CN106479566A - A kind of method for hydrogen cracking for producing premium and diesel oil - Google Patents

A kind of method for hydrogen cracking for producing premium and diesel oil Download PDF

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CN106479566A
CN106479566A CN201510797913.5A CN201510797913A CN106479566A CN 106479566 A CN106479566 A CN 106479566A CN 201510797913 A CN201510797913 A CN 201510797913A CN 106479566 A CN106479566 A CN 106479566A
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oil
vegetable
accordance
product
animals oils
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CN106479566B (en
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彭冲
曾榕辉
刘涛
刘淑鹤
黄新露
吴子明
白振民
方向晨
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02Gasoline
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04Diesel oil

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a kind of method for hydrogen cracking for producing premium and diesel oil.Vegetable and animals oils hydrogenated pretreatment after, enter hydrocracking reactor, with hydrocracking catalyst I under relative low temperature, large volume space velocities haptoreaction;After gained product is mixed with poor ignition quality fuel hydrofinishing product again, with II haptoreaction of hydrocracking catalyst;Product is separated and fractionation obtains premium and diesel oil.The present invention has taken into full account the features of vegetable and animals oils hydro-upgrading and poor ignition quality fuel hydroconversion process, reasonably effectively combines two kinds of techniques, can produce high octane gasoline products and diesel product simultaneously, and improve the greasy property of diesel product.

Description

A kind of method for hydrogen cracking for producing premium and diesel oil
Technical field
The invention discloses a kind of method for hydrogen cracking, more specifically a kind of with high arene content diesel oil distillate and dynamic Vegetable oil is raw material, and produce high-knock rating gasoline and fine-quality diesel oil is hydrocracked combined method.
Background technology
Enter 21st century since, with people's environmental consciousness increasingly strengthen, national environmental protection regulation increasingly strict And the fast development of national economy, countries in the world are all being continuously increased to the demand for cleaning automotive fuel.
Catalytic cracking(FCC)Technology is one of main technique means of heavy oil lighting, in the oil refining enterprise of countries in the world In all occupy important status.In Chinese heavy oil lighting processing unit (plant), catalytic cracking unit working ability institute accounting Example is more projected, and in petrol and diesel oil product are constituted, catalytically cracked gasoline accounts for 80% or so, and catalytic diesel oil accounts for 30% or so.In recent years, With the increasingly heaviness of crude oil, the raw material processed by catalytic cracking also heaviness and in poor quality increasingly, in addition many enterprises be The purpose for improving quality of gasoline or propylene enhancing is reached, catalytic cracking unit has been carried out transforming or improve catalytic cracking dress The operating severity that puts, causes the quality of the product of catalytic cracking, particularly catalytic diesel oil more to deteriorate, and its performance is predominantly close Degree is high, and arene content is high, and sulphur nitrogen content is high, and Cetane number is low.Also include coal tar with above-mentioned property diesel oil distillate raw material, Coal direct liquefaction oil etc..
Existing diesel oil distillate Raw material processing mode mainly includes hydrofinishing, hydro-upgrading and is hydrocracked.Hydrogenation essence System can only remove the impurity such as sulphur in raw material, nitrogen, and Cetane number can only typically improve several units, and refined products are evaporated for diesel oil Point, but product cannot meet other index requests of vehicle fuel.Hydro-upgrading purpose product be diesel product, removing sulphur, While nitrogen change molecular structure, to effectively improve Cetane number index, in general can by raw material Cetane number improve 10 ~ 15 units, but for the too low raw material of Cetane number, the diesel oil that the method is obtained cannot still meet use requirement.It is hydrocracked It is small molecule by macromolecular cleavage to be, during with catalytic diesel oil as raw material, main purpose product is gasoline fraction, but art technology Personnel know that the octane number for being hydrocracked gasoline is too low, it is impossible to for blended gasoline product, the gasoline fraction in general obtaining It is divided into light naphthar and heavy naphtha two parts, light naphthar octane number is slightly higher, can be used for blended gasoline product, it is also possible to use Preparing ethylene by steam cracking raw material is done, heavy naphtha octane number is lower, and reformer feed is generally used for, and is in addition hydrocracked gasoline fraction Can be also used for producing solvent oil product.
As world oil reserves are fewer and feweri, the utilization of the renewable resource such as vegetable and animals oils is also increasingly taken seriously. The main component of animal and plant fat is straight chain fatty acid triglyceride, and wherein aliphatic acid face length is generally C12~C24, and In the majority with C16 and C18.The Typical fatty acid that animal and plant fat contains includes saturated acid(Palmitic acid, stearic acid), unitary unsaturated Acid(Oleic acid)And polyunsaturated polycarboxylic acid(Linoleic acid, leukotrienes), vegetable oil based on a unsaturated diluted acid and dienoic acid, tallow Then based on saturated fatty acid.Generation oil of these vegetable and animals oils after hydrogenation is exactly diesel component, and which is mainly straight chain Alkane, therefore, condensation point is higher, it is impossible to meet the requirement of condensation point of diesel oil, but Cetane number is very high.Meanwhile, vegetable and animals oils are hydrogenated with The greasy property of the diesel oil for arriving is relatively low, causes its wearability also poor.
Than larger, operating cost is also higher for hydrocracking unit one-time investment.Therefore, each big research in countries in the world is public Department all carries out substantial amounts of research positive for reducing the cost being hydrocracked, and makes great progress.In terms of catalyst: The emphasis that each big patent business in the world is all developed the update of catalyst as oneself technology, in recent years, constantly in catalysis The material of agent, the aspect such as the activity of catalyst, life-span, stability and reduction catalyst cost have done substantial amounts of work.In work In terms of skill:Distillate hydrocracking technology is quite ripe, and each major oil companies are optimizing the same of hydrocracking operation further When, innovative point is placed on and is hydrocracked on related group technology, by optimum organization technique come reduces cost;In addition, logical The further investigation to being hydrocracked is crossed, seeks the inherent connection between catalyst performance and feedstock property and purpose product quality System, sets up the emphasis that suitable catalyst grade part system is also the current area research.
Existing animal and plant fat hydrogenation method produces the process technology of automotive fuel, US20060186020, EP1693432, CN201110217561.3、CN101321847A、CN200710012090.6、CN200680045053.9、 CN200710065393.4, CN200780035038.0, CN200710012208.5, CN200780028314.0 and The patents such as CN101029245A disclose vegetable oil hydroconversion process, using coker naphtha, diesel oil distillate(Straight run bavin Oil, LCO and coker gas oil), the petroleum hydrocarbon such as wax oil cut cut and bio-oil be mixed into hydrogenation catalyst bed, Production diesel product or preparing ethylene by steam cracking raw material etc..US5705722 is disclosed containing plants such as unrighted acid, fat Oil and animal oil mixing back end hydrogenation produce the diesel oil blending component of diesel oil distillate scope.EP1741767 and EP1741768 are disclosed A kind of method for producing diesel oil distillate with animal and plant fat, predominantly animal and plant fat first pass around hydrotreating, Ran Houtong Isomerization catalyst bed layer is crossed, obtains low freezing point diesel fuel component.
US 4676887 discloses a kind of technique for producing high-knock rating gasoline.By catalytic cracking diesel oil (LCO) etc., first First passing through refining reaction area carries out imurity-removal, and carries out aromatic moiety saturation, and the cracking reaction area of entrance afterwards carries out open loop and splits Change reaction, be hydrocracked the diesel oil distillate for obtaining afterwards and enter into catalyst cracker and processed, the essence that the technique is adopted Catalyst processed is also existing commercial catalyst for refining.The technology refining stage severe reaction conditions, polycyclic aromatic hydrocarbon can be supersaturated, difficult To reach the purpose of production high-knock rating gasoline.
Content of the invention
For the deficiencies in the prior art, the invention provides one kind is with high arene content poor-quality diesel-oil by cut fraction and vegetable and animals oils For raw material, produce high-knock rating gasoline and fine-quality diesel oil is hydrocracked combined method.The inventive method has given full play to beta molecule Sieve and Y molecular sieve type hydrocracking catalyst couple advantage, while scientific utilization reaction heat, can produce high-octane rating vapour The good diesel oil of oil and super-low sulfur, high cetane number, greasy property.
The present invention a kind of produce high-knock rating gasoline and fine-quality diesel oil be hydrocracked combined method, including following interior Hold:
(1)Vegetable and animals oils and hydrogen are mixed into vegetable and animals oils hydrofining reactor, and poor ignition quality fuel is mixed into bad with hydrogen Matter diesel oil hydrofining reactor, is contacted with Hydrobon catalyst, carries out hydrofining reaction respectively;
(2)Vegetable and animals oils hydrofinishing effluent together with hydrogen, is entered from reactor head and is hydrocracked instead after dehydration Device is answered, is contacted with the hydrocracking catalyst I containing beta-molecular sieve first, under the conditions of hydroisomerizing, carry out isomerization-visbreaking anti- Should;
(3)Step(2)Gained reaction product, then mix with the poor ignition quality fuel hydrofinishing product of reactor middle and upper part introducing Afterwards, contact with the hydrocracking catalyst II containing Y molecular sieve, under hydrocracking condition, carry out hydroconversion reactions;
(4)Step(3)The reaction effluent for obtaining carries out gas-liquid separation, obtains hydrogen-rich gas and fluid product;Hydrogen-rich gas can To be recycled by circulating hydrogen compressor after purification, fluid product carries out fractionation and obtains gas, gasoline, diesel oil and a small amount of Tail oil fraction.
In the inventive method, described vegetable and animals oils include vegetable oil and/or animal fat.Described vegetable oil is selected from big Soya-bean oil, peanut oil, castor oil, rapeseed oil, corn oil, olive oil, palm oil, coconut oil, tung oil, linseed oil, sesame oil, cottonseed One or more in one group of materials of composition such as oil, sunflower oil and rice bran oil, animal fat are selected from butter, lard, sheep oil With one or more in one group of material of the compositions such as fish oil.Described poor ignition quality fuel is catalytic diesel oil and/or coker gas oil etc.. Arene content in poor ignition quality fuel is generally 70 more than w%, and preferably more than 80w%, its Cetane number are generally less than 30, are It is qualified that the unmanageable inferior raw material of commonsense method, common hydrofining technology or hydrogenation modifying process are difficult to be processed as Diesel product or diesel oil blending component.
In the inventive method, the hydrogenation metal component of described Hydrobon catalyst and hydrocracking catalyst is being used Sulphided state is under state.Hydrogenation metal component is generally one or more in W, Mo, Ni and Co.In terms of oxide weight In Hydrobon catalyst and hydrocracking catalyst, the content of hydrogenation metal component is generally 15wt%~45wt%.Catalyst exists Hydrogenation metal component is converted into sulphided state using front being vulcanized, vulcanization process is well known to those skilled in the art.
In the inventive method, described Hydrobon catalyst typically with aluminum oxide as carrier, or with containing auxiliary agent oxygen Change aluminium is carrier, and auxiliary agent is generally one or more in silicon, phosphorus, boron, fluorine, titanium, zirconium etc., and auxiliary agent can be in carrier preparation process Middle introducing, it is also possible to introduce in hydrogenation metal component loading process.The hydrogenation loaded in vegetable and animals oils hydrofining reactor Catalyst for refining, Main Function be the hydrogenation saturation of unrighted acid in vegetable and animals oils, hydrogenation deoxidation, hydrogenation decarboxylation, plus Hydrogen decarboxylation reaction etc..Hydrobon catalyst can select suitable commercial catalyst, it is also possible to commonly be known according to this area Know and prepare suitable catalyst.
In poor ignition quality fuel hydrofining reactor load Hydrobon catalyst, Main Function poor ignition quality fuel is carried out plus Hydrogen desulfurization, hydrodenitrogeneration etc. are reacted.Hydrobon catalyst can be conventional for processing diesel oil distillate or heavy oil fraction Hydrobon catalyst, can such as select suitable commercial catalyst, it is also possible to be prepared according to this area general knowledge.
In the inventive method, containing molecular sieve and/or amorphous silica-alumina in the carrier of described hydrocracking catalyst, point Son sieve is generally one or two in Y molecular sieve, beta-molecular sieve, general simultaneously containing aluminum oxide etc. in hydrocracking catalyst Inorganic refractory oxide.
In described hydrocracking catalyst I, the weight content of beta-molecular sieve is 3~50 wt%, preferably 10~25 wt%, The acid amount of beta-molecular sieve is generally 0.1~0.4mmol/g.In described hydrocracking catalyst II containing Y molecular sieve 3~ 50wt%, preferably 15~25wt%, the lattice constant of Y molecular sieve are generally 2.425~2.435nm, the SiO of Y molecular sieve2/ Al2O3Mol ratio is general 5.0~50.0, its relative crystallinity generally 80%~130%.Hydrocracking catalyst I and hydrogenation split Change catalyst II and can select suitable commercial catalyst as needed, it is also possible to be prepared according to this area general knowledge.
In the inventive method, the volume ratio of hydrocracking catalyst I and hydrocracking catalyst II is generally 1:5~5: 1, preferably 1:3~3:1.
In the inventive method, the operating condition of hydrogenation reaction is generally:Reaction pressure 3.0MPa~20.0MPa, hydrogen oil body Product is than being 200:1~3000:1, during the liquid of feedstock oil, volume space velocity is 0.1h-1~6.0h-1, 180 DEG C of average reaction temperature~ 465℃;Preferred operating condition is reaction pressure 4.0MPa~18.0MPa, hydrogen to oil volume ratio 300:1~2500:1.
Hydrocracking catalyst I containing beta-molecular sieve should be reacted under conditions of relative low temperature, large volume air speed, subtracted Few raw material hydro carbons is in the time of contact of catalyst active center, it is to avoid the excessive second pyrolysis of vegetable and animals oils, to ensure animals and plants Only there is either shallow cracking in oil, while there is depth isomerization reaction.The condition of hydroisomerizing is preferably, and during liquid, volume space velocity is 2.0h-1~4.0h-1, average reaction temperature is 340 DEG C~385 DEG C.
The effect of the hydrocracking catalyst II containing Y molecular sieve is so that most of aromatic hydrocarbons is converted into mononuclear aromatics and be distributed to In gasoline fraction, and while retaining a certain amount of(Typically ≮ 1.0wt%)Polycyclic aromatic hydrocarbon in diesel oil distillate.Inventor is grinding Study carefully middle discovery, when polycyclic aromatic hydrocarbon content is more than 1.0% in diesel oil distillate, the abrasion resistance of diesel oil strengthens.The big bavin inferior of molecular weight Oily raw material on hydrocracking catalyst containing Y molecular sieve II, at a relatively high temperature(The balance controlled area of aromatic hydrogenation reaction) Preferential there is cracking reaction, orients most of aromatic hydrocarbons and is transformed in gasoline fraction.Laboratory and Commercial application show, when When the poor ignition quality fuel of arene content > 70wt% is more than 210 DEG C of yield > 50wt%, in diesel oil distillate product, polycyclic aromatic hydrocarbon content can To be more than 1.0wt%.For making up the deficiency of vegetable and animals oils hydrogenated diesel oil product greasy property difference, it is contemplated that vegetable and animals oils are hydrogenated Cracking catalyst I and hydrocracking catalyst II can occur a small amount of either shallow cracking, generate the cut of 210 DEG C a small amount of of <, this The reactive moieties of the invention control II of hydrocracking catalyst containing Y molecular sieve, vegetable and animals oils are more than with catalytic diesel oil miscella inferior 210 DEG C of yield ≮ 60wt%, preferably 65~75 wt%.During preferred raw material fluid, volume space velocity is 0.8h-1~1.5h-1, Preferred 390 DEG C~435 DEG C of average reaction temperature.
The processing capacity of vegetable and animals oils and poor ignition quality fuel can be arbitrarily determined in principle according to actual needs, and preferably 1:3 ~3:1.
Compared with prior art, the method for hydrogen cracking of the present invention has advantages below:
1st, the present invention has taken into full account the features of vegetable and animals oils hydro-upgrading and poor ignition quality fuel hydroconversion process, reasonably Two kinds of techniques are effectively combined:After the hydrogenated pretreatment of vegetable and animals oils, hydrocracking reactor is entered, is urged with being hydrocracked The haptoreaction under relative low temperature, large volume space velocities of agent I, while reduction condensation point improves product quality, produces reaction Heat, generates oil and generates oil with poor ignition quality fuel hydrofinishing again and mixes, and II haptoreaction of hydrocracking catalyst is scientific and effective Make use of vegetable and animals oils hydro-upgrading and the hydrorefined reaction heat of poor ignition quality fuel.
2nd, the beta molecule sieve-type hydrocracking catalyst of hydrocracking reactor top filling, due to ten binary of beta-molecular sieve The straight pore passage structure of ring is conducive to the shape-selective isomery of alkane and cracking, be also beneficial to react generate small molecule hydro carbons quickly from Open, while vegetable and animals oils condensation point is reduced, avoid unnecessary second pyrolysis to greatest extent, reduce dry gas yield; The Y molecular sieve type hydrocracking catalyst of reactor lower part filling, as Y molecular sieve is supercage structure, which contributes to polycyclic ring The selective opening cracking of shape hydrocarbon and aromatic hydrocarbons, by controlling suitable acidity, retains mononuclear aromatics to gasoline component as far as possible, The inventive method can produce high octane gasoline products and high cetane number, ultra-low-sulphur diesel product simultaneously.
3rd, in hydrocracking reactor, be hydrocracked through the either shallow of top vegetable and animals oils/isomery after, atmosphere is reacted in bottom The hydrogen dividing potential drop that encloses reduces, and is conducive to suppressing aromatic hydrogenation saturation in poor ignition quality fuel, so that more aromatic hydrocarbons remain into gasoline product In product.
4th, the present invention solve vegetable and animals oils hydro-upgrading generation diesel oil wear no resistance and poor ignition quality fuel hydro-conversion The exceeded and low problem of Cetane number of production high-knock rating gasoline by-product diesel oil sulfur content, in production high cetane number, super-low sulfur While diesel oil, arene content in diesel product is suitably increased, so as to improve the greasy property of diesel product.
5th, two kinds of technology depth couplings, share hydrocracking reactor, a set of separation, fractionation and a recycle hydrogen System, technical process are simple, and equipment investment and operating cost are low, flexible operation, good economy performance.
Description of the drawings
Fig. 1 is a kind of principle process flow diagram of the inventive method.
Specific embodiment
Below in conjunction with the accompanying drawings the method for the present invention is described in detail.
As shown in figure 1, a kind of technological process of the method for hydrogen cracking for producing premium and diesel oil of the present invention is as follows:Dynamic Vegetable oil 1 is mixed into vegetable and animals oils hydrofining reactor 2 with hydrogen 12, carries out the hydrogenation saturation of unrighted acid, adds Hydrogen deoxidation, hydrogenation decarboxylation, the hydrogenation reaction such as dehydroxylation, generate oil 5 after dehydration, enter together with hydrogen 12 be hydrocracked anti- Device 6 is answered, and modification reaction is carried out with hydrocracking catalyst I 7 under conditions of relative low temperature, large volume air speed;Poor ignition quality fuel 3 with After hydrogen mixing, poor ignition quality fuel hydrofining reactor 4 is entered, the reaction such as hydrodesulfurization, hydrodenitrogeneration, reaction effluent occur 8 directly enter reactor from the middle and upper part of hydrocracking reactor 6 without isolation, mixed with vegetable and animals oils hydroisomerizing product Close, obtain through piece-rate system 11 with II 9 haptoreaction of hydrocracking catalyst, reaction effluent 10 after obtaining certain heat Gas purified after recycle with new hydrogen, the fluid product 13 of acquisition enters fractionating system 14, obtains gas 15, gasoline 16th, diesel oil 17 and a small amount of hydrogenation tail oil 18.
A kind of method for hydrogen cracking for producing premium and diesel oil of the present invention is made followed by specific embodiment Further instruction.
Embodiment 1-2 is the embodiment of the inventive method, the weight ratio of vegetable and animals oils and catalytic diesel oil inferior in embodiment Example is 1:1.Reference Example 1 is the implementation result of catalytic diesel oil hydro-conversion technology, and Reference Example 2 is vegetable and animals oils hydro-upgrading technology Implementation result.Table 1 is feedstock property, lists the property of hydrocracking catalyst used, be classified as operation in table 3 in table 2 Condition and result.
1 raw material oil nature of table.
2 hydrocracking catalyst property of table.
3 operating condition of table and result.
* the lubricity in derv fuel quality standard is typically characterized with 60 DEG C of grinding defect diameter of correction, it is desirable to which which is not more than 460μm.
The present invention has taken into full account the features of vegetable and animals oils hydro-upgrading and poor ignition quality fuel hydroconversion process, rationally Two kinds of techniques are effectively combined.Embodiment 1 is 385 DEG C in the reaction temperature of catalyst I, and the reaction temperature of catalyst II is Under conditions of 400 DEG C, at the same obtain gasoline products that octane number is 93.8 and Cetane number be 59, sulfur content be 8 μ g g-1's Diesel product;Embodiment 2 is 365 DEG C in the reaction temperature of catalyst I, under conditions of the reaction temperature of catalyst II is 425 DEG C, While obtain gasoline products that octane number is 94.4 and Cetane number be 63, sulfur content be 7 μ g g-1Diesel product, effect show Write, all achieve the purpose of this technology invention.
Additionally, the correction grinding defect diameter as shown by data of the diesel product of embodiment and comparative example, the present invention solves dynamic plant The problem that the diesel oil that thing oil hydro-upgrading is generated wears no resistance.

Claims (14)

1. a kind of produce high-knock rating gasoline and fine-quality diesel oil be hydrocracked combined method, including herein below:
(1)Vegetable and animals oils and hydrogen are mixed into vegetable and animals oils hydrofining reactor, and poor ignition quality fuel is mixed into bad with hydrogen Matter diesel oil hydrofining reactor, is contacted with Hydrobon catalyst, carries out hydrofining reaction respectively;
(2)Vegetable and animals oils hydrofinishing effluent together with hydrogen, is entered from reactor head and is hydrocracked instead after dehydration Device is answered, is contacted with the hydrocracking catalyst I containing beta-molecular sieve first, under the conditions of hydroisomerizing, carry out isomerization-visbreaking anti- Should;
(3)Step(2)Gained reaction product, then mix with the poor ignition quality fuel hydrofinishing product of reactor middle and upper part introducing Afterwards, contact with the hydrocracking catalyst II containing Y molecular sieve, under hydrocracking condition, carry out hydroconversion reactions;
(4)Step(3)The reaction effluent for obtaining carries out gas-liquid separation, obtains hydrogen-rich gas and fluid product;Fluid product enters Row fractionation obtains gas, gasoline, diesel oil and tail oil fraction.
2. in accordance with the method for claim 1, it is characterised in that described vegetable and animals oils include vegetable oil and/or animal oil Fat.
3. in accordance with the method for claim 2, it is characterised in that described vegetable oil is selected from soybean oil, peanut oil, castor-oil plant Oil, rapeseed oil, corn oil, olive oil, palm oil, coconut oil, tung oil, linseed oil, sesame oil, cottonseed oil, sunflower oil and rice One group of material that oil extracted from rice husks is constituted, described animal fat include one or more in butter, lard, sheep oil and fish oil.
4. in accordance with the method for claim 1, it is characterised in that the arene content in described poor ignition quality fuel be 70 w% with On.
5. according to the method described in claim 1 or 4, it is characterised in that the arene content in described poor ignition quality fuel is 80w% More than.
6. in accordance with the method for claim 4, it is characterised in that described poor ignition quality fuel is catalytic diesel oil and/or coking bavin Oil.
7. in accordance with the method for claim 1, it is characterised in that the weight of beta-molecular sieve in described hydrocracking catalyst I Content is 3~50 wt%, and the acid amount of beta-molecular sieve is 0.1~0.4 mmol/g.
8. according to the method described in claim 1 or 7, it is characterised in that contain Y molecule in described hydrocracking catalyst II 3~50 wt% of sieve, the lattice constant of Y molecular sieve is 2.425~2.435nm, the SiO of Y molecular sieve2/Al2O3Mol ratio be 5.0~ 50.0, its relative crystallinity is 80%~130%.
9. in accordance with the method for claim 1, it is characterised in that described hydrocracking catalyst I and hydrocracking catalyst The volume ratio of agent II is 1:5~5:1.
10. in accordance with the method for claim 1, it is characterised in that described hydroisomerizing and the operating condition being hydrocracked For:Reaction pressure 3.0MPa~20.0MPa, hydrogen to oil volume ratio are 200:1~3000:1, during the liquid of feedstock oil, volume space velocity is 0.1h-1~6.0h-1, 180 DEG C~465 DEG C of average reaction temperature.
11. in accordance with the method for claim 10, it is characterised in that the condition of described hydroisomerizing is that volume is empty during liquid Speed is 2.0h-1~4.0h-1, average reaction temperature is 340 DEG C~385 DEG C.
12. according to the method described in claim 10 or 11, it is characterised in that the described process conditions being hydrocracked are, liquid When volume space velocity be 0.8h-1~1.5h-1, 390 DEG C~435 DEG C of average reaction temperature.
13. in accordance with the method for claim 12, it is characterised in that step(3)Middle control vegetable and animals oils and catalysis bavin inferior Yield ≮ 60wt% of the oily miscella more than 210 DEG C.
14. in accordance with the method for claim 1, it is characterised in that described vegetable and animals oils with the weight ratio of poor ignition quality fuel are 1:3~3:1.
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Cited By (1)

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CN114479931A (en) * 2020-10-27 2022-05-13 中国石油化工股份有限公司 Method and system for producing lubricating oil base oil from Fischer-Tropsch wax

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