direct coal liquefaction circulating solvent, it is characterised in that by the preparation side as according to any one of claim 1 to 8
Method prepares.
DCL/Direct coal liquefaction circulating solvent the most according to claim 9, it is characterised in that in described DCL/Direct coal liquefaction circulating solvent
Total arene content is 70～86wt%, and wherein, the content of total mononuclear aromatics is 45～65wt%, and the content of total double ring arene is
16～28wt%；It is 20.5～26.5mg/g for hydrogen index (HI).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610237828.8A CN105925304B (en) | 2016-04-15 | 2016-04-15 | DCL/Direct coal liquefaction cycle solvent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610237828.8A CN105925304B (en) | 2016-04-15 | 2016-04-15 | DCL/Direct coal liquefaction cycle solvent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105925304A true CN105925304A (en) | 2016-09-07 |
| CN105925304B CN105925304B (en) | 2018-06-26 |
Family
ID=56839169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610237828.8A Active CN105925304B (en) | 2016-04-15 | 2016-04-15 | DCL/Direct coal liquefaction cycle solvent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105925304B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106479564A (en) * | 2016-09-21 | 2017-03-08 | 神华集团有限责任公司 | Circulating solvent and preparation method thereof |
| CN107118799A (en) * | 2017-04-20 | 2017-09-01 | 神华集团有限责任公司 | DCL/Direct coal liquefaction circulation solvent and preparation method thereof |
| CN108504378A (en) * | 2017-02-28 | 2018-09-07 | 中科合成油技术有限公司 | A kind of preparation method of coal hydrogenation pyrolysis hydrogen supply dissolvent oil, the hydrogen supply dissolvent oil and application thereof thus prepared |
| WO2024148467A1 (en) * | 2023-01-09 | 2024-07-18 | 中国神华煤制油化工有限公司 | Recycled hydrogen-donor solvent for direct coal liquefaction and preparation method therefor and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103468315A (en) * | 2013-09-27 | 2013-12-25 | 神华集团有限责任公司 | Direct coal liquefaction circulation solvent and preparation method and application of direct coal liquefaction circulation solvent |
| CN104194830A (en) * | 2014-08-29 | 2014-12-10 | 神华集团有限责任公司 | Direct coal liquefaction circulating solvent and processing method thereof as well as direct coal liquefaction method utilizing direct coal liquefaction circulating solvent |
| CN104910961A (en) * | 2015-06-03 | 2015-09-16 | 神华集团有限责任公司 | Direct-coal-liquefied circulating hydrogen-donor solvent and preparation method thereof |
-
2016
- 2016-04-15 CN CN201610237828.8A patent/CN105925304B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103468315A (en) * | 2013-09-27 | 2013-12-25 | 神华集团有限责任公司 | Direct coal liquefaction circulation solvent and preparation method and application of direct coal liquefaction circulation solvent |
| CN104194830A (en) * | 2014-08-29 | 2014-12-10 | 神华集团有限责任公司 | Direct coal liquefaction circulating solvent and processing method thereof as well as direct coal liquefaction method utilizing direct coal liquefaction circulating solvent |
| CN104910961A (en) * | 2015-06-03 | 2015-09-16 | 神华集团有限责任公司 | Direct-coal-liquefied circulating hydrogen-donor solvent and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106479564A (en) * | 2016-09-21 | 2017-03-08 | 神华集团有限责任公司 | Circulating solvent and preparation method thereof |
| CN108504378A (en) * | 2017-02-28 | 2018-09-07 | 中科合成油技术有限公司 | A kind of preparation method of coal hydrogenation pyrolysis hydrogen supply dissolvent oil, the hydrogen supply dissolvent oil and application thereof thus prepared |
| CN108504378B (en) * | 2017-02-28 | 2020-04-17 | 中科合成油技术有限公司 | Preparation method of coal hydropyrolysis hydrogen-donating solvent oil, hydrogen-donating solvent oil prepared by same and application thereof |
| CN107118799A (en) * | 2017-04-20 | 2017-09-01 | 神华集团有限责任公司 | DCL/Direct coal liquefaction circulation solvent and preparation method thereof |
| WO2024148467A1 (en) * | 2023-01-09 | 2024-07-18 | 中国神华煤制油化工有限公司 | Recycled hydrogen-donor solvent for direct coal liquefaction and preparation method therefor and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105925304B (en) | 2018-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2017181813A1 (en) | Method and equipment thereof for producing high-quality diesel using low-temperature fischer-tropsch synthetic oil and low-grade oil feedstock | |
| CN105647573A (en) | Method for producing light-weight aromatic hydrocarbons and clean fuel oil by moving bed hydrocracking | |
| CN105925304A (en) | Coal direct liquefying and circulating solvent and preparation method thereof | |
| CN102344828B (en) | Processing method of inferior residual oil | |
| CN103468314B (en) | DCL/Direct coal liquefaction circulating solvent and its preparation method and application | |
| CN108102709B (en) | Processing method of catalytic diesel oil | |
| CN105623725B (en) | A kind of group technology of heavy/Residual cracking | |
| CN101343557B (en) | Method for preparing high-quality ethylene raw material with petroleum naphtha hydrogenation | |
| CN103468315B (en) | DCL/Direct coal liquefaction circulating solvent and its preparation method and application | |
| CN109988606B (en) | Flexible reverse hydrocracking process | |
| CN103773462B (en) | A kind of two-segment hydrocracking method producing high-quality industrial chemicals | |
| CN102344829A (en) | Combination method for residue hydrotreatment, catalytic cracking heavy oil hydrogenation and catalytic cracking | |
| CN109988631B (en) | Method for producing gasoline and base oil by catalyst grading technology | |
| CN108102702B (en) | Method for processing catalytic diesel oil | |
| CN109988623B (en) | Flexible reverse hydrocracking process | |
| CN106520197B (en) | A kind of method for hydrogen cracking that boat coal is produced by inferior feedstock oil | |
| CN109988651B (en) | Method for producing gasoline by catalyst grading technology | |
| CN104419461B (en) | The slurry bed system of a kind of coal tar and fixed bed serial hydrogenation technique | |
| CN109988625B (en) | Hydrofining and hydrocracking combined process | |
| CN109988632B (en) | Method for producing gasoline and diesel oil by catalyst grading technology | |
| CN108102703A (en) | A kind of processing and treating method of catalytic diesel oil | |
| CN109988620A (en) | Produce the flexible hydrocracking process of lube base oil | |
| CN114437804B (en) | Hydrocracking method of high-nitrogen raw oil | |
| CN114736708B (en) | Wax oil liquid phase hydrotreating method | |
| CN109988618B (en) | Flexible single-stage two-agent hydrocracking process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |