CN1952070A - Method for producing cleaning oil from coal-tar oil - Google Patents
Method for producing cleaning oil from coal-tar oil Download PDFInfo
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- CN1952070A CN1952070A CN 200510047462 CN200510047462A CN1952070A CN 1952070 A CN1952070 A CN 1952070A CN 200510047462 CN200510047462 CN 200510047462 CN 200510047462 A CN200510047462 A CN 200510047462A CN 1952070 A CN1952070 A CN 1952070A
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Abstract
The invention relates to the method to produce clean oil by coal tar, especially the hydrocracking technology of the coal tar. The characteristic of the invention includes: after removing the mechanical impurities and water, the coal tar enters the hydrogenation refining reactor to hydrogenate, remove the metal, remove sulphur, remove nitrogen and remove oxygen to get the refined oil; the refined oil enters the fractionator to separate the heavy magnesium carbonate distillate and the light magnesium carbonate distillate; part of the heavy magnesium carbonate distillate enters the refining reactor and the other part enters the cracking reactor or all the heavy magnesium carbonate distillate enters the cracking reactor to get the hydrocracked oil; the hydrocracked oil enters the fractionator to be separated into light magnesium carbonate distillate and heavy magnesium carbonate distillate. Compared to the present technologies, the invention can broaden the source for clean oil producing and improve the quality of the coal tar products; besides, the catalyst in the invention has long service life and the device can operate steadily.
Description
Technical field
The invention discloses a kind of method of producing cleaning oil from coal-tar oil, is raw material with coal tar, by the method production high-quality cleaning oil product of hydrofining and hydrocracking.
Background technology
World economy develops rapidly at present, and is more and more to the demand of fuel oil, and also more and more stricter to the specification of quality of oil product.The reserves that world's crude oil has been verified calculate by present produced quantity, can only keep the lasting use in over one hundred year, petroleum resources short extremely urgent.Therefore and the storage capacity of coal is very abundant, and using coal to produce the vehicle fuel oil product is a kind of approach, comprises the direct liquefaction of coal and the indirect liquefaction of coal etc. by the major technique of coal system oil, but these technical costs height, technical sophistication.Another produces the technology of coke, can be when producing coke, and byproduct is a coal tar, this is the technology that extensively adopts at present.But the further processing means of coal tar is fewer, utilizes means more single, and price comparison is low, and product outlet also has some setbacks very much, is the waste to existing resource, especially in use environment is had very large influence.
CN93107496.7 provides a kind of method of producing diesel oil by middle coalite tar, and promptly the direct chemical purifying method is handled the diesel oil distillate of coal tar with the method for removal of impurities-refining-washing-breakdown of emulsion-allotment, and refining goes out to reach the diesel oil of service requirements.CN94112466.5 relates to the method for making diesel oil with coal tar, and coal tar is main raw material, adds auxiliary material, through mixing stirring, catalyzed oxidation-distillation and synthetic three technological processs, can obtain 0-35# diesel oil.CN88105117 has introduced a kind of prescription and compound method thereof of fuel reagent replacing diesel, and its product only acts as a fuel, and is not suitable for diesel engine.These methods all are that coal tar is carried out chemical treatment, poor product quality, and the light-end products yield is low, does not reach the comprehensive utilization to tar resource.
US4855037 has introduced a kind of Catalyst And Method of hydrogenation treatment for coal tar, and the coal tar after its hydrotreatment is used for delayed coking, for delayed coking provides charging, improves the quality of delayed coking product, rather than the direct production fuel oil.
CN1331130A has introduced the method that a kind of coal tar hydrogenating is produced diesel oil, mainly be that coal tar is through fractionation, the following cut of the diesel oil that obtains carries out hydrofining, but direct production meets the diesel oil of fuel oil index or produces blend component as diesel product, but it just carries out hydrotreatment to comparing the light-weight cut in the coal tar, does not utilize coal tar fully.
CN1464031A has introduced the catalyzer of a kind of coal tar hydrogenation process and use.Adopt hydrogenation pre-treatment and hydro-upgrading tandem process, pretreatment catalyst adopts the catalyzer of titaniferous and hydrogenation component, and modifying catalyst adopts the catalyzer that contains titanium and molecular sieve.But coal tar is a kind of special hydrocarbon raw material, and experimental result shows, adopts this technology mode can not keep the catalyzer long-term operation, and particularly modifying catalyst can produce non-renewable inactivation within a short period of time.
Summary of the invention
At the deficiencies in the prior art, the object of the present invention is to provide a kind of technology of producing cleaning oil from coal-tar oil, technological process of the present invention can maximally utilise coal tar raw material, obtains quality products, characteristics such as it is long to have catalyst life simultaneously, and running is stable.
The method of producing cleaning oil from coal-tar oil of the present invention comprises the steps:
A, the coal tar raw material that is obtained by the coal tar process are at first handled through physical process, remove wherein mechanical impurity and water etc., obtain the charging of hydrogenation system.
B, the charging that step a is obtained and hydrogen under hydroprocessing condition with by the protective material bed, remove impurity such as wherein metal, carbon residue.
C, effluent that step b is obtained by the Hydrobon catalyst bed, remove impurity such as wherein sulphur, nitrogen, oxygen under the hydrofining condition, obtain hydrofining and generate oil.The hydrofining effluent is through isolating hydrogen-rich gas, light ends, heavy ends and water, and hydrogen-rich gas loops back reactive system, and water is discharged reactive system, and light ends can be used as the component of the finished product.
D, heavy ends and hydrogen that step c is obtained pass through the hydrocracking catalyst bed under hydrocracking condition, reaction effluent separates the hydrogen-rich gas that obtains and loops back reactive system, separate the light ends that obtains and can directly go out system, separating the heavy ends that obtains can partly or entirely circulate as the charging of hydrocracking.Hydrocracking catalyst can be various common hydrocracking catalysts, preferably contains the hydrocracking catalyst that amorphous aluminum silicide is acid cracking component.
Step c separates with the described reaction effluent of d can adopt a cover separation system, also can adopt two cover separation systems.When adopting a cover separation system, two separators and a fractionation plant be can adopt, a separator and a fractionation plant also can be adopted.When adopting two cover separation systems, adopt two separators and two fractionation plants.The described hydrogen-rich gas circulation of step c and d can adopt the two cover recycle systems to circulate respectively, also can adopt a cover recycle system.Weight cut among the step c can be as the criterion by diesel oil, and diesel oil and the component lighter than diesel oil are counted lighting end, and the cut that overweights diesel oil is counted last running.
The present invention has determined technological process of the present invention by analyzing the characteristics of component in the coal tar.Particularly higher at oxygen level in the coal tar, in unifining process, produce the situation of more water, separate after dividing hydrofining with coal tar fractional distillation, can discharge the water of reaction on the one hand, reduce water to follow-up hydrogenation cracking catalyst Effect on Performance, light ends needn't enter the hydrocracking reaction section on the other hand, reduces the reaction load of cracking zone, improves the yield of light-end products.If selecting with the amorphous aluminum silicide is the catalyzer of acidic components, then can further improve the flexibility of operation of technology of the present invention, because this type of catalyzer is very not strict to nitrogen content in the charging and water-content requirement, and nitrogen in the coal tar and oxygen level are all higher.Compared with prior art, process of the present invention can be converted into coal tar the fine light-end products to greatest extent, and does not need special equipment and catalyzer, and the device running is stable, the catalyzer long service life.Process of the present invention can be transformed existing hydroeracking unit, also can meet equipment and all satisfactory new hydroeracking unit of flow process by a newly-built cover.Facing under the hydrogen operational condition like this, selecting existing equipment and catalyzer, coal tar all is being converted into the lightweight cleaning product that conforms to quality requirements.
Description of drawings
Fig. 1 is the schematic flow sheet of a fractionation plant of a kind of employing of the present invention.
Fig. 2 is the schematic flow sheet of two fractionation plants of a kind of employing of the present invention.
Embodiment
Physical process in the inventive method comprises that liquid-solid separation equipment and heating demulsification type divide dried up equipment.
The protective material bed is made up of a kind of heavy, catalyst for hydrotreatment of residual oil at least, preferably is made of by the rule that reaction liquid stream flow direction bed voidage reduces, hydrogenation activity increases 1～10 kind of protective material.Protective material can be selected weight, the residual hydrogenation protective material of this area routine, weight, residuum hydrogenating and metal-eliminating catalyst, weight, residuum hydrodesulfurization catalyzer, one or more formations in weight, the residual hydrogenation denitrification catalyst etc.When reactant flow is passed through beds, can flow from the top down, also can flow from bottom to top, the preferred latter is because this kind operating method can more effectively prolong running period.
Hydrogenation protecting catalyst in the inventive method is conventional catalyst for hydrotreatment of residual oil series, comprises protective material, metal remover, sweetening agent, denitrfying agent etc.Wherein protective material is divided into several classes; a kind of has been the inertia protective material of logistics distributional effects; comprise the protective material that plays the active transition effect in addition; be active ingredient generally with group vib and/or group VIII metal; with aluminum oxide or siliceous aluminum oxide is carrier; the group vib metal is generally Mo and/or W, and the group VIII metal is generally Co and/or Ni.In the weight of catalyzer, the group vib metal content is counted 0.5wt%～20wt% with oxide compound, and the group VIII metal content is counted 0.5wt%～10wt% with oxide compound, and shape can be hollow cylinder etc.It is that the metal content in the raw material is reduced that metal remover mainly acts on, the poisoning that minimizing causes the rear portion catalyzer, be active ingredient generally with group vib and/or group VIII metal, with aluminum oxide or siliceous aluminum oxide is carrier, the group vib metal is generally Mo and/or W, and the group VIII metal is generally Co and/or Ni.In the weight of catalyzer, the group vib metal content is counted 1wt%～20wt% with oxide compound, and the group VIII metal content is counted 0.5wt%～10wt% with oxide compound, and shape can be right cylinder, trifolium shape, Herba Galii Bungei or spherical etc.Characteristics such as protective material series mainly contains granularity, hydrogenation activity has gradient transition, and pore volume is big.
Concrete catalyzer can be selected the ICR of Chevron company system catalyst:
| Kind | Function | Shape | Diameter/mm | Voidage/% | Active |
| ICR122SA ICR114ZF | The support catalyst support catalyst | Spherical trilobal | 4.2 4.2 | 55～65 55～65 | Low |
| ICR122ZSH ICR122LSB ICR122LSH ICR133H ICR132H ICR114L ICR114H ICR130H | Catalyst for demetalation catalyst for demetalation catalyst for demetalation catalyst for demetalation catalyst for demetalation desulphurization catalyst desulphurization catalyst denitrogenation/reforming catalyst | Spherical cylindricality cylindricality cylindricality cylindricality cylindricality | 4.2 1.6 1.6 0.79 0.79 1.6 0.79 0.79 | 55～65 45～50 45～50 40～45 40～45 45～55 35～40 35～40 | Low low low high high high with the highest |
Or Fushun Petrochemical Research Institute's research and development, the FZC series residual hydrocracking catalyst series that Fushun new and high-tech development zone catalyst plant is produced:
| Kind | Function | Shape | Diameter/mm | Voidage/% | Active |
| FZC-100 FZC-102 FZC-103 FZC-200 FZC-201 FZC-204 FZC-301 | Protective agent protective agent protective agent catalyst for demetalation catalyst for demetalation catalyst for demetalation desulphurization catalyst | Seven apertures in the human head ball Raschig ring Raschig ring bunge bedstraw herb bunge bedstraw herb bunge bedstraw herb bunge bedstraw herb | 16 5.0 3.5 1.3 1.3 1.3 1.2 | 55 51 47 42 42 42 40 | Low low low low higher with |
Material can adopt conventional heavy-oil hydrogenation treatment condition during by the protective material bed; as reaction pressure is 3～20MPa; preferred 12～18MPa; temperature of reaction is 250～450 ℃; be preferably 300～400 ℃, volume space velocity is 0.1～5h-1 during liquid, is preferably 0.5～2.5h-1; hydrogen to oil volume ratio is 300～3000, is preferably 500～1500.Protective material can be seated in the independent reactor; also can be seated in the reactor with Hydrobon catalyst; also can a protectant part be seated in the independent reactor, remainder and Hydrobon catalyst are seated in the reactor.
Hydrobon catalyst in the inventive method is conventional hydrocracking pretreatment catalyst, be active ingredient generally with group vib and/or group VIII metal, with aluminum oxide or siliceous aluminum oxide is carrier, and the group vib metal is generally Mo and/or w, and VII family metal is generally Co and/or Ni.In the weight of catalyzer, the group VIB metal content is counted 10wt%～35wt% with oxide compound, and VII family metal content is counted 3wt%～15wt% with oxide compound, and its character is as follows: specific surface is 100～350m
2/ g, pore volume are 0.15～0.6ml/g.Main catalyzer have that China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute develops 3936,3996, Hydrobon catalysts such as FF-16, FF-26, the function class that also can be external catalyst Co. exploitation is like catalyzer, HC-K, HC-P as Uop Inc., KF-847, the KF-848 etc. of the TK-555 of Topsor company, TK-565 catalyzer and AKZO company.The used reactor of hydrofining system is conventional hydrogenator.The operational condition of hydrofining system adopts conventional operational condition, is generally stagnation pressure 3.0MPa～19.0MPa, and average reaction temperature is 300 ℃～440 ℃, volume space velocity 0.1h during liquid
-1～4.0h
-1, hydrogen to oil volume ratio is 300: 1～5000: 1, generates oily organic sulfur content less than 1500 μ g/g, organonitrogen content is less than 500 μ g/g.
Hydrocracking process catalyst system therefor in the inventive method is conventional hydrocracking catalyst, is active ingredient with group vib and/or VII family metal generally, and the group vib metal is generally Mo and/or W, and VII family metal is generally Co and/or Ni.The carrier of this catalyzer be in aluminum oxide, siliceous aluminum oxide and the molecular sieve one or more.Because oxygen level is than higher in the coal tar raw material, and the composition more complicated of oxygenatedchemicals in oil, therefore still containing the nitrogen and the oxygen of some amount in the tail oil that process hydrofining and fractionation obtain, is the hydrocracking catalyst of carrier so hydrocracking catalyst of the present invention is preferably with the amorphous silicon aluminium.Weight in catalyzer, the group vib metal content is counted 10wt%～35wt% with oxide compound, and VII family metal content is counted 3wt%～15wt% with oxide compound, and molecular sieve content is 5wt%-40wt%, alumina content is 10wt%～80wt%, and its specific surface is 100m
2/ g～650m
2/ g, pore volume are 0.15ml/g～0.50ml/g.Main catalyzer has single-stage hydrocracking catalyzer such as FC-28, FC-14 that China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute develops, ZHC-01, ZHC-02, ZHC-04, and DHC39, the DHC-8 of Uop Inc. of offshore company's exploitation, the hydrocracking catalysts such as ICR126 of CHERON company.Wherein ZHC-02, ICR126 are more suitable for process of the present invention for being the hydrocracking catalyst of cracking component with the amorphous aluminum silicide.The used reactor of hydrocracking system is conventional hydrogenator.The operational condition of hydrocracking process can adopt conventional operational condition, and be generally: stagnation pressure 3.0MPa～18.0MPa, average reaction temperature is 300 ℃～440 ℃, volume space velocity 0.3h during liquid
-1～4.0h
-1, hydrogen to oil volume ratio is 300: 1～5000: 1.
Figure 1 shows that a schematic flow sheet of the present invention; coal tar raw material 1 at first enters pretreatment system 2; isolate behind mechanical impurity and the water and the hydrogen 3 mixed hydrogenation protecting agent reactors 4 that enter; obtain effluent 5; further mixed with hydrogen 6; or enter hydrofining reactor 7 separately; obtain hydrofining and generate oil 8; the refining generation oil 8 of oxygenation enters high-pressure separator 9 subsequently and carries out gas-liquid separation; the gas 10 that obtains loops back reactor 7; the liquid substance that obtains can directly separate water outlet 11 and liquid oil 12 because of density difference with capacitive not; water 11 directly goes out system and carries out purifying treatment; liquid oil 12 enters separation column 13; fractionation obtains gas products 14; gasoline products 15; boat product of coal 16; diesel product 17 wherein 16 and 17 can mix and is wide cut diesel fuel, and tail oil; tail oil can be used as 18, and getting rid of a part goes out system outward; also can be used as 19 mixedly, all enter hydrocracking reactor 21, through hydrocracking reaction with hydrogen 20; obtain hydrocracking and generate oil 22; continue to enter high-pressure separator 23, loop back use after separating the gas products 25 obtain and new hydrogen 26 mixing, entering separation column 13 after the liquid product 24 that separation obtains and 12 mixes.
Fig. 2 is another schematic flow sheet of the present invention; the key distinction of it and Fig. 1 is to use two fractionating systems; protective material and Hydrobon catalyst are seated among the reactor 2-1; the hydrofining effluent separates with hydrogenation refining fractionation tower 2-3 through hydrofining high-pressure separator 2-2, and the effluent of hydrocracking reactor 2-4 separates with hydrocracking separation column 2-6 through hydrocracking high-pressure separator 2-5.The advantage of this boiling range is the practical situation according to product property, and two separation columns can adopt different fractionation scheme, makes that operation is more flexible.
Below by embodiment the present invention program and effect are described
Embodiment 1～5
The stock oil character that embodiment uses sees Table 1.(wherein wt% is weight percentage)
Table 1 stock oil character
| Stock oil | 1# | 2# |
| Density/gcm -3 | 1.05 | 1.12 |
| Boiling range/℃ | 128～550 | 150～600 |
| Carbon residue, wt% | 540 | 9.80 |
| Mechanical impurity, wt% | 0.17 | 0.22 |
| Sulphur content/, wt% | 0.16 | 0.35 |
| Nitrogen content, wt% | 0.92 | 1.10 |
| Metal content/μ gg -1 | 82 | 152 |
| Oxygen level, wt% | 6.20 | 5.30 |
| Aromaticity content, wt% | 79.0 | 82.5 |
At first coal tar and hydrogen mix and enter the hydrogenation protecting reactor; continue to enter hydrofining reactor then; obtain hydrofining generation oil and carry out fractionation; the tail oil that obtains enters hydrocracking reactor; obtain hydrocracking generation oil and also carry out fractionation; the light ends of the different boiling ranges that obtain above, processing condition and product property see Table 2.
Table 2 processing condition and product property
| Embodiment 1 | Comparative example | Embodiment 2 | |
Embodiment 4 | Embodiment 5 | |
| Stock oil | 1# | 1# | 1# | 1# | 2# | 2# |
| The hydrogenation protecting condition | ||||||
| Catalyzer | FZC102/ FZC103/ FZC202 | FZC102/ FZC103/ FZC202 | FZC102/ FZC103/ FZC202 | FZC102/ FZC103/ FZC202 | FZC102B/ FZC103/ FZC202 | FZC102B/ FZC103/ FZC202 |
| Catalyst ratio | 1∶2∶2 | 1∶2∶2 | 1∶2∶3 | 1∶3∶4 | 1∶1∶2 | 1∶2∶4 |
| Pressure, MPa | 16.0 | 16.0 | 12.0 | 6.0 | 16.0 | 10.0 |
| Medial temperature, ℃ | 320 | 320 | 330 | 330 | 320 | 340 |
| Volume space velocity, h -1 | 1.2 | 1.2 | 1.5 | 1.8 | 1.0 | 2.0 |
| Hydrogen to oil volume ratio | 500∶1 | 500∶1 | 400∶1 | 800∶1 | 1500∶1 | 1000∶1 |
| The hydrofining condition | ||||||
| Catalyzer | 3936 | 3936 | 3936 | FF-26 | FF-26 | FF-26 |
| Pressure, MPa | 16.0 | 16.0 | 12.0 | 6.0 | 16.0 | 10.0 |
| Medial temperature, ℃ | 380 | 380 | 385 | 390 | 375 | 390 |
| Volume space velocity, h -1 | 0.4 | 0.4 | 0.8 | 0.5 | 0.3 | 0.6 | |
| Hydrogen to oil volume ratio | 1500∶1 | 1500∶1 | 1000∶1 | 1500∶1 | 800∶1 | 2000∶1 | |
| Hydrofining tail oil nitrogen content, μ g/g | 280 | 280 | 1400 | 620 | 260 | 450 | |
| Hydrocracking condition | |||||||
| Catalyzer | FC-28 | 3976 | FC-28 | ZHC-02 | ZHC-02 | ZHC-02 | |
| Pressure, Mpa | 16.0 | 16.0 | 12.0 | 6.0 | 16.0 | 10.0 | |
| Medial temperature, ℃ | 390 | 390 | 400 | 405 | 390 | 405 | |
| Volume space velocity, h -1 | 0.80 | 0.80 | 0.60 | 0.6 | 0.35 | 0.20 | |
| Hydrogen to oil volume ratio | 1500∶1 | 1500∶1 | 1000∶1 | 800∶1 | 1200∶1 | 1500∶1 | |
| The very fast inactivation of cracking catalyst | |||||||
| Product yield and product property | |||||||
| Gasoline fraction | Yield, wt% | 35.0 | - | 35.6 | 38.0 | 28.5 | 20.3 |
| Sulphur content/μ g/g | 200 | 260 | 160 | 120 | 260 | ||
| Octane value | 70 | - | 66 | 65 | 67 | 63 | |
| Diesel oil distillate | Yield, wt% | 57.2 | - | 55.4 | 50.2 | 65.2 | 73.1 |
| Sulphur content/μ g/g | 310 | 320 | 150 | 180 | 280 | ||
| Condensation point/℃ | -12 | - | -10 | -12 | -10 | -8 | |
| Cetane value | 46 | - | 43 | 42 | 42 | 40 | |
By embodiment as can be seen,, can under hydro condition, adopt existing catalytic hydroprocessing technology and equipment, coal tar is converted into the high-quality clean fuel to greatest extent by technology of the present invention.
Wherein comparative example is catalyzer and a catalyst proportion of selecting for use embodiment 1 identical, identical processing condition, difference is to select for use the single hop series connection once to pass through flow process, be not separate between hydrofining reactor and the hydrocracking reactor, cause the very fast inactivation of hydrocracking catalyst, the generation oil poor yields that hydrofining obtains among tail oil yield and the embodiment 1 is few.
Claims (10)
1, a kind of method of producing cleaning oil from coal-tar oil comprises the steps:
A, the coal tar raw material that is obtained by the coal tar process are at first handled through physical process, remove wherein mechanical impurity and water etc., obtain the charging of hydrogenation system;
B, the charging that step a is obtained and hydrogen under hydroprocessing condition with by the protective material bed, remove wherein metal, carbon residue impurity;
C, the effluent that step b is obtained pass through the Hydrobon catalyst bed under the hydrofining condition, remove wherein sulphur, nitrogen, oxygen impurities, obtain hydrofining and generate oil; The hydrofining effluent is through isolating hydrogen-rich gas, light ends, heavy ends and water, and hydrogen-rich gas loops back reactive system, and water is discharged reactive system;
D, heavy ends and hydrogen that step c is obtained pass through the hydrocracking catalyst bed under hydrocracking condition, reaction effluent separates the hydrogen-rich gas that obtains and loops back reactive system, and separating the heavy ends that obtains can partly or entirely circulate as the charging of hydrocracking.
2, in accordance with the method for claim 1, it is characterized in that the described hydrocracking catalyst of steps d is to contain the hydrocracking catalyst that amorphous aluminum silicide is acid cracking component.
3, in accordance with the method for claim 1, it is characterized in that the described reaction effluent of step c and d separates employing one cover separation system, or adopt two cover separation systems.
4, in accordance with the method for claim 1, it is characterized in that the described hydrogen-rich gas circulation of step c and d, adopt the two cover recycle systems to circulate respectively, or adopt a cover recycle system.
5, in accordance with the method for claim 1, it is characterized in that the weight cut among the step c is as the criterion with diesel oil, diesel oil and the component lighter than diesel oil are counted lighting end, and the cut that overweights diesel oil is counted last running.
6, in accordance with the method for claim 1, it is characterized in that the described protective material bed of step b is made up of a kind of heavy, catalyst for hydrotreatment of residual oil at least.
7, in accordance with the method for claim 6, it is characterized in that described protective material bed is made of by the rule that reaction liquid stream flow direction bed voidage reduces, hydrogenation activity increases 1～10 kind of protective material.
8, in accordance with the method for claim 6; it is characterized in that described heavy, catalyst for hydrotreatment of residual oil can be selected heavily, the residual hydrogenation protective material; weight, residuum hydrogenating and metal-eliminating catalyst, weight, residuum hydrodesulfurization catalyzer, one or more formations in weight, the residual hydrogenation denitrification catalyst etc.
9, in accordance with the method for claim 1, the condition when it is characterized in that described material by the protective material bed is, reaction pressure is 3～20MPa, and temperature of reaction is 250～450 ℃, and volume space velocity is 0.1～5h-1 during liquid, and hydrogen to oil volume ratio is 300～3000; Described hydrofining condition is, stagnation pressure 3.0MPa～19.0MPa, and average reaction temperature is 300 ℃～440 ℃, volume space velocity 0.1h during liquid
-1～4.0h
-1, hydrogen to oil volume ratio is 300: 1～5000: 1; Described hydrocracking condition is, stagnation pressure 3.0MPa～18.0MPa, and average reaction temperature is 300 ℃～440 ℃, volume space velocity 0.2h during liquid
-1～3.0h
-1, hydrogen to oil volume ratio is 300: 1～5000: 1.
10, in accordance with the method for claim 1; it is characterized in that described protective material bed can be seated in the independent reactor; also can be seated in the reactor with Hydrobon catalyst; also can a protectant part be seated in the independent reactor, remainder and Hydrobon catalyst are seated in the reactor.
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