CN103756723A - Method for producing high-cetane number diesel fuel by hydrogenating biodiesel fuel and coal tar - Google Patents
Method for producing high-cetane number diesel fuel by hydrogenating biodiesel fuel and coal tar Download PDFInfo
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Abstract
The invention discloses a method for producing a high-cetane number diesel fuel by hydrogenating biodiesel fuel and coal tar. The method comprises the following steps: mixing the biodiesel fuel and the coal tar according to a mass ratio to form a mixed raw material, sequentially performing hydrogenation pretreatment and hydrogenation modification on the mixed raw material and hydrogen, and performing cooling, high and low-pressure separation and fractional distillation on an effluent product to obtain light distillate and high-cetane number diesel fuel distillate. The method has the advantages that the biodiesel fuel has the function of dissolving and diluting the coal tar, and the biodiesel fuel and the coal tar are mixed to be used as a raw material, so that difficulty in the hydrogenation of the coal tar and requirements on equipment are lowered, the investment and the operating cost are reduced, and the economy of a production process is improved; the quality, ultralow sulfur number and high cetane number of the diesel fuel are remarkably improved, and the requirements of national IV or V standards for automotive diesel fuels can be met; a catalyst is long in service life.
Description
Technical field
The present invention relates to a kind of production method of diesel oil, particularly a kind of method with biofuel and coal tar hydrogenating production high-quality clean diesel.
Background technology
From the diesel oil of oil production, be widely used as the power fuel of diesel motor.The production and consumption of diesel oil has not only promoted countries in the world economy and cultural tremendous development, and has greatly improved the mankind's standard of living.Along with the development of world economy, the continuous increase of population, the demand of diesel oil can be more and more large, and the raising of day by day exhausted and people's environmental consciousness of petroleum resources has promoted again countries in the world to accelerate the exploitation paces of the alternative oil product of engine greatly.China attaches great importance to the development of alternative fuel, and as far back as the developing direction of the Eleventh Five-Year Plan period just having determined alternative fuel, the advantage energy (coal) substitutes the rare energy (oil), and renewable energy source substitutes fossil energy.Therefore with the biofuel of producing by waste grease and coal tar production high-quality clean diesel, meet the direction of national encourage growth.
Biofuel is generally by various animal-plant oil, to be reacted the fatty acid methyl ester generating with methyl alcohol.China worked out specially biofuel (GB/T20828-2007) and with the Blended fuel standard (B5) of petroleum diesel (GB/T25199-2010), the specifications of quality of strict and system is proposed.Country encourages to adopt waste grease production biofuel, prevents that waste grease from mixing in edible oil after treatment.But, biofuel is oxygenatedchemicals, and ordinary diesel oil is comprised of hydrocarbon compound, on physico-chemical property, there is certain difference in them, particularly biofuel often has higher cold filter clogging temperature or condensation point, the possibility of result causes the Blended fuel cold flowability of biofuel and conventional diesel oil composition poor, has affected and has sold and promote the use of.
Coal tar is the liquid product that coal obtains in destructive distillation or pyrolysis and gasification.According to the difference of production method, can obtain three kinds of coal tar, i.e. coal-tar heavy oil (900～1000 ℃), coal-tar middle oil (700～900 ℃) and coalite tar (450～650 ℃).In the last thirty years, China's coal tar industry development is rapid, and coal tar annual production is constantly risen.Coal tar can be used for extracting chemical, also can directly concoct production oil fuel, by coking processing tar light oil and coke, improve quality etc. by hydrotreatment.In the process of coal tar extraction chemical process, can produce a large amount of sewage containing Refractory organic compounds, and Residual oil and residue after extraction chemical are more difficult, still have serious pollution problem; Coal tar sulphur nitrogen content is high, and directly burning can a large amount of SO of discharge
xand NO
x, cause serious environmental pollution; Coal tar is produced to the processing and treating method that clean fuel oil product is a kind of clean, environmental protection through shortening upgrading, not only improved economic benefit, and protected environment.Coal tar hydrogenating technology is very fast in China's development in recent years, produced petroleum naphtha, gasoline and the diesel oil of low-sulfur, but diesel-fuel cetane number is low.As: a kind of combination process of producing clean fuel oil by hydrogenation of coal tar and catalyzer thereof (country origin: China, publication number: 101885984A, publication date: 2010-11-17) disclose use through carry phenol and carry lightweight coal tar after naphthalene or coal tar full cut as hydrogenating materials, by the combination processing of hydrofining-hydro-upgrading, obtain can obtaining petroleum naphtha and diesel oil distillate after product fractionation, wherein only 20 left and right of the cetane value of diesel oil distillate; A kind of full liquid phase hydrogenating method (country origin: China of coal tar, publication number: 102585899A, publication date: 2012-07-18) generation oil is disclosed through oil-gas-liquid separation, distillation, isolate naphtha product, diesel product, tail oil product, wherein the cetane value of diesel product also only reaches 40 left and right.These diesel oil distillates can not directly be used, and can only be admixed in straight-run diesel oil and use as blending component.
Diesel cetane-number is an important quality standard, flammability when its reflection diesel oil burns in engine.Diesel cetane-number is too low can extend the delay period of diesel oil in combustion chamber, when serious, pinking can occur, and engine power is declined, and causes mechanical wear and oil consumption to rise; Simultaneously a large amount of fuel can not fully burn, and makes engine over-emitting black exhaust, causes environmental pollution.Along with the reinforcement of environmental consciousness, the require increasingly stringent of people to diesel cetane-number.Being defined as of state's III that China has carried out in an all-round way is not less than 49, and in state IV derv fuel oil standard, the requirement of cetane value further brought up to 51.
The straight-run diesel oil output that China's cetane value is higher is lower, and secondary processing obtains catalytic cracking diesel oil and coker gas oil output is very high, but these diesel qualities are poor, and particularly cetane value is low, generally only has 20～30.Therefore, the derv fuel oil difficulty that prior art production cetane value exceedes 49, meet state's III or state IV is very large, development new technologies or seek new way to produce the clean diesel that meets national standard be the task of top priority.
A kind of method of hydrotreating (country origin: China that improves cetane number of secondary processing diesel oil, publication number: 101760234A, publication date: 2010-06-30) disclose secondary processing diesel oil, as catalytic cracking diesel oil or coker gas oil mix with animal-plant oil, under comparatively mitigation condition, by hydrotreatment, obtain clean diesel product, diesel yield is high, and cetane value can improve 15 unit left and right on the basis of secondary diesel oil.
For the hydrotreatment (country origin: the U.S. of biofuel machine fuel and admixture, enter Chinese publication number: 102216427A, publication date: 2011-10-12), a kind of (country origin: China of the method by vegetable oil production clean diesel, publication number: 101768464A, publication date: 2010-07-07), a kind of Hydrogenation is for the method (country origin: China of biofuel, publication number: 102876348A, publication date: 2013-01-16) disclosed be all the method that adopts vegetables oil hydrogenation or vegetables oil and low-quality diesel fuel mixtures hydrogenation production high hexadecane value diesel oil blending component.But be raw material owing to directly using animal-plant oil, viscosity is high, the easy coking and deactivation of catalyzer can affect the continuous and steady operation of device.
Summary of the invention
Goal of the invention: for the problems referred to above, the object of this invention is to provide a kind of mixing raw material with biofuel and coal tar composition, by the method for hydrogenation production super low sulfur, high hexadecane value clean diesel, and can alleviate catalyst deactivation, the extension fixture production run cycle.
Technical scheme: a kind of biofuel and coal tar hydrogenating are produced the method for high hexadecane value diesel oil, comprise the following steps:
Step (1): biofuel and coal tar 95: 5 in mass ratio～5: 95 composition mixing raw material is sent into and added hydrogen pretreatment in fixed-bed reactor together with hydrogen, with hydrogenation pretreatment catalyst contact reacts, remove oxygen, sulphur, nitrogen and metal impurities wherein, temperature of reaction is 280～440 ℃, hydrogen dividing potential drop is 4～18MPa, hydrogen to oil volume ratio is 600: 1～3200: 1, and during liquid, volume space velocity is 0.1～5h
-1;
Step (2): the product flowing out in fixed-bed reactor after step (1) is sent into reactor and carry out hydro-upgrading, with catalyst for hydro-upgrading contact reacts, temperature of reaction is 260～410 ℃, hydrogen dividing potential drop is 4～14MPa, hydrogen to oil volume ratio is 300: 1～1800: 1, and during liquid, volume space velocity is 0.1～5h
-1;
Step (3):, high-low pressure cooling by carrying out through the product flowing out in step (2) post-reactor separates and fractionation, obtains benzoline and described high hexadecane value diesel oil distillate oil.
Described hydrogenation pretreatment catalyst comprises carrier and active ingredient, described carrier is aluminum oxide, amorphous silicon aluminium, silicon-dioxide or titanium oxide etc., described active ingredient is the base metal of VIII family and/or group VIB, take catalyst weight as benchmark, tungsten and/or molybdenum are counted 10wt%～30wt% with oxide compound, and nickel and/or cobalt are counted 1wt%～15wt% with oxide compound; Best, tungsten and/or molybdenum are counted 15wt%～25wt% with oxide compound, and nickel and/or cobalt are counted 2wt%～10wt% with oxide compound.
Described catalyst for hydro-upgrading comprises carrier and active ingredient, and described active ingredient is supported on ZSM type molecular sieve and γ-Al with oxide form
2o
3or contain a small amount of SiO
2γ-Al
2o
3on carrier Deng solid acid, described active ingredient is the metal in VIII family, and take catalyst weight as benchmark, nickel and/or cobalt are counted 5wt%～25wt% with oxide compound; Best, nickel and/or cobalt are counted 10wt%～20wt% with oxide compound.
Described biofuel is the fatty acid ester being generated by animal-plant oil and short carbon chain alcohol, wherein: described animal-plant oil is genetically engineered soybean oil, rapeseed oil, sunflower seed oil, palm wet goods vegetables oil, the animal tallows such as pig, ox, sheep, chicken, food and drink give up sewer oil, acidifying wet goods waste grease, described short carbon chain alcohol is that carbonatoms is not more than four monohydroxy-alcohol; Described coal tar is the mixture of the lighting end, coal tar of full cut, the coal-tar heavy oil of full cut, coalite tar and the coal-tar middle oil mixture of full cut, the coal-tar middle oil of coalite tar and lighting end or dephenolize arbitrarily arbitrarily, naphthalene lighting end, described coal tar is before mixing with described biofuel, first, through dehydration, de-solid impurity and fractionation processing, intercept the distillate that is not more than 420 ℃.
Best, described animal-plant oil is waste grease, described short carbon chain alcohol is methyl alcohol, ethanol; Described coal tar is the full cut of coalite tar and coal-tar middle oil mixture.
Best, in step (1), temperature of reaction is 320～420 ℃, and hydrogen dividing potential drop is 6～16MPa, and hydrogen to oil volume ratio is 800: 1～2800: 1, and during liquid, volume space velocity is 0.5～2h
-1; In step (2), temperature of reaction is 300～380 ℃, and hydrogen dividing potential drop is 6～12MPa, and hydrogen to oil volume ratio is 600: 1～1500: 1, and during liquid, volume space velocity is 0.5～2h
-1.
Best, 80: 20 in mass ratio～20: 80 composition mixing raw materials of described biofuel and described coal tar.
Principle of the present invention is: the definition of (1) cetane value be exactly n-hexadecane be 100, the main chemical compositions of biofuel is positive 16 carbon fatty acid methyl esters and positive 18 carbon fatty acid methyl esters, after hydrogenation, being converted into Pentadecane, n-hexadecane, n-heptadecane and Octadecane, is all high hexadecane value component; (2) sulphur content of biofuel own is generally lower than 10ppm, and the finished product sulphur content after hydrogenation is lower, and state V diesel oil is to sulphur content, requirement is to be not more than 10ppm; (3) biofuel hydrogenation is low to operational condition requirement, after mixing, because biofuel has the effect of dissolving and diluting coal tar, has reduced the hydrogenation difficulty of coal tar with coal tar.
Beneficial effect: compared with prior art, advantage of the present invention is:
1, biofuel has the effect of dissolving and diluting coal tar, adopts biofuel and coal tar to mix as raw material, has reduced hydrogenation difficulty and the requirement to equipment of coal tar, has saved investment and process cost, has improved the economy of production process;
2, obviously improved diesel quality, super low sulfur, high hexadecane value, can meet the requirement of derv fuel oil state IV or state V standard;
3, catalyst life is long.
Embodiment
Below in conjunction with specific embodiment, further illustrate the present invention, should understand these embodiment is only not used in and limits the scope of the invention for the present invention is described, after having read the present invention, those skilled in the art all fall within the application's claims limited range to the modification of the various equivalent form of values of the present invention.
Embodiment 1: the biofuel of using coal-tar heavy oil and waste cooking oil to produce is raw material.The quality index of coal-tar heavy oil is: density 1.12g/cm
3, mass ratio C: H=13.8, total sulfur content 5500 μ g/g, total nitrogen content 9600 μ g/g, mechanical impurity 2.83wt%, metal content 158.1 μ g/g, aromaticity content 36.7wt%, colloid 20.5wt%, bituminous matter 38.5wt%, moisture 3.1wt%.The quality index of biofuel is: density 0.87g/cm
3, sulphur content 5 μ g/g, mechanical impurity 0, metal content 2.3 μ g/g, fatty acid methyl ester 97.8wt%, moisture 0.025wt%.
By coal-tar heavy oil through dehydration and remove mechanical impurity process after, the cut that intercepts 220～420 ℃ mixes in mass ratio with biofuel at 3: 2, then boost and fully mix with high pressure hydrogen, successively by adding hydrogen pretreatment fixed-bed reactor and hydro-upgrading reactor reacts.
Add catalyzer and operational condition that hydrogen pretreatment is used: catalyzer is that mass content is 10%NiO-30%WO
3/ Al
2o
3, temperature of reaction is 410 ℃, and hydrogen dividing potential drop is 15MPa, and hydrogen to oil volume ratio is 1600, and during liquid, volume space velocity is 0.5h
-1; Catalyzer and operational condition that hydro-upgrading is used: catalyzer is that mass content is 20%CoO/Al
2o
3, temperature of reaction is 350 ℃, and hydrogen dividing potential drop is 10MPa, and hydrogen to oil volume ratio is 1000, and during liquid, volume space velocity is 0.5h
-1.
The product flowing out through hydro-upgrading reactor is first cooling, then enter gas-liquid separator and carry out gas-oil separation, to separating the oil that obtains, carry out cut cut apart by 180 ℃ of benzolines of <, 180～380 ℃ of intermediate oils and 380 ℃ of tail oils of >, the yield of each cut is respectively 12.4wt%, 82wt% and 5.6wt%.Wherein intermediate oil, i.e. high hexadecane value diesel oil of the present invention, its quality character is: cetane value 50.1, density 0.852g/cm
3, sulphur content 48 μ g/g, 10% steam 63 ℃ of excess carbon residue 0.16%, condensation point-13 ℃, flash-points.
Embodiment 2: substantially the same manner as Example 1, difference is: coal-tar heavy oil mixes in mass ratio with biofuel at 1: 3.
The product flowing out through hydro-upgrading reactor is first cooling, then enter gas-liquid separator and carry out gas-oil separation, to separating the oil that obtains, carry out cut cut apart by 180 ℃ of benzolines of <, 180～380 ℃ of intermediate oils and 380 ℃ of tail oils of >, the yield of each cut is respectively 8.6wt%, 89.3wt% and 2.1wt%.Wherein intermediate oil, i.e. high hexadecane value diesel oil of the present invention, its quality character is: cetane value 68.4, density 0.856g/cm
3, sulphur content 11 μ g/g, 10% steam 58 ℃ of excess carbon residue 0.11%, condensation point-23 ℃, flash-points.
Comparative example 1: using the coal-tar heavy oil in embodiment 1 is raw material, through dehydration with after removing mechanical impurity and processing, then boosts and fully mixes with high pressure hydrogen, successively by adding hydrogen pretreatment fixed-bed reactor and hydro-upgrading reactor reacts.The catalyzer and the operational condition that add hydrogen pretreatment, hydro-upgrading use are identical with embodiment 1.
The product flowing out through hydro-upgrading reactor is first cooling, then enter gas-liquid separator and carry out gas-oil separation, to separating the oil that obtains, carry out cut cut apart by 180 ℃ of benzolines of <, 180～380 ℃ of intermediate oils and 380 ℃ of tail oils of >, the yield of each cut is respectively 16.7wt%, 72.7wt% and 10.6wt%.Wherein intermediate oil, the quality character of diesel oil is: cetane value 22, density 0.845g/cm
3, sulphur content 35 μ g/g, 10% steam 57 ℃ of excess carbon residue 0.25%, condensation point-8 ℃, flash-points.
Embodiment 3: the biofuel of using coalite tar and soybean acidified oil to produce is raw material.The quality index of coalite tar is: density 0.93g/cm
3, mass ratio C: H=16.3, total sulfur content 3100 μ g/g, total nitrogen content 6600 μ g/g, mechanical impurity 2.33wt%, metal content 119.1 μ g/g, aromaticity content 28.79wt%, Determination of Alkane Content 25.62wt%, colloid 27.76wt%, bituminous matter 18.31wt%, moisture 2.24wt%.The quality index of biofuel is: density 0.865g/cm
3, sulphur content 11 μ g/g, mechanical impurity 0, metal content 2.4 μ g/g, fatty acid methyl ester 98.2wt%, moisture 0.034wt%.
Coalite tar, through dehydration with after removing mechanical impurity and processing, is mixed in mass ratio with biofuel at 4: 1, then boost and fully mix with high pressure hydrogen, successively by adding hydrogen pretreatment fixed-bed reactor and hydro-upgrading reactor reacts.
Add catalyzer and operational condition that hydrogen pretreatment is used: catalyzer is that mass content is 5%CoO-20%MoO
3/ Al
2o
3, temperature of reaction is 380 ℃, and hydrogen dividing potential drop is 12MPa, and hydrogen to oil volume ratio is 1400, and during liquid, volume space velocity is 1h
-1; Catalyzer and operational condition that hydro-upgrading is used: catalyzer is that mass content is 10%NiO/Al
2o
3, temperature of reaction is 360 ℃, and hydrogen dividing potential drop is 10MPa, and hydrogen to oil volume ratio is 1000, and during liquid, volume space velocity is 1h
-1.
The product flowing out through hydro-upgrading reactor is first cooling, then enter gas-liquid separator and carry out gas-oil separation, to separating the oil that obtains, carry out cut cut apart by 180 ℃ of benzolines of <, 180～380 ℃ of intermediate oils and 380 ℃ of tail oils of >, the yield of each cut is respectively 14.3wt%, 79.6wt% and 6.1wt%.Wherein intermediate oil, i.e. high hexadecane value diesel oil of the present invention, its quality character is: cetane value 50.6, density 0.858g/cm
3, sulphur content 22 μ g/g, 10% steam 59 ℃ of excess carbon residue 0.23%, condensation point-8 ℃, flash-points.
Comparative example 2: using the coalite tar in embodiment 3 is raw material, through dehydration with after removing mechanical impurity and processing, then boosts and fully mixes with high pressure hydrogen, successively by adding hydrogen pretreatment fixed-bed reactor and hydro-upgrading reactor reacts.The catalyzer and the operational condition that add hydrogen pretreatment, hydro-upgrading use are identical with embodiment 3.
The product flowing out through hydro-upgrading reactor is first cooling, then enter gas-liquid separator and carry out gas-oil separation, to separating the oil that obtains, carry out cut cut apart by 180 ℃ of benzolines of <, 180～380 ℃ of intermediate oils and 380 ℃ of tail oils of >, the yield of each cut is respectively 17.1wt%, 75.7wt% and 7.2wt%.Wherein intermediate oil, the quality character of diesel oil is: cetane value 39, density 0.841g/cm
3, sulphur content 30 μ g/g, 10% steam 58 ℃ of excess carbon residue 0.27%, condensation point-11 ℃, flash-points.
Embodiment 4: the biofuel that in use, coalite tar and rapeseed oil are produced is raw material.The quality index of middle coalite tar is: density 0.97g/cm
3, mass ratio C: H=15.1, total sulfur content 3400 μ g/g, total nitrogen content 7400 μ g/g, mechanical impurity 2.57wt%, metal content 141.3 μ g/g, aromaticity content 23.46wt%, Determination of Alkane Content 21.78wt%, colloid 31.03wt%, bituminous matter 23.94wt%, moisture 2.88wt%.The quality index of biofuel is: density 0.872g/cm
3, sulphur content 2 μ g/g, mechanical impurity 0, metal content 1.4 μ g/g, fatty acid methyl ester 97.3wt%, moisture 0.028wt%.
Middle coalite tar, through dehydration with after removing mechanical impurity and processing, is mixed in mass ratio with biofuel at 2: 1, then boost and fully mix with high pressure hydrogen, successively by adding hydrogen pretreatment fixed-bed reactor and hydro-upgrading reactor reacts.
Add catalyzer and operational condition that hydrogen pretreatment is used: catalyzer is that mass content is 7%NiO-25%WO
3/ Al
2o
3, temperature of reaction is 400 ℃, and hydrogen dividing potential drop is 14MPa, and hydrogen to oil volume ratio is 1600, and during liquid, volume space velocity is 1h
-1; Catalyzer and operational condition that hydro-upgrading is used: catalyzer is that mass content is 15%NiO/Al
2o
3, temperature of reaction is 380 ℃, and hydrogen dividing potential drop is 12MPa, and hydrogen to oil volume ratio is 1100, and during liquid, volume space velocity is 1h
-1.
The product flowing out through hydro-upgrading reactor is first cooling, then enter gas-liquid separator and carry out gas-oil separation, to separating the oil that obtains, carry out cut cut apart by 180 ℃ of benzolines of <, 180～380 ℃ of intermediate oils and 380 ℃ of tail oils of >, the yield of each cut is respectively 10.2wt%, 85.6wt% and 4.2wt%.Wherein intermediate oil, i.e. high hexadecane value diesel oil of the present invention, its quality character is: cetane value 49.4, density 0.860g/cm
3, sulphur content 16 μ g/g, 10% steam 58 ℃ of excess carbon residue 0.19%, condensation point-9 ℃, flash-points.
Comparative example 3: using the middle coalite tar in embodiment 4 is raw material, through dehydration with after removing mechanical impurity and processing, then boosts and fully mixes with high pressure hydrogen, successively by adding hydrogen pretreatment fixed-bed reactor and hydro-upgrading reactor reacts.The catalyzer and the operational condition that add hydrogen pretreatment, hydro-upgrading use are identical with embodiment 4.
The product flowing out through hydro-upgrading reactor is first cooling, then enter gas-liquid separator and carry out gas-oil separation, to separating the oil that obtains, carry out cut cut apart by 180 ℃ of benzolines of <, 180～380 ℃ of intermediate oils and 380 ℃ of tail oils of >, the yield of each cut is respectively 16.4wt%, 73.4wt% and 10.2wt%.Wherein intermediate oil, the quality character of diesel oil is: cetane value 33, density 0.839g/cm
3, sulphur content 35 μ g/g, 10% steam 57 ℃ of excess carbon residue 0.28%, condensation point-10 ℃, flash-points.
Embodiment 5: using the benzoline of 200～300 ℃ of boiling ranges during coal tar fractional distillation and biofuel that animal tallow is produced is raw material.The quality index of benzoline is: density 1.03g/cm
3, total sulfur content 6200 μ g/g, total nitrogen content 8100 μ g/g, mechanical impurity 0, metal content 18.3 μ g/g, hydrocarbon content 91.3wt%, colloid 2.3wt%, moisture 0.84wt%.The quality index of biofuel is: density 0.869g/cm
3, sulphur content 4 μ g/g, mechanical impurity 0, metal content 1.9 μ g/g, fatty acid methyl ester 97.6wt%, moisture 0.021wt%.
Benzoline, through dehydration, is mixed in mass ratio with biofuel at 7: 3, then boost and fully mix with high pressure hydrogen, successively by adding hydrogen pretreatment fixed-bed reactor and hydro-upgrading reactor reacts.
Add catalyzer and operational condition that hydrogen pretreatment is used: catalyzer is that mass content is 3%NiO-15%WO
3/ Al
2o
3, temperature of reaction is 360 ℃, and hydrogen dividing potential drop is 8MPa, and hydrogen to oil volume ratio is 800, and during liquid, volume space velocity is 2h
-1; Catalyzer and operational condition that hydro-upgrading is used: catalyzer is that mass content is 8%NiO/Al
2o
3, temperature of reaction is 330 ℃, and hydrogen dividing potential drop is 6MPa, and hydrogen to oil volume ratio is 600, and during liquid, volume space velocity is 2h
-1.
The product flowing out through hydro-upgrading reactor is first cooling, then enter gas-liquid separator and carry out gas-oil separation, to separating the oil that obtains, carry out cut cut apart by 180 ℃ of benzolines of <, 180～380 ℃ of intermediate oils and 380 ℃ of tail oils of >, the yield of each cut is respectively 2.7wt%, 96.7wt% and 0.6wt%.Wherein intermediate oil, i.e. high hexadecane value diesel oil of the present invention, its quality character is: cetane value 50.3, density 0.853g/cm
3, sulphur content 17 μ g/g, 10% steam 57 ℃ of excess carbon residue 0.15%, condensation point-17 ℃, flash-points.
Embodiment 6: using the benzoline of 300～500 ℃ of boiling ranges during coal tar fractional distillation and biofuel that soybean oil is produced is raw material.The quality index of benzoline is: density 1.15g/cm
3, total sulfur content 4760 μ g/g, total nitrogen content 9800 μ g/g, mechanical impurity 0, metal content 39.4 μ g/g, hydrocarbon content 92.7wt%, colloid 6.9wt%, moisture 0.92wt%.The quality index of biofuel is: density 0.871g/cm
3, sulphur content 1 μ g/g, mechanical impurity 0, metal content 0.9 μ g/g, fatty acid methyl ester 98.4wt%, moisture 0.017wt%.
Benzoline, through dehydration, is mixed in mass ratio with biofuel at 65: 35, then boost and fully mix with high pressure hydrogen, successively by adding hydrogen pretreatment fixed-bed reactor and hydro-upgrading reactor reacts.
Add catalyzer and operational condition that hydrogen pretreatment is used: catalyzer is that mass content is 5%CoO-20%CoO
3/ Al
2o
3, temperature of reaction is 390 ℃, and hydrogen dividing potential drop is 12MPa, and hydrogen to oil volume ratio is 1100, and during liquid, volume space velocity is 1.5h
-1; Catalyzer and operational condition that hydro-upgrading is used: catalyzer is that mass content is 12%CoO/Al
2o
3, temperature of reaction is 360 ℃, and hydrogen dividing potential drop is 8MPa, and hydrogen to oil volume ratio is 800, and during liquid, volume space velocity is 1.5h
-1.
The product flowing out through hydro-upgrading reactor is first cooling, then enter gas-liquid separator and carry out gas-oil separation, to separating the oil that obtains, carry out cut cut apart by 180 ℃ of benzolines of <, 180～380 ℃ of intermediate oils and 380 ℃ of tail oils of >, the yield of each cut is respectively 8.7wt%, 76.9wt% and 14.4wt%.Wherein intermediate oil, i.e. high hexadecane value diesel oil of the present invention, its quality character is: cetane value 51.1, density 0.848g/cm
3, sulphur content 27 μ g/g, 10% steam 63 ℃ of excess carbon residue 0.22%, condensation point-11 ℃, flash-points.
In sum, by the comparison of embodiment 1-2 and comparative example 1, embodiment 3 and comparative example 2, embodiment 4 and comparative example 3, and embodiment 5,6, the diesel oil that visible the inventive method makes, its cetane value obviously improves, sulphur content obviously reduces, and meets the requirement of derv fuel oil state IV or state V standard, has obviously improved diesel quality.
Claims (9)
1. biofuel and coal tar hydrogenating are produced a method for high hexadecane value diesel oil, it is characterized in that comprising the following steps:
Step (1): biofuel and coal tar 95: 5 in mass ratio～5: 95 composition mixing raw material is sent into and added hydrogen pretreatment in fixed-bed reactor together with hydrogen, with hydrogenation pretreatment catalyst contact reacts, remove oxygen, sulphur, nitrogen and metal impurities wherein, temperature of reaction is 280～440 ℃, hydrogen dividing potential drop is 4～18MPa, hydrogen to oil volume ratio is 600: 1～3200: 1, and during liquid, volume space velocity is 0.1～5h
-1;
Step (2): the product flowing out in fixed-bed reactor after step (1) is sent into reactor and carry out hydro-upgrading, with catalyst for hydro-upgrading contact reacts, temperature of reaction is 260～410 ℃, hydrogen dividing potential drop is 4～14MPa, hydrogen to oil volume ratio is 300: 1～1800: 1, and during liquid, volume space velocity is 0.1～5h
-1;
Step (3):, high-low pressure cooling by carrying out through the product flowing out in step (2) post-reactor separates and fractionation, obtains benzoline and described high hexadecane value diesel oil distillate oil.
2. a kind of biofuel according to claim 1 and coal tar hydrogenating are produced the method for high hexadecane value diesel oil, it is characterized in that: described hydrogenation pretreatment catalyst comprises carrier and active ingredient, described carrier is aluminum oxide, amorphous silicon aluminium, silicon-dioxide or titanium oxide etc., described active ingredient is the base metal of VIII family and/or group VIB, take catalyst weight as benchmark, tungsten and/or molybdenum are counted 10wt%～30wt% with oxide compound, and nickel and/or cobalt are counted 1wt%～15wt% with oxide compound.
3. a kind of biofuel according to claim 2 and coal tar hydrogenating are produced the method for high hexadecane value diesel oil, it is characterized in that: take catalyst weight as benchmark, tungsten and/or molybdenum are counted 15wt%～25wt% with oxide compound, and nickel and/or cobalt are counted 2wt%～10wt% with oxide compound.
4. a kind of biofuel according to claim 1 and coal tar hydrogenating are produced the method for high hexadecane value diesel oil, it is characterized in that: described catalyst for hydro-upgrading comprises carrier and active ingredient, described active ingredient is supported on ZSM type molecular sieve and γ-Al with oxide form
2o
3or contain a small amount of SiO
2γ-Al
2o
3on carrier Deng solid acid, described active ingredient is the metal in VIII family, and take catalyst weight as benchmark, nickel and/or cobalt are counted 5wt%～25wt% with oxide compound.
5. a kind of biofuel according to claim 4 and coal tar hydrogenating are produced the method for high hexadecane value diesel oil, it is characterized in that: take catalyst weight as benchmark, nickel and/or cobalt are counted 10wt%～20wt% with oxide compound.
6. a kind of biofuel according to claim 1 and coal tar hydrogenating are produced the method for high hexadecane value diesel oil, it is characterized in that: described biofuel is the fatty acid ester being generated by animal-plant oil and short carbon chain alcohol, wherein: described animal-plant oil is genetically engineered soybean oil, rapeseed oil, sunflower seed oil, palm wet goods vegetables oil, the animal tallows such as pig, ox, sheep, chicken, food and drink give up sewer oil, acidifying wet goods waste grease, described short carbon chain alcohol is that carbonatoms is not more than four monohydroxy-alcohol; Described coal tar is the mixture of the lighting end, coal tar of full cut, the coal-tar heavy oil of full cut, coalite tar and the coal-tar middle oil mixture of full cut, the coal-tar middle oil of coalite tar and lighting end or dephenolize arbitrarily arbitrarily, naphthalene lighting end, described coal tar is before mixing with described biofuel, first, through dehydration, de-solid impurity and fractionation processing, intercept the distillate that is not more than 420 ℃.
7. a kind of biofuel according to claim 6 and coal tar hydrogenating are produced the method for high hexadecane value diesel oil, it is characterized in that: described animal-plant oil is waste grease, and described short carbon chain alcohol is methyl alcohol, ethanol; Described coal tar is the full cut of coalite tar and coal-tar middle oil mixture.
8. a kind of biofuel according to claim 1 and coal tar hydrogenating are produced the method for high hexadecane value diesel oil, it is characterized in that: in step (1), temperature of reaction is 320～420 ℃, hydrogen dividing potential drop is 6～16MPa, hydrogen to oil volume ratio is 800: 1～2800: 1, and during liquid, volume space velocity is 0.5～2h
-1; In step (2), temperature of reaction is 300～380 ℃, and hydrogen dividing potential drop is 6～12MPa, and hydrogen to oil volume ratio is 600: 1～1500: 1, and during liquid, volume space velocity is 0.5～2h
-1.
9. a kind of biofuel according to claim 1 and coal tar hydrogenating are produced the method for high hexadecane value diesel oil, it is characterized in that: 80: 20 in mass ratio～20: 80 composition mixing raw materials of described biofuel and described coal tar.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112029533A (en) * | 2020-09-09 | 2020-12-04 | 西安石油大学 | Method and system for preparing gasoline and diesel oil by mixing and hydrogenating coal tar and biomass oil |
| CN112029532A (en) * | 2020-09-09 | 2020-12-04 | 西安石油大学 | Method and process system for preparing gasoline and diesel oil by using coal tar and biomass oil through co-hydrogenation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1741767A1 (en) * | 2005-07-04 | 2007-01-10 | Neste Oil OYJ | Process for the manufacture of diesel range hydrocarbons |
| CN102464998A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化工股份有限公司 | Method by catalyzing and hydrogenating animal and vegetable oil to produce high-quality diesel |
-
2014
- 2014-01-26 CN CN201410037418.XA patent/CN103756723A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1741767A1 (en) * | 2005-07-04 | 2007-01-10 | Neste Oil OYJ | Process for the manufacture of diesel range hydrocarbons |
| CN102464998A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化工股份有限公司 | Method by catalyzing and hydrogenating animal and vegetable oil to produce high-quality diesel |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112029533A (en) * | 2020-09-09 | 2020-12-04 | 西安石油大学 | Method and system for preparing gasoline and diesel oil by mixing and hydrogenating coal tar and biomass oil |
| CN112029532A (en) * | 2020-09-09 | 2020-12-04 | 西安石油大学 | Method and process system for preparing gasoline and diesel oil by using coal tar and biomass oil through co-hydrogenation |
| CN112029533B (en) * | 2020-09-09 | 2022-07-05 | 西安石油大学 | Method and system for preparing gasoline and diesel oil by mixing and hydrogenating coal tar and biomass oil |
| CN112029532B (en) * | 2020-09-09 | 2022-07-29 | 西安石油大学 | Method and process system for preparing gasoline and diesel oil by using coal tar and biomass oil through co-hydrogenation |
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