CN100558863C - A kind of combined method of producing cleaning oil from coal-tar oil - Google Patents
A kind of combined method of producing cleaning oil from coal-tar oil Download PDFInfo
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- CN100558863C CN100558863C CNB2005100475162A CN200510047516A CN100558863C CN 100558863 C CN100558863 C CN 100558863C CN B2005100475162 A CNB2005100475162 A CN B2005100475162A CN 200510047516 A CN200510047516 A CN 200510047516A CN 100558863 C CN100558863 C CN 100558863C
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Abstract
The invention discloses a kind of method of producing cleaning oil from coal-tar oil, mainly is a kind of hydrofining-hydro-upgrading-hydrocracking combined process of coal tar.Principal feature enters hydrofining reactor with hydrogen and carries out hydrodemetallation (HDM), desulfurization, denitrogenation, deoxygenation after being coal tar at first removed mechanical impurity and water.Compared with prior art, the inventive method can be widened the source of high-quality cleaning Oil Production, promotes the quality of coal-tar products, produces the lightweight cleaning product that meets more high quality requirement.And the catalyzer long service life of the inventive method, the device running is stable.
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 higher high-quality cleaning oil product of the method quality of production of hydrofining-hydro-upgrading-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, and especially the specification of motor for automobile fuel will be strict more.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, the automotive fuel that obtains with oil presses for the exploitation substitute energy like this with continuing to keep very high price at present.The storage capacity of coal is but very abundant, and the main composition of coal also is carbon and hydrogen, and using coal to produce the vehicle fuel oil product like this is a kind of very effective approach.Major technique by coal system oil comprises the direct liquefaction of coal and the indirect liquefaction of coal etc. at present, but these technical costs height, technical sophistication is difficult to large-scale promotion.Another produces the technology of coke, when producing coke, can produce the coal tar byproduct, 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, product outlet also has some setbacks very much, is the waste to existing resource, in the process of utilizing coal tar environment is caused very large pollution simultaneously.
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.
CN1351130A 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 fine lightweight cleaning product more, 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.
Diesel oil distillate in d, the light ends that step c is obtained and hydrogen under the hydro-upgrading condition by the catalyst for hydro-upgrading bed, reaction effluent separates the hydrogen-rich gas obtain and loops back reactive system, separate the liquid distillate that obtains behind stripping as product;
E, 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, d separate with the described reaction effluent of e can adopt a cover separation system, also can adopt two cover separation systems, perhaps three 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, d and e can adopt the three cover recycle systems to circulate respectively, also 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 carries out hydro-upgrading on the other hand, further improve the quality of product, and needn't enter the hydrocracking reaction section, and reduce the reaction load of cracking zone, improve 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 hydrogen gas system of employing of the present invention.
Fig. 2 is the schematic flow sheet of two hydrogen gas systems 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:
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:
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 500～2500.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 the group VIII 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 the group VIII 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 catalyzer 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.
Hydro-upgrading process catalyst system therefor in the inventive method is hydro-upgrading special-purpose catalyst or Hydrobon catalyst and catalyst for hydro-upgrading combination.Wherein Hydrobon catalyst is an active ingredient with group vib and/or group VIII metal generally, is carrier with aluminum oxide or siliceous aluminum oxide, and 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 10wt%～35wt% with oxide compound, and the group VIII 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 has Hydrobon catalysts such as FH-5, FH-98 that China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute develops, FH-FS, the function class that also can be external catalyst Co. exploitation is like catalyzer, HC-K, HC-P catalyzer as Uop Inc., KF-847, the KF-848 etc. of the TK-555 of Topsor company, TK-565 catalyzer and AKZO company.Catalyst for hydro-upgrading is an active ingredient with group vib and/or group VIII metal generally, and the group vib metal is generally Mo and/or W, and the group VIII 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.Weight in catalyzer, the group vib metal content is counted 10wt%～35wt% with oxide compound, and the group VIII 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.Molecular sieve can be Y zeolite and/or beta molecular sieve etc.3963 and FC-18 as China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute's development.The operational condition of hydro-upgrading process is 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.
Hydrocracking process catalyst system therefor in the inventive method is conventional hydrocracking catalyst, is active ingredient with group vib and/or group VIII metal generally, and the group vib metal is generally Mo and/or W, and the group VIII 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 the group VIII 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 the charging 3 and the hydrogen 4 mixed filling protective materials that enter that obtain behind mechanical impurity and the water; the reactor 5 of metal remover and Hydrobon catalyst; obtain hydrofining and generate oil 6; the generation oil 6 that obtains enters high-pressure separator 7 subsequently and carries out gas-liquid separation; the gas 8 that obtains enters the mixed hydrogen jar 34 before the circulating hydrogen compressor; the liquid substance that obtains can directly separate water outlet 36 and liquid oil 9 because of density difference with capacitive not; water 36 directly goes out system and carries out purifying treatment; liquid oil 9 enters separation column 10; fractionation obtains gas products 11; gasoline products 12; diesel product 13; and tail oil 14; diesel oil 13 is mixed into hydro-upgrading reactor 28 with hydrogen 27 and carries out the hydro-upgrading reaction; the hydro-upgrading that obtains generates oil 29 and enters high-pressure separator 30; the gas of here separating 31 enters 34 and recycle; the liquid product that separation obtains enters separation column 21 and carries out fractionation; the tail oil 14 that obtains from separation column can beyond get rid of a part and go out system; also can be mixed with hydrogen 15; all enter hydrocracking reactor 21; through hydrocracking reaction; obtain hydrocracking and generate oil 17; continue to enter high-pressure separator 18; in 18, separate the gas products 19 that obtains and enter 34; and recycle; separate and enter separation column 21 after the liquid product 20 and 32 that obtains mixes; obtain gas products 22 in 21 fractionation; gasoline products 23; boat product of coal 24, diesel product 25 and tail oil 26, tail oil can loop back hydrocracking reactor 21; also hydrofining reactor 5 can be looped back, also system can be gone out.
Fig. 2 is another schematic flow sheet of the present invention; the key distinction of it and Fig. 1 is to use two hydrogen gas circulating systems; protective material and Hydrobon catalyst are seated among the reactor 2-1; the hydrofining effluent is through hydrofining high-pressure separator 2-2; the gas of separating partly recycles in hydrofining and hydrocracking; the liquid of separating separates at hydrogenation refining fractionation tower 2-3; the diesel oil distillate that separation column 2-3 comes out enters hydro-upgrading reactor 2-7; the upgrading cut that comes out enters 2-8 to be separated; the gas of separating partly recycles at hydro-upgrading; the liquid product of separating can be used as product behind the stripping and goes out system in stripping tower 2-9; the hydrofining tail oil that separation column 2-3 fractionation is come out enters hydrocracking reactor 2-4, effluent separate 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, circulates in the different system of hydrogen, can adjust the working pressure of different system, effectively reduces process cost.
Below by embodiment the present invention program and effect are described, it is described that Fig. 1 is pressed in concrete technical process.
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% | 5.40 | 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-hydrofining (containing the protection section) condition
| Embodiment 1 | Comparative example 1 | Embodiment 2 | Embodiment 3 | 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 |
Continuous table 2 processing condition and product property-hydrotreated product character
| Embodiment 1 | Comparative example 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Hydrofining mink cell focus nitrogen content, μ g/g | 280 | 280 | 1400 | 620 | 260 | 450 |
| Diesel yield, wt% (accounting for total raw material) | 70.8 | 70.8 | 62.5 | 65.4 | 42.6 | 50.5 |
| The hydrofining diesel oil cetane value | 38.5 | 38.5 | 31.4 | 34.5 | 38.4 | 33.6 |
Continuous table 2 processing condition and product property-hydro-upgrading operational condition
| Embodiment 1 | Comparative example 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Charging | The hydrofining lighter products | Do not carry out upgrading | The hydrofining lighter products | The hydrofining lighter products | The hydrofining lighter products | The hydrofining lighter products |
| Catalyzer | FH-98/3963 | / | FH-98/3963 | FH-98/3963 | FC-18 | FC-18 |
| Catalyst ratio | 2∶1 | 1∶1 | 1∶2 | |||
| Pressure, MPa | 16.0 | / | 12.0 | 6.0 | 16.0 | 10.0 |
| Medial temperature, ℃ | 360/380 | / | 350/370 | 350/350 | 365 | 360 |
| Volume space velocity, h -1 | 1.0 | / | 0.8 | 1.2 | 1.1 | 0.6 |
| Hydrogen to oil volume ratio | 500∶1 | / | 500∶1 | 700∶1 | 1000∶1 | 800∶1 |
| The hydro-upgrading diesel cetane-number | 48.5 | 38.5 | 40.4 | 41.5 | 49.4 | 45.6 |
Continuous table 2 processing condition and product property-hydrocracking operational condition
| Embodiment 1 | Comparative example 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Stock oil is the hydrofining tail oil | ||||||
| Hydrocracking condition | ||||||
| Catalyzer | FC-28 | FC-28 | 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 hydrocracking diesel cetane-number | 57.5 | 50.5 | 55.4 | 56.5 | 53.4 | 55.6 |
Continuous table 2 processing condition and product property-mixing prod yield and character
By embodiment as can be seen, by technology of the present invention, can adopt existing catalytic hydroprocessing technology and equipment under hydro condition, coal tar is converted into the high-quality clean fuel to greatest extent, specification meets stricter specification requirement.
Comparative example 1
Press the method for embodiment 1, but the diesel oil distillate after the hydrofining does not carry out hydro-upgrading, directly mix with hydrocracking diesel oil.The character of Medium diesel oil is as follows: yield 55.3wt%; Condensation point-12 ℃, cetane value 46, S, 310 μ g/g N, 50.3 μ g/g.As can be seen from the test results, foreign matter contents such as the bigger and sulphur nitrogen of the amplitude that lifting, the especially cetane value that is arrived very much through the quality of diesel oil behind the hydro-upgrading improves reduce significantly, can meet the requirement of harsh more automotive fuel specification.
Claims (9)
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, obtain the charging of hydrogenation system;
B, charging and hydrogen that step a is obtained pass through protective material bed and demetalization bed under hydroprocessing condition, remove wherein metal and carbon residue impurity; Described protective material bed is made up of a kind of catalyst for hydrotreatment of residual oil at least;
C, the effluent that step b is obtained pass through the Hydrobon catalyst bed under the hydrofining condition, remove wherein sulphur, nitrogen and 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; Wherein said Hydrobon catalyst is conventional hydrocracking pretreatment catalyst;
Diesel oil distillate in d, the light ends that step c is obtained and hydrogen under the hydro-upgrading condition by the catalyst for hydro-upgrading bed, reaction effluent separates the hydrogen-rich gas obtain and loops back reactive system, separate the liquid distillate that obtains behind stripping as product; Wherein said catalyst for hydro-upgrading is hydro-upgrading special-purpose catalyst or Hydrobon catalyst and catalyst for hydro-upgrading combination;
E, 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 step e 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, d and e separates employing one cover separation system, perhaps adopt two cover separation systems, perhaps adopt three 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, d and the e employing two cover recycle systems 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 in the steps d 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 described protective material bed is made of by the rule that reaction liquid stream flow direction bed voidage reduces to increase with hydrogenation activity 1～10 kind of protective material.
7, in accordance with the method for claim 1; it is characterized in that described catalyst for hydrotreatment of residual oil selection residual hydrogenation protective material, one or more formations in residuum hydrogenating and metal-eliminating catalyst, residuum hydrodesulfurization catalyzer and the residual hydrogenation denitrification catalyst.
8, in accordance with the method for claim 1, 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 ℃, volume space velocity is 0.1～5h-1 during liquid, and hydrogen to oil volume ratio is 300: 1～3000: 1; 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 0.3h during liquid
-1～4.0h
-1, hydrogen to oil volume ratio is 300: 1～5000: 1; Described hydro-upgrading condition is, stagnation pressure 3.0MPa～18.0MPa, and 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.
9, in accordance with the method for claim 1; it is characterized in that described protective material bed is seated in the independent reactor; perhaps protective material and Hydrobon catalyst are seated in the reactor; a perhaps protectant part is seated in the independent reactor, and remainder and Hydrobon catalyst are seated in the reactor.
Priority Applications (1)
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|---|---|---|---|
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| CN101294107B (en) * | 2007-04-24 | 2011-11-30 | 中国石油化工股份有限公司 | Method for preparing fuel oil with coal oil hydrogenation |
| CN101575533A (en) * | 2008-05-06 | 2009-11-11 | 牟艳春 | Improved method for preparing fuel oil by coal tar hydrogenation |
| CN101928601B (en) * | 2009-06-25 | 2014-04-30 | 中国石油化工股份有限公司 | Processing method for catalytic cracking heavy oil |
| CN102311782B (en) * | 2010-06-29 | 2013-11-27 | 中国石油化工股份有限公司 | Method for producing diesel oil by purifying coal tar through hydrogenating |
| CN102485844B (en) * | 2010-12-03 | 2014-04-02 | 中国石油天然气股份有限公司 | Poor quality wax oil hydrotreatment method |
| CN102776020A (en) * | 2012-08-08 | 2012-11-14 | 赵世洲 | Safe and environment-friendly oil refining process and device |
| CN102851071B (en) * | 2012-08-27 | 2014-08-13 | 王小英 | Two-stage hydrogenation process of coal tar |
| CN102851066B (en) * | 2012-08-27 | 2014-08-13 | 王小英 | Two-stage combined hydrogenation process of coal tar |
| CN103789034B (en) * | 2012-11-05 | 2015-04-01 | 中国石油化工股份有限公司 | Method for hydrogenation of medium-low temperature coal tar to produce large-specific weight aviation kerosene |
| CN103789032B (en) * | 2012-11-05 | 2015-04-15 | 中国石油化工股份有限公司 | Method for hydrogenation of medium-low temperature coal tar to produce refrigerator oil base oil |
| CN103275758B (en) * | 2013-06-07 | 2015-02-18 | 华电重工股份有限公司 | Heavy oil full-fraction hydrotreatment method and system thereof |
| CN104611021B (en) * | 2013-11-05 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of hydrocracking process |
| US9222034B2 (en) | 2013-11-19 | 2015-12-29 | Uop Llc | Process for removing a product from coal tar |
| CN103695031B (en) * | 2013-12-27 | 2015-07-22 | 成都博晟能源科技有限公司 | Method for producing diesel oil and bunker fuel blend component from coal tar |
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