CN103059987B - Hydrotreatment method for coal tar - Google Patents
Hydrotreatment method for coal tar Download PDFInfo
- Publication number
- CN103059987B CN103059987B CN201110355711.7A CN201110355711A CN103059987B CN 103059987 B CN103059987 B CN 103059987B CN 201110355711 A CN201110355711 A CN 201110355711A CN 103059987 B CN103059987 B CN 103059987B
- Authority
- CN
- China
- Prior art keywords
- reactor
- reaction
- oil
- accordance
- coal tar
- 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.)
- Active
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a hydrotreatment method for coal tar. The method disclosed by the invention comprises the following steps of: pumping coal tar which is high in the contents of impurities, colloid, asphaltene, oxygen element and the like into a prehydrogenation reactor, and then performing hydrogenation pre-treatment; filtering to separate out tiny impurities suspended in the generated oil; sequentially performing hydrodemetallization reaction and deep hydrofining reaction; separating out water and light-weight components from the material flow generated by the reactions, and conveying the water and the light-weight components in a hydrocracking reactor; and then cutting out gasoline fraction, diesel oil and hydrocracking tail oil via a distillation device, wherein a magnetic catalyst is filled in the prehydrogenation reactor, and the operation is performed by means of a magnetically stabilized bed. Compared with the prior art, with the adoption of the method disclosed by the invention, the long-period stable running of the device can be ensured.
Description
Technical field
The present invention relates to a kind of Hydrotreatment method for coal tar, particularly with the distillate of coal tar or full fraction of coal tar for raw material, adopt the multi-stek hydrogenation explained hereafter of magnetic stablizing bed pre-treatment and fixed bed catalyst grading loading to clean the technological process of light Fuel.
Background technology
Coal tar is the by product of coal coking, destructive distillation and gasification.Coal tar is different from natural oil, and composition is complicated, and condensed-nuclei aromatics, resin and asphalt content are high, containing a large amount of containing oxygen polar material and a certain amount of unsaturated hydrocarbons and sulphur, nitrogen and metal impurities.Simultaneously, containing inorganic impurity tiny in a large number and organic impurity in coal tar, inorganic impurity mainly particle diameter is about 10 μm of iron filings and oxide powder thereof, organic impurity is mainly the high-temperature hot polymers that median size is aromatic hydrocarbon molecule in the coal of 0.5 μm, above-mentioned fine impurities is dispersed in coal tar under the effect of polar material, adopts the means such as conventional filtration, sedimentation and centrifugation to be difficult to remove.The fixed bed of employing routine, ebullated bed and suspension bed can be made to process dead oil for a large amount of condensed-nuclei aromaticss contained in the existence of these impurity and raw material or full cut all exists certain difficulty, and such as fixed bed solid matter easily occurs and blocks bed problem; Ebullated bed requires that gas-liquid flow velocity in reactor is between certain operational zone, and the boiling state of catalyzer is very strong to the composition of logistics, flow velocity and catalyst property dependency; And floating bed hydrogenation effect is remarkable, be unfavorable for removing of impurity in charging, and the catalyzer added and hydrogenation tail oil be separated the difficult problem being still and cannot properly settling at present.
CN1464031A describes a kind of coal tar hydrogenation process and catalyzer.When mentioning the undressed coal tar of direct processing in this patent, before hydrogenator, set up one to four switch protecting reactors.Switch protecting reactor is built with hydrofining catalyzer.This catalyzer with the mixture of aluminum oxide and titanium oxide for carrier, with the metallic sulfide of molybdenum, nickel, cobalt etc. for active metal component.Hydrogenator can be suspended-bed reactor, fixed-bed reactor, moving-burden bed reactor or ebullated bed reactor, use in reactor with aluminum oxide and titanium oxide as carrier, the metallic sulfide of molybdenum, nickel, cobalt etc. is active metal component, and molecular sieve is the loaded catalyst of promotor.Although be provided with guard reactor in this technique before hydrotreating reactor; if but guard reactor adopts fixed bed operation, is easy to block; the problem that tail oil difficulty is separated and after hydrogenation, logistics impurity removal percentage is low that then can run into containing solid is operated as adopted suspension bed; gas-liquid flow velocity is controlled between the operational zone of regulation, if gas-liquid flow velocity will not affect the steady running of device in this span of control as adopted ebullated bed manipulation require.
CN101962572A describes coal tar heavy fractioning boiling bed hydrogenation cracking method and system.Although ebullated bed is strong to adaptability to raw material, but keep the catalyzer in reactor to be in boiling state and require that gas-liquid flow velocity is between certain operational zone, very strong to the composition of logistics in reactor, flow velocity, character and catalyst property dependency, there is certain operation limitation, and ebullated bed and fixed bed are compared, its impurity removal percentage is relatively low.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of coal tar hydrotreating process, especially arrange a coal tar pre-hydrotreating section, this section uses magnetically stabilized bed reactor and has ferromagnetic hydrogenation catalyst.This pretreatment section can make a large amount of tiny solid impurity pass or be trapped in catalyst void, and simultaneously containing oxygen isopolarity material hydrogenation and removing oxygen, this can be avoided the accumulation of impurity on beds, the long-term operation of assurance device.
Hydrotreatment method for coal tar of the present invention, comprises following content:
(a), in magnetically stabilized bed reactor, by the mixture of coal tar raw material and hydrogen with there is ferromagnetic hydrogenation catalyst contact, at pressure 3 ~ 16MPa, temperature 150 ~ 280 DEG C, hydrogen to oil volume ratio 200 ~ 2000, during liquid, volume space velocity is 0.1 ~ 10h
-1, magneticstrength is carry out unsaturated hydrocarbons and the hydrogenation reaction containing materials such as oxygen under the reaction conditions of 50 ~ 1000 oersteds, discharges the fine impurities of this material parcel; Wherein said magnetically stabilized bed reactor is that inside exists uniform magnetic field and loaded the reactor with ferromagnetic hydrogenation catalyst;
B (), step (a) obtain the fine solid particles that pre-hydrotreating reaction generates separating of oil fuel-displaced middle suspension;
(c), isolate fine solid particles after logistics carry out hydrodemetallation (HDM) reaction;
D (), step (c) gained hydrodemetallation (HDM) reaction effluent carry out hydrofining reaction;
E (), step (d) gained hydrofining reaction effluent, through being separated, are separated water outlet and light constituent and heavy constituent;
According to coal tar processing treatment process of the present invention, wherein also comprise step (f): the isolated heavy constituent of step (e) carries out hydrocracking reaction; With step (g): step (f) gained isocrackate cuts out gasoline fraction, diesel oil distillate and cracking tail oil through water distilling apparatus.
Pre-hydrotreating section wherein described in step (a) adopts magnetically stabilized bed reactor, and in reactor, filling has ferromagnetic hydrogenation catalyst, this hydrogenation catalyst attract each other due to the magnetization in magnetic field and stable existence in reactor.Described has the catalyzer that ferromagnetic hydrogenation catalyst is the magnetic carrier load hydrogenation active metals be made up of magnetic-particle, and the granular size of catalyzer is 10 ~ 1000 μm.Wherein magnetic carrier is by SiO
2, Al
2o
3or its mixture and magnetic-particle form, magnetic-particle is wherein by SiO
2coating layer and magnetic particle kernel composition.Magnetic particle wherein can be selected from one or more in magneticmetal iron (Curie temperature is 1043K), cobalt (Curie temperature is 1388K) and nickel (Curie temperature is 627K) and alloy thereof and oxides-containing iron, is preferably Fe, Fe
3o
4(Curie temperature is 820 ~ 986K) and γ-Fe
2o
3one or more in (Curie temperature is 850K).Wherein the particle diameter of magnetic particle is 0.02 ~ 200 μm, and during selection iron powder, particle diameter is preferably 20 ~ 150 μm; For Fe
3o
4with γ-Fe
2o
3particle diameter is preferably 3 ~ 50nm.The hydrogenation active component composition of catalyzer is by weight percentage: molybdenum oxide 1% ~ 5%, nickel oxide 0.1% ~ 4%, can also contain conven-tional adjuvants, and all the other are the refractory oxide such as silicon-containing alumina or aluminum oxide carrier.
In the inventive method, said magnetically stabilized bed reactor is made up of reactor and externally-applied magnetic field, externally-applied magnetic field is the uniform steady magnetic field along reactor axis, uniform magnetic field by direct supply and a series of helmholtz coil of coaxially arranging with reactor or evenly high-density solenoid provide, reactor and other parts of reactor are made up of the material that magnetic permeability is good.
Described pre-hydrotreating operational condition is: pressure 3 ~ 16MPa, temperature: 150 ~ 280 DEG C, preferably 180 ~ 260 DEG C, hydrogen to oil volume ratio 200 ~ 2000, and during liquid, volume space velocity is 0.1 ~ 10h
-1, magneticstrength is 50 ~ 1000 oersteds (Oe).
The described fine solid particles isolating suspension from pre-treatment generation oil of step (b) can adopt various tripping device, as filtration unit or centrifugal separating device etc.
The said hydrodemetallation (HDM) reaction of step (c) uses fixed-bed reactor, the catalyzer selected is conventional hydro catalyst for demetalation, catalyzer composition is by weight percentage: molybdenum oxide 1% ~ 10%, nickel oxide 0.1% ~ 5%, can contain conven-tional adjuvants, all the other are the refractory oxide such as silicon-containing alumina or aluminum oxide carrier.Catalyzer pore volume is 0.20 ~ 0.70mL/g, and specific surface is 100 ~ 200m
2/ g.
Deep hydrofinishing reaction described in step (d) uses fixed-bed reactor, the catalyzer selected is conventional hydro catalyst for refining, catalyzer composition is by weight percentage: molybdenum oxide 5% ~ 25%, nickel oxide 1% ~ 10%, can contain conven-tional adjuvants, all the other are the refractory oxide such as silicon-containing alumina or aluminum oxide carrier.Catalyzer pore volume is 0.20 ~ 0.50mL/g, and specific surface is 100 ~ 200m
2/ g.
The device of the described separation of step (e) can be high-pressure separator or flashing tower etc., and wherein the cut point of light constituent and heavy constituent is 130 ~ 210 DEG C.
Hydrocracking reaction described in step (f) uses fixed-bed reactor, and the catalyzer of selection is hydrocracking catalyst.Catalyzer composition is by weight percentage: Tungsten oxide 99.999 10% ~ 30%, nickel oxide 5% ~ 15%, a certain amount of molecular sieve can be contained, as one or both in Y zeolite and beta-molecular sieve, generally can contain molecular sieve 1% ~ 30%, all the other are the refractory oxide carriers such as amorphous aluminum silicide, silicon-containing alumina, aluminum oxide.Catalyzer pore volume is 0.10 ~ 0.50 mL/g, and specific surface is 120 ~ 350 m
2/ g.
Said Hydrodemetalation catalyst and deep hydrofinishing catalyzer can be seated in same reactor above, or use multiple reactor.
The reaction conditions of the fixed bed hydrogenation demetalization reaction described in step (c) is: pressure 10 ~ 20MPa, temperature: 300 ~ 380 DEG C, hydrogen to oil volume ratio 200 ~ 3000, volume space velocity is 0.1 ~ 10h
-1.
The reaction conditions of the fixed bed deep hydrofinishing conversion zone described in step (d) is: pressure 10 ~ 20MPa, temperature: 340 ~ 400 DEG C, hydrogen to oil volume ratio 200 ~ 3000, and volume space velocity is 0.1 ~ 10h
-1.
The reaction conditions of the fixed bed hydrogenation soaking section described in step (f) is: pressure 10 ~ 20MPa, temperature: 350 ~ 420 DEG C, hydrogen to oil volume ratio 200 ~ 3000, and volume space velocity is 0.1 ~ 10h
-1.
Coal tar is that a kind of character is poor, condensed-nuclei aromatics, resin and asphalt content are high, the non-natural oil that mechanical impurity, metal content (especially iron and calcium), oxygen level are very high, simply can not apply mechanically the processing scheme and catalyst loading technology that use in existing refining of petroleum.Organic and the inorganic impurity tiny in a large number contained in coal tar containing oxygen isopolarity material effect under the uniform and stable larger coal tar raw material of density that is suspended in (density of usual coal tar is 1100 ~ 1300kg/m
3) in, be difficult to adopt the methods such as conventional filtration to remove.Carrying out coal tar deep processing at employing fixed bed produces in light Fuel process, and along with the carrying out of hydrogenation reaction, carry out the reactions such as hydrogenation deoxidation containing oxygen isopolarity material after, tiny impurity is released, and is easy to be deposited in reactor bed.Simultaneously conventional heavy oil fixed bed catalyst filling scheme is along reactant flow flow direction, catalyzer aperture is more and more less, this is easy to cause reactor bed to block, especially the reaction bed position that deoxidation rear impurity discharges is easier to blocking, affects the long period smooth operation of whole reaction unit.The magnetically stabilized bed reactor adopting the present invention that ferromegnetism load hydrogenation catalyst is housed carries out coal tar hydrogenating pre-treatment, higher void among particles rate can be provided, raw material is through hydrogenation and removing oxygen isopolarity impurity, discharge the fine solid particles wrapped up by polar material, make it pass through or be trapped between high voidage granules of catalyst, then namely conveniently can be removed by simple modes such as filtrations, the steady running of follow up device can be ensured.
Specifically, the inventive method has the following advantages:
(1) magnetic stablizing bed operating method is adopted to carry out coal tar hydrogenating pre-treatment, be conducive to the release of the solia particle of raw material heteroatoms and hydrogenation of unsaturated hydrocarbons and parcel thereof, and unimpeded impurity passage and detention space can be provided, the coal tar pre-treatment high for foreign matter content provides a kind of selection scheme.
(2) prior art of magnetic stablizing bed and magnetic catalyst being combined for hydrogenation is mainly used in low-carbon (LC) hydrogenation of unsaturated hydrocarbons, light petroleum fraction (as gasoline or diesel oil) adsorption desulfurize, compound selec-tive hydrogenation prepare the reactions such as new compound, the advantage of said process is can by conversion magneticstrength, realize catalyzer and add row online, magnetic catalyst can be reclaimed re-use, reduce catalyzer running cost.And the present invention proposes to adopt magnetic stablizing bed associating with magnetic catalyst to carry out coal tar pre-treatment, except there is above-mentioned advantage, also take into full account that coal tar contains Ferromagnetic Impurities (oxide compound of iron and iron), its under the action of a magnetic field with coal tar logistics separate out suspended in the reactor, hydrogenation can be played at reaction conditions and carry a burnt effect.
(3) adopt multistage combination process, make each section process raw material with processing condition and catalyzer reasonably combined, give full play to the activity of catalyzer, ensure quality product.
(4) adopt the coal tar processing scheme progressively increasing temperature of reaction relaxed to produce light-weight fuel oil, condensed-nuclei aromatics condensation carbon deposit in hydrogenation coal tar can be avoided under single hop high temperature, thus has a strong impact on the problem in the work-ing life of catalyzer.
Accompanying drawing explanation
Fig. 1 is coal tar hydrotreating process schema of the present invention.
Embodiment
The embodiment of this programme is briefly described below in conjunction with device schema:
Wherein sequence number 1 is head tank, and 2 is pre-hydrogenator, and 3 is tripping device, 4 is hydrodemetallation (HDM) reactor, and 5 is deep hydrofinishing reactor, and 6 is tripping device, 7 is hydrocracking reactor, 8 is water distilling apparatus, and 9 is water, and 10 is gasoline, 11 is diesel oil, 12 is hydrocracking tail oil, and 13 is hydrogen, and all the other are pipeline.
The principle process flow diagram (Fig. 1) of coal tar hydrogenating process for producing light-weight fuel oil: the coal tar raw material first in head tank 1 and hydrogen are mixed into pre-hydrogenator to carry out hydrogenation of unsaturated hydrocarbons saturated.Pre-hydrogenator adopts magnetically stabilized bed reactor, and in reactor, filling has ferromagnetic hydrogenation catalyst, and this catalyzer is the catalyzer of the magnetic carrier load hydrogenation active metals be made up of magnetic-particle, and the granular size of catalyzer is 10 ~ 1000 μm.Wherein magnetic carrier is by SiO
2, Al
2o
3or its mixture and magnetic-particle form, magnetic-particle is wherein by SiO
2coating layer and forming containing the kernel of magnetic particle, magnetic particle wherein can be selected from one or more in magneticmetal iron (Curie temperature is 1043K), cobalt (Curie temperature is 1388K) and nickel (Curie temperature is 627K) and alloy thereof and ferriferous oxide, is preferably Fe, Fe
3o
4(Curie temperature is 820 ~ 986K) and γ-Fe
2o
3one or more in (Curie temperature is 850K).Wherein the particle diameter of magnetic particle is 3 ~ 50nm.The hydrogenation active component composition of catalyzer is by weight percentage: molybdenum oxide 1% ~ 5%, nickel oxide 0.1% ~ 4%, can contain conven-tional adjuvants, and all the other are the refractory oxide such as silicon-containing alumina or aluminum oxide carrier.Pre-hydrogenation logistics after filtration or tripping device (as centrifuge separator) isolate the fine solid particles suspended in product stream after enter hydrodemetallation (HDM) reactor, carry out demetalization reaction.From the hydrodemetallation (HDM) reactor bottom all or part of penetration depth hydrofining reactor of logistics out, mainly remove the heteroatoms such as sulphur, nitrogen.The reacted logistics of deep hydrofinishing is separated water outlet, lighting end and last running, and hydrocracking reaction is carried out in last running.Hydrocracking reaction product fractionation goes out gasoline, diesel oil and hydrocracking tail oil.
For further illustrating all main points of the present invention, enumerate following examples.Catalyzer composition and raw material form and character percentage composition is weight percentage.
Wherein catalyst for pre-hydrogenation be microspheroidal with alumina-coated Fe
3o
4magnetic particle forms magnetic-particle, more coated Al
2o
3form magnetic carrier back loading molybdenum-nickel active ingredient to be prepared from.Wherein the weight ratio of each component of Magnetic Spherical carrier is: Fe
3o
4: SiO
2: Al
2o
3=7: 13: 80; Containing MoO in catalyzer
3for 4.6wt%, be 2.4wt% containing NiO.The granular size of catalyzer is 75 μm.Hydrodemetalation catalyst is the FZC-202 catalyzer of Fushun Petrochemical Research Institute's Development and Production, deep hydrofinishing catalyzer is the FF-16 catalyzer of Fushun Petrochemical Research Institute's Development and Production, and hydrocracking catalyst is the FC-28 catalyzer of Fushun Petrochemical Research Institute's Development and Production.
Embodiment 1
The present embodiment is the hydropyrolysis experiment that coal tar hydrogenation process carries out coal-tar heavy oil distillate, and the magnetically stabilized bed reactor of pre-hydrogenation adopts outside upflowing operating method, the operating method that all the other each reactors adopt gas and liquid flowing to flow downward.Wherein coal tar raw material character is: density (20 DEG C): 1.1365 g/cm
3; Carbon residue: 3.4%; Sulphur: 6000 μ g/g; Nitrogen: 10000 μ g/g, saturated point: 0%; Fragrance point: 69.1%; Colloid is 27.9%, and bituminous matter is 3%; Wherein content of impurities is 1.8%.First enter magnetic stablizing bed pre-hydrogenator after the coal tar raw material in head tank 1 mixes with hydrogen and carry out hydrogenation deoxidation and hydrogenation reaction of unsaturated hydrocarbon, in pre-hydrotreating reaction effluent, content of impurities is 0.9%, pre-hydrotreating reaction effluent isolates fine solid particles through centrifugal separating device (Taixing City turns settling centrifuge up to the horizontal spiral shell of the LW220 type that whizzer company limited produces), and after being separated, content of impurities is lower than 20 μ g/g.Enter hydrodemetallation (HDM) reactor after separation machinery impurity, remove metallic impurity; From hydrodemetallation (HDM) reactor bottom logistics penetration depth hydrofining reactor out, mainly remove the heteroatomss such as nitrogen; Enter high pressure hot separator from the logistics out of deep hydrofinishing reactor bottom, be separated water outlet, the light ends oil of <160 DEG C and the mink cell focus of >160 DEG C; Then the mink cell focus of >160 DEG C enters hydrocracking reactor, carries out aromatic hydrogenation cracking ring-opening reaction; Product introduction atmospheric distillation plant after cracking, cuts out gasoline (<160 DEG C), diesel oil (160 ~ 350 DEG C) and hydrocracking tail oil (>350 DEG C).Reaction conditions and test-results list in table 1 and table 2 respectively.Each reactor all can keep longer running period.
Table 1 reaction conditions
| Numbering | Embodiment 1 |
| Pre-hydrotreating reaction | |
| Temperature, DEG C | 200 |
| Pressure, MPa | 4 |
| Hydrogen-oil ratio, v/v | 600 |
| Air speed, h -1 | 1.5 |
| Magneticstrength, oersted | 600 |
| Hydrodemetallation (HDM) is reacted | |
| Temperature, DEG C | 346 |
| Pressure, MPa | 15 |
| Hydrogen-oil ratio, v/v | 900 |
| Air speed, h -1 | 1.0 |
| Deep hydrofinishing reacts | |
| Temperature, DEG C | 380 |
| Pressure, MPa | 15 |
| Hydrogen-oil ratio, v/v | 1500 |
| Air speed, h -1 | 0.82 |
| Hydrocracking reaction | |
| Temperature, DEG C | 395 |
| Pressure, MPa | 15 |
| Hydrogen-oil ratio, v/v | 1600 |
| Air speed, h -1 | 0.7 |
Table 2 embodiment 1 product property
| Gasoline | Diesel oil | |
| Density (20 DEG C), g/cm 3 | 0.7838 | 0.8846 |
| S，μg/g | 3.2 | 15 |
| N，μg/g | 1.0 | 1.4 |
| Flash-point (closing), DEG C | — | 72 |
| Acidity, mgKOH/100mL | — | 1.00 |
| Cetane value | — | 45 |
| Copper corrosion (50 DEG C, 3h), level | — | 1 |
| Viscosity (20 DEG C), mm 2/s | — | 3.325 |
| Condensation point, DEG C | — | -26 |
Embodiment 2
The present embodiment is the hydropyrolysis experiment that coal tar hydrogenation process carries out the full cut of coal-tar heavy oil.Wherein full fraction of coal tar character is: density (20 DEG C): 1.1653 g/cm
3; Carbon residue: 23.4%; Sulphur: 6800 μ g/g; Nitrogen: 12000 μ g/g, saturated point: 0.17%; Fragrance point: 33.1%; Colloid is 10.73; Bituminous matter is 56%; Wherein content of impurities is 4.8%.The operating process of this test is substantially the same manner as Example 1.In pre-hydrotreating reaction effluent, content of impurities is 3.0%, pre-hydrotreating reaction effluent after filtration (the CLBY-302A type full-automatic back washing filter that clean water industry is produced founds in Beijing section) isolates fine solid particles, and after being separated, content of impurities is lower than 10 μ g/g.Reaction conditions and test-results are in table 3 and table 4.
Table 3 reaction conditions
| Numbering | Embodiment 2 |
| Pre-hydrotreating reaction | |
| Temperature, DEG C | 235 |
| Pressure, MPa | 6 |
| Hydrogen-oil ratio, v/v | 800 |
| Air speed, h -1 | 1.0 |
| Magneticstrength, oersted | 850 |
| Hydrodemetallation (HDM) is reacted | |
| Temperature, DEG C | 345 |
| Pressure, MPa | 20 |
| Hydrogen-oil ratio, v/v | 1500 |
| Air speed, h -1 | 0.8 |
| Deep hydrofinishing reacts | |
| Temperature, DEG C | 382 |
| Pressure, MPa | 20 |
| Hydrogen-oil ratio, v/v | 1500 |
| Air speed, h -1 | 0.8 |
| Hydrocracking reaction | |
| Temperature, DEG C | 400 |
| Pressure, MPa | 20 |
| Hydrogen-oil ratio, v/v | 1000 |
| Air speed, h -1 | 0.6 |
Table 4 product property
| Gasoline | Diesel oil | |
| Density (20 DEG C), g/cm 3 | 0.7868 | 0.8966 |
| S，μg/g | 9.2 | 28 |
| N，μg/g | 1.0 | 2.1 |
| Flash-point (closing), DEG C | — | 74 |
| Acidity, mgKOH/100mL | — | 1.32 |
| Cetane value | — | 43 |
| Copper corrosion (50 DEG C, 3h), level | — | 1 |
| Viscosity (20 DEG C), mm 2/s | — | 3.585 |
| Condensation point, DEG C | — | -20 |
Comparative example 1
The present embodiment is the comparative example of processing dead oil, test raw material and process of the test and test conditions substantially the same manner as Example 1, difference is that pre-hydrogenator uses conventional fixed-bed reactor, loads hydrogenation protecting agent FZC-102 in reactor.Find in process of the test, due to solid impurity deposition in pre-hydrogenator, namely this reactor can only operate continuously needs to change protective material for 6 ~ 8 months.
Comparative example 2
The present embodiment is the comparative example of processing full fraction of coal tar, process of the test and test raw material and test conditions substantially the same manner as Example 2, difference is that preatreating reactors uses ebullated bed reactor, molybdenum-the nickel catalyzator of what the boiling-bed catalyst wherein used was microspheroidal with aluminum oxide is carrier, wherein in catalyzer containing MoO
3for 12wt%, be 6wt% containing NiO.The bulk density of catalyzer is 0.72g/cm
3, surface-area is 230m
2/ g, granules of catalyst mean diameter is 0.5mm.Reaction conditions and test-results are in table 5 and table 6.
Table 5 reaction conditions
| Numbering | Embodiment 2 |
| Pre-hydrotreating reaction | |
| Temperature, DEG C | 240 |
| Pressure, MPa | 7 |
| Hydrogen-oil ratio, v/v | 800 |
| Air speed, h -1 | 0.9 |
| Hydrodemetallation (HDM) is reacted | |
| Temperature, DEG C | 345 |
| Pressure, MPa | 20 |
| Hydrogen-oil ratio, v/v | 1500 |
| Air speed, h -1 | 0.6 |
| Deep hydrofinishing reacts | |
| Temperature, DEG C | 382 |
| Pressure, MPa | 20 |
| Hydrogen-oil ratio, v/v | 1500 |
| Air speed, h -1 | 0.7 |
| Hydrocracking reaction | |
| Temperature, DEG C | 400 |
| Pressure, MPa | 20 |
| Hydrogen-oil ratio, v/v | 1000 |
| Air speed, h -1 | 0.6 |
Table 6 product property
| Gasoline | Diesel oil | |
| Density (20 DEG C), g/cm 3 | 0.7866 | 0.8976 |
| S，μg/g | 9.0 | 29 |
| N，μg/g | 1.0 | 2.0 |
| Flash-point (closing), DEG C | — | 70 |
| Acidity, mgKOH/100mL | — | 1.52 |
| Cetane value | — | 43 |
| Copper corrosion (50 DEG C, 3h), level | — | 1 |
| Viscosity (20 DEG C), mm 2/s | — | 3.385 |
| Condensation point, DEG C | — | -22 |
As can be seen from above-mentioned test-results, magnetic stablizing bed pre-treatment and multistage catalyst grade is adopted to join the effect of art breading coal tar best, can according to coal tar oil composition and feature, progressively improve temperature of reaction and catalyst activity, obtain the light ends of high-quality, and adopting traditional fixed bed catalyst grading distribution scheme process coal tar not take into full account the feature that in coal tar, solid impurity content is high, running period is subject to remarkably influenced.Although ebullated bed is wide to adaptability to raw material, but fixed bed relatively, its hydrogenation removing impurities matter poor-performing, the product property identical with embodiment 2 to be obtained so adopt during ebullated bed pre-treatment full fraction of coal tar, need the operating severity improving ebullated bed and downstream fixed bed device, and in operation because boiling state and the logistics composition in reactor of bed, gas-liquid flow velocity are relevant with catalyzer physico-chemical property, so narrow between operational zone, very flexible.
Claims (12)
1. a Hydrotreatment method for coal tar, comprises following content:
(a), in magnetically stabilized bed reactor, by the mixture of coal tar raw material and hydrogen with there is ferromagnetic hydrogenation catalyst contact, at pressure 3 ~ 16MPa, temperature 150 ~ 280 DEG C, hydrogen to oil volume ratio 200 ~ 2000, during liquid, volume space velocity is 0.1 ~ 10h
-1, magneticstrength is the hydrogenation reaction of carrying out unsaturated hydrocarbons and oxygen carrier under the reaction conditions of 50 ~ 1000 oersteds, discharges the fine impurities of this material parcel; Wherein said magnetically stabilized bed reactor is that inside exists uniform magnetic field and loaded the reactor with ferromagnetic hydrogenation catalyst;
B (), step (a) obtain the fine solid particles that pre-hydrotreating reaction generates separating of oil fuel-displaced middle suspension;
(c), isolate fine solid particles after logistics carry out hydrodemetallation (HDM) reaction;
D (), step (c) gained hydrodemetallation (HDM) reaction effluent carry out hydrofining reaction;
E (), step (d) gained hydrofining reaction effluent, through being separated, are separated water outlet and light constituent and heavy constituent.
2. in accordance with the method for claim 1, it is characterized in that, also comprise step (f): the isolated heavy constituent of step (e) carries out hydrocracking reaction;
With step (g): step (f) gained isocrackate cuts out gasoline fraction, diesel oil distillate and cracking tail oil through water distilling apparatus.
3. in accordance with the method for claim 1, it is characterized in that, the described hydrogenation active metals having ferromagnetic hydrogenation catalyst and comprise magnetic carrier and load, wherein magnetic carrier comprises SiO
2and/or Al
2o
3, and magnetic particle kernel, one or more in described magnetic particle chosen from Fe, cobalt and nickel and alloy thereof and oxides-containing iron.
4. in accordance with the method for claim 3, it is characterized in that, described in there is ferromegnetism hydrogenation catalyst granular size be 10 ~ 1000 μm, the particle diameter of magnetic particle is 0.02 ~ 200 μm.
5. according to the method described in claim 3 or 4, it is characterized in that, described magnetic particle is iron powder, and particle diameter is 20 ~ 150 μm; Or be Fe
3o
4or γ-Fe
2o
3powder, particle diameter is 3 ~ 50nm.
6. in accordance with the method for claim 3, it is characterized in that, hydrogenation active metals composition is by weight percentage: molybdenum oxide 1% ~ 5%, nickel oxide 0.1% ~ 4%.
7. in accordance with the method for claim 1, it is characterized in that, described magnetically stabilized bed reactor is made up of reactor and externally-applied magnetic field, externally-applied magnetic field is the uniform steady magnetic field along reactor axis, uniform magnetic field by direct supply and a series of helmholtz coil of coaxially arranging with reactor or evenly high-density solenoid provide, reactor and other parts of reactor are made up of the material that magnetic permeability is good.
8. in accordance with the method for claim 1, it is characterized in that, in step (b), adopt filtration unit or centrifugal separating device to obtain from step (a) fine solid particles that pre-hydrotreating reaction generates separating of oil fuel-displaced middle suspension.
9. in accordance with the method for claim 1, it is characterized in that, the reaction conditions of the hydrodemetallation (HDM) reaction described in step (c) is: pressure 10 ~ 20MPa, temperature: 300 ~ 380 DEG C, hydrogen to oil volume ratio 200 ~ 3000, volume space velocity is 0.1 ~ 10h
-1; The reaction conditions of the hydrofining reaction described in step (d) is: pressure 10 ~ 20MPa, temperature: 340 ~ 400 DEG C, hydrogen to oil volume ratio 200 ~ 3000, and volume space velocity is 0.1 ~ 10h
-1.
10. in accordance with the method for claim 2, it is characterized in that, the reaction conditions of the hydrocracking reaction described in step (f) is: pressure 10 ~ 20MPa, temperature: 350 ~ 420 DEG C, hydrogen to oil volume ratio 200 ~ 3000, and volume space velocity is 0.1 ~ 10h
-1.
11. in accordance with the method for claim 1, it is characterized in that, the separation described in step (e) adopts high-pressure separator or flashing tower, and wherein the cut point of light constituent and heavy constituent is 130 ~ 210 DEG C.
12. in accordance with the method for claim 1, it is characterized in that, the reaction of step (c) described hydrodemetallation (HDM) is carried out with the described hydrofining reaction of step (d) or carries out in a plurality of reactors respectively in same reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110355711.7A CN103059987B (en) | 2011-10-21 | 2011-11-11 | Hydrotreatment method for coal tar |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103213383 | 2011-10-21 | ||
| CN201110321338.3 | 2011-10-21 | ||
| CN201110321338 | 2011-10-21 | ||
| CN201110355711.7A CN103059987B (en) | 2011-10-21 | 2011-11-11 | Hydrotreatment method for coal tar |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103059987A CN103059987A (en) | 2013-04-24 |
| CN103059987B true CN103059987B (en) | 2015-06-17 |
Family
ID=48102892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110355711.7A Active CN103059987B (en) | 2011-10-21 | 2011-11-11 | Hydrotreatment method for coal tar |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103059987B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150136657A1 (en) * | 2013-11-19 | 2015-05-21 | Uop Llc | Hydrotreating process and multifunction hydrotreater |
| CN104862004A (en) * | 2015-04-28 | 2015-08-26 | 袁继海 | Combined coal tar whole fraction hydroprocessing system and application thereof |
| CN108070397A (en) * | 2017-12-21 | 2018-05-25 | 安徽工业大学 | A kind of method for considering catalytic pyrolysis high temperature coal-tar to be worth doing with useless Fe |
| CN114540078A (en) * | 2020-11-24 | 2022-05-27 | 何巨堂 | Simulated deposition filtration method for hydrocarbon raw material in fixed bed hydrogenation reaction process |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1152605A (en) * | 1995-12-20 | 1997-06-25 | 中国石油化工总公司石油化工科学研究院 | Saturation hydrogenating process for removing olefines from reforming produced oil |
| CN1465438A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | Spherical aluminium oxide carrier material and preparation process thereof |
| CN101318148A (en) * | 2007-06-06 | 2008-12-10 | 中国石油化工股份有限公司 | Method for preparation of spherical magnetic alumina support |
| CN101343545A (en) * | 2007-07-09 | 2009-01-14 | 中国石油化工股份有限公司 | Technique for hydrogenation of coal oil |
| CN101570695A (en) * | 2008-04-29 | 2009-11-04 | 中国石油化工股份有限公司 | Method for producing diesel and ethylene pyrolysis feedstock by gasoline containing olefin |
-
2011
- 2011-11-11 CN CN201110355711.7A patent/CN103059987B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1152605A (en) * | 1995-12-20 | 1997-06-25 | 中国石油化工总公司石油化工科学研究院 | Saturation hydrogenating process for removing olefines from reforming produced oil |
| CN1465438A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | Spherical aluminium oxide carrier material and preparation process thereof |
| CN101318148A (en) * | 2007-06-06 | 2008-12-10 | 中国石油化工股份有限公司 | Method for preparation of spherical magnetic alumina support |
| CN101343545A (en) * | 2007-07-09 | 2009-01-14 | 中国石油化工股份有限公司 | Technique for hydrogenation of coal oil |
| CN101570695A (en) * | 2008-04-29 | 2009-11-04 | 中国石油化工股份有限公司 | Method for producing diesel and ethylene pyrolysis feedstock by gasoline containing olefin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103059987A (en) | 2013-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11421166B2 (en) | Process for the production of fuels of heavy fuel type from a heavy hydrocarbon-containing feedstock using a separation between the hydrotreatment stage and the hydrocracking stage | |
| RU2430957C2 (en) | Procedure and installation for conversion of heavy oil fractions in boiling layer by integrated production of middle distallate with extremly low sulphur contents | |
| RU2360948C2 (en) | Utilisation of gas from reservoir for preliminary processing natural crude oil into preliminary refined raw material not containing pyrobitumens for processing pa oil and liquid residual raw material for processing oil pb | |
| AU2012350179B2 (en) | Method for the hydroconversion of petroleum feedstocks in fixed beds for the production of fuel oils having a low sulphur content | |
| RU2657898C2 (en) | Complex method for processing oil raw material for liquid fuel production with low sulfur content | |
| TWI691591B (en) | Process for the conversion of feeds, comprising a hydrotreatment step, a hydrocracking step, a precipitation step and a step of separating sediments, for the production of fuel oils | |
| KR20160052435A (en) | Process for converting petroleum feedstocks comprising an ebullating-bed hydrocracking stage, a maturation stage and a stage of separating the sediments for the production of fuel oils with a low sediment content | |
| CN101343545B (en) | Technique for hydrogenation of coal oil | |
| CN103059981B (en) | Coal tar hydrogenation method | |
| CN100345946C (en) | Coal tar whole fraction hydrotreatment process | |
| KR102340467B1 (en) | Integrated multi-step solvent deasphalting and delayed coking process to produce high quality coke | |
| CN106167717A (en) | A kind of up flow type heat from hydrogenation cracking method of high aromatic carbon rate poor quality hydrocarbon branch charging | |
| CN104862004A (en) | Combined coal tar whole fraction hydroprocessing system and application thereof | |
| CN106190283B (en) | The hydrocarbon heat from hydrogenation cracking method inferior for adding hydrogen aromatic hydrocarbons either shallow saturated reaction process is set | |
| CN108102710A (en) | A kind of method for preparing needle coke | |
| CN103059987B (en) | Hydrotreatment method for coal tar | |
| CN109749778A (en) | A kind of hydrogenation modification reaction method of the material of the high aromatic hydrocarbons containing higher boiling | |
| EP0026508A1 (en) | Process and apparatus for the demetallization of a hydrocarbon oil | |
| CN104232157A (en) | Hydrocarbon hydrogenation method with particulate matter settling region and reactor adopting hydrocarbon hydrogenation method | |
| CN105623724A (en) | Hydrogenation thermal cracking method for producing low-carbon-number single-six-membered ring hydrocarbon from high aromatic hydrocarbon | |
| CN109609185A (en) | Content of wax oil plant adds hydrogen, adds the combined method of hydrogen, catalyst circulation containing oil of dreg | |
| CN112980484B (en) | Method for producing special marine heavy fuel oil by using coal tar as raw material | |
| CN109852418A (en) | The hydrocarbon suspended bed hydrogenation method of size particle size dispersion type catalyst is applied in combination | |
| CN104263407A (en) | Hydrocarbon hydrogenation method with up-flow bed layer and fixed bed operated in series | |
| CN103965960B (en) | A kind of heavy-oil hydrogenation prepares the technique of diesel oil and petroleum naphtha |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |