CN109988651A - A kind of method of the catalyst grade with technology production gasoline - Google Patents
A kind of method of the catalyst grade with technology production gasoline Download PDFInfo
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- CN109988651A CN109988651A CN201711469242.5A CN201711469242A CN109988651A CN 109988651 A CN109988651 A CN 109988651A CN 201711469242 A CN201711469242 A CN 201711469242A CN 109988651 A CN109988651 A CN 109988651A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/54—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A kind of method the invention discloses catalyst grade with technology production gasoline.After conventional heavy charge is carried out restricted plus hydrogen saturation by this method, hydroconversion reactions are carried out again, production high-quality gasoline or blend component under conditions of certain process conditions limit and special catalyst grade is matched, while the other fuel oils or high-quality ethylene cracking material of high-quality can also be produced to the progress cracking reaction of the liquid phase component of by-product.The method of the present invention can produce to greatest extent purpose product on the basis of selectively processing to heavy end.
Description
Technical field
The present invention relates to a kind of processing methods of wax oil component, specifically process wax oil with technology by catalyst grade
Raw material produces high-quality gasoline, the production method of the high-quality liquid-phase product of by-product.
Background technique
Gasoline is one of maximum oils of dosage, is a kind of important fuel of engine, can be by petroleum refining
Different units obtain, in crude oil processing, distillation, catalytic cracking, thermal cracking, be hydrocracked, the units such as catalytic reforming all
Output gasoline component, but octane number is different, it, cannot be separately as engine fuel if octane number of direct distillation gasoline is low；In addition, impurity
Sulfur content is also different, therefore the high gasoline component of sulfur content also needs to be subject to desulfuration purification, finally, above-mentioned gasoline component is adjusted
With, need when necessary be added antiknock component, finally obtain gasoline products that meet national standards.
The main path of the gasoline of China's production at present is catalytic cracking and catalytic reforming.Catalytic cracking is current petroleum refining
Most important secondary processing process and the core process of heavy oil lighting in industry, with Global Oil increasingly heaviness,
The processing capacity of FCC apparatus is also continuously improved, and using various mink cell focuses as raw material, obtains major product just by catalytic cracking reaction
It is high-knock rating gasoline, but due to the raising of current gasoline discharge standard, the preceding essence of the production requirement raw material of catalytically cracked gasoline
The rear purification of system and product；Catalytic reforming is to carry out being rearranged into new molecule to the hydrocarbon molecules structure in gasoline fraction
The process of structure is the important means for improving quality of gasoline and producing petrochemical materials, is that current production gasoline is essential
Technique, but due to its reaction process and the characteristic requirements of catalyst, source and cleanliness for raw material have very high
Requirement.
Hydrocracking technology has that adaptability to raw material is strong, products scheme is flexible, liquid product yield is high, good product quality etc.
Plurality of advantages is constantly subjected to the favor of countries in the world oil refining enterprise for many years.One of main technique as heavy oil deep processing
Gasoline component can also be produced indirectly by being hydrocracked, due to the characteristic of its technique, the heavy naphtha impurity content of output it is extremely low but
Octane number is not high, exactly the opposite with catalytic gasoline, this part adds the charging for splitting heavy naphtha as catalytic reforming units, is divided
Minor structure can produce high-knock rating gasoline after resetting, in addition, industrially also occurring at present directly raw using catalytic cracking diesel oil
The hydrogenating conversion process of high-knock rating gasoline is produced, hydrocracking reaction should be attributed in reacting quintessence, but on the whole, still
Do not occur handling heavy oil ingredient (such as decompressed wax oil, catalytic slurry) and directly producing high-knock rating gasoline or blend component
Method.
CN104611029A discloses a kind of catalytic cracking diesel oil hydrogenating conversion process, and catalytic diesel oil is first after mixing with hydrogen
Hydrofining reaction is carried out into hydrofining reactor, hydrocracking reactor is then entered back into and carries out hydrocracking reaction.
Although producing high-knock rating gasoline by hydroconversion process, be substantially still using catalytic cracking diesel oil be raw material, and
The raw materials for production range of premium is not expanded, there is certain limitation.
CN101724454A describes a kind of method for hydrogen cracking for producing high-knock rating gasoline, and feedstock oil is mixed with hydrogen
Enter reactor afterwards and successively carry out hydrofinishing and hydrocracking reaction, although raw material more inferior can be processed, urge by having
The features such as agent operation cycle is long and hydrocracked product is high-quality.But the raw material used is still diesel component, and weight is not used
Matter oil directly produces high-knock rating gasoline.
CN103184073A describes a kind of method for hydrogen cracking for producing high-knock rating gasoline blend component, feedstock oil into
Row controlled hydrofinishing and hydroconversion reactions, although it is high-octane rating that purpose product, which may be implemented, by technologic control
Gasoline or blend component, but the range of choice of raw material is still relatively simple, can not be produced using heavy oil product, is catalyzed simultaneously
It is not also improved effectively for technique in agent.
Summary of the invention
In view of the problems of the existing technology, it is raw that the technical problem to be solved in the present invention is to provide a kind of processing heavy charges
Produce the hydrocracking method of high-knock rating gasoline.This method carries out conventional heavy charge after restricted plus hydrogen is saturated again
Hydroconversion reactions are carried out, produce a certain amount of Gao Pin under conditions of certain process conditions limit and special catalyst grade is matched
Matter gasoline or blend component, while other fuel oil of high-quality can also be produced to the progress cracking reaction of the liquid phase component of by-product
Product can be used as high-quality ethylene cracking material etc., raw to greatest extent on the basis of realizing to heavy end selectively processing
Produce purpose product.
The present invention provides a kind of methods for producing premium, include the following steps:
A) under Hydrofinishing conditions, heavy oil feed passes through reacting containing Hydrobon catalyst bed after mixing with hydrogen
Area carries out restricted hydrofining reaction；
B) the resulting reaction effluent of step a) is under the conditions of hydroconversion process, by containing gradation wax oil hydrogenation conversion catalyst
The reaction zone of agent bed carries out restricted hydroconversion reactions；
C) reaction effluent obtained by step b) carries out the processes such as gas-liquid separation, fractionation, obtains conversion gasoline, conversion diesel oil and does not turn
Carburetion etc., converting diesel oil and unconverted oil can be used as oil product discharge and can also carry out two sections of conventional hydrocracking reactions, to obtain
Good liquid phase purpose product.
The end point of distillation of heavy oil feed described in step a) is generally 450~580 DEG C, preferably 480~570 DEG C, density one
As in 0.90g/cm3More than, preferably 0.93g/cm3More than, in 40wt% or more, preferably 45wt% or more, nitrogen contains total aromatic hydrocarbons in raw material
Amount is in 800mgg-1More than, preferably 1000mgg-1More than.One generally in decompressed wax oil, deasphalted oil or wax tailings
Plant perhaps several said components that can be obtained selected from processing middle-eastern crude or LIAOHE CRUDE, other contaminant characteristics of raw material
It should be the general knowledge of this field, it is necessary to be to meet the requirement that can be used as hydrocracking unit charging.
Hydrofining technology condition described in step a) are as follows: 6.0~13.0 MPa of reaction pressure, hydrogen to oil volume ratio 200: 1
~3000: 1, volume space velocity is 0.1~5.0 h-1, 260 DEG C~435 DEG C of reaction temperature；Preferred operating condition is reaction pressure
7.0~12.0 MPa, hydrogen to oil volume ratio 300: 1~900: 1,1.0~3.0 h of volume space velocity-1, reaction temperature 300 DEG C~430
℃。
Restricted hydrofining reaction described in step a), which refers to, will control certain plus hydrogen saturation depth, avoid mink cell focus
Aromatic component supersaturation in raw material is to influence the octane number of gasoline fraction product, according to aromatic hydrocarbons in raw material and nitrogen content
Difference, generally require control refined oil (i.e. the resulting reaction effluent of step a)) nitrogen content be 50 ~ 250mgg-1, excellent
Select 100 ~ 200mgg-1, the aromatic hydrocarbons in raw material can be retained to greatest extent while reducing refined oil nitrogen content in this way
Component.What needs to be explained here is that during hydrofining reaction, by controlling above-mentioned refined oil nitrogen content, reaction stream
The constituent content of tricyclic or more is less in the aromatic component in object out, and general total amount is in 1 ~ 20wt%, preferably 2 ~ 15wt%.
Hydroconversion process condition described in step b) are as follows: 6.0~13.0 MPa of reaction pressure, hydrogen to oil volume ratio 300: 1
~2000: 1, volume space velocity is 0.1~5.0 h-1, 280 DEG C~455 DEG C of reaction temperature；Preferred operating condition is reaction pressure
7.0~12.0 MPa, hydrogen to oil volume ratio 400: 1~1000: 1,1.0~3.0 h of volume space velocity-1, reaction temperature 310 DEG C~440
℃。
Restricted hydroconversion reactions described in step b), which refer to, will control certain hydro-conversion depth, avoid step a)
In reaction effluent in non-aromatic component overcracking to influence the octane number of gasoline fraction product, according to raw material and
Aromatic hydrocarbons difference in reaction effluent in step a), generally require control output aggregate in premium fraction yield 10 ~
40wt% can retain the aromatic component in raw material to greatest extent and convert to vapour while processing heavy oil raw material in this way
In oil distillate, to improve the octane number of gasoline products.
Hydrobon catalyst described in step a) includes carrier and the hydrogenation metal that is loaded.It is with the weight of catalyst
Benchmark generally includes metal component of group VIB in the periodic table of elements, if tungsten and/or molybdenum are calculated as 10% ~ 35% with oxide, preferably
It is 15% ~ 30%；Group VIII metal such as nickel and/or cobalt are calculated as 1% ~ 7%, preferably 1.5% ~ 6% with oxide.Carrier is inorganic refractory
Oxide is selected generally from aluminium oxide, amorphous silicon aluminium, silica, titanium oxide etc..Wherein conventional hydrocracking pretreatment catalysis
Agent can choose existing various commercial catalysts, for example, Fushun Petrochemical Research Institute (FRIPP) develop 3936,
3996, the Hydrobon catalysts such as FF-16, FF-26, FF-36, UDS-6；Also it can according to need the common sense progress by this field
Preparation.The catalyst for refining should be seated in the upstream of reforming catalyst.
Gradation hydrogenation conversion catalyst described in step b) is the difference filling at least three according to aromatic hydrocarbon type in feedstock oil
Hydrocracking catalyst of the kind containing molecular sieve, the type catalyst are the catalyst especially prepared according to this method.By reactant
It flows direction and successively loads heavy aromatics hydrogenation conversion catalyst, light aromatic hydrocarbons hydrogenation conversion catalyst and mononuclear aromatics guarantor from top to bottom
Stay catalyst.
Corresponding heavy aromatics hydrogenation conversion catalyst is the hydrogenation conversion catalyst containing molecular sieve, is special according to this method
The catalyst of preparation.The hydrogenation conversion catalyst includes hydrogenation active metals, molecular sieve component and alumina support.Generally
Hydrogenation conversion catalyst by structures such as the hydrogenation active metal components such as W, Mo, Co, Ni, Y type molecular sieve component and alumina supports
At.The heavy aromatics hydrogenation conversion catalyst includes WO by weight3(or MoO3) 9~29wt%, NiO (or CoO) 5~
20~50wt% of 10wt%, 15~45wt% of Y type molecular sieve and aluminium oxide.In heavy aromatics hydrogenation conversion catalyst, the Y type point
Son sieve is small crystal grain Y-shaped molecular sieve.The partial size of small crystal grain Y-shaped molecular sieve is 400~600nm, infrared 0.3~0.7mmol/ of total acid
G, middle strong acid ratio are 50% or more (mmolg-1/mmol·g-1), 2.435~2.440nm of cell parameter；Hole holds 0.5~0.7
cm3/ g, wherein the ratio of 2-8nm secondary pore Kong Rongzhan total pore volume is 60% or more.The Y type molecular sieve has more accessible
And the acid centre exposed, be conducive to the diffusion of hydrocarbon molecule, the preferential of cyclic hydrocarbon especially tricyclic and the above aromatic hydrocarbons can be improved
Aromatic ring among thrcylic aromatic hydrocarbon is saturated and is broken by conversion capability, orientation, the maximum amount of high-octane gasoline of production
Component.Hydrogenation conversion catalyst containing the small crystal grain Y-shaped molecular sieve, main function is can be for three cyclophanes in raw material
Hydrocarbon carries out the reaction of selectivity, and the selectivity of two rings and mononuclear aromatics to non-tricyclic is poor.The Y type molecular sieve and routine Y
Type molecular sieve has a certain difference, and conventional modified molecular screen grain size is generally 800~1200nm, Kong Rongwei 0.35~0.50
cm3/ g, the ratio general 30~50% of secondary pore Kong Rongzhan total pore volume, 50~70%(mmolg of middle strong acid ratio-1/mmol·g-1).The hydrogenation conversion catalyst can prepare satisfactory catalyst according to the common sense of this field as described above.
Corresponding light aromatic hydrocarbons hydrogenation conversion catalyst is the hydrogenation conversion catalyst containing molecular sieve, is special according to this method
The catalyst of preparation.The hydrogenation conversion catalyst includes hydrogenation active metals, molecular sieve component and alumina support.Generally
Hydrogenation conversion catalyst by hydrogenation active metal components such as Wo, Mo, Co, Ni, molecular sieve component and alumina support etc. are constituted.
It is exclusively used in the preferred Ni of hydrogenation conversion catalyst promoter metal of the invention, by weight includes WO3(or MoO3) 5~15wt%,
NiO (or CoO) 3~8wt%, 5~30wt% of 50~60wt% of molecular sieve and aluminium oxide；The molecular sieve can be Y type molecular sieve.
Further, the Y type molecular sieve has the property that 600~800nm of partial size, cell parameter 2.438~2.442nm, red
Outer 0.6~0.8mmol/g of total acid, middle strong acid ratio is in 80%(mmolg-1/mmol·g-1), wherein 2-8nm secondary pore hole holds
The ratio of total pore volume is accounted for 50% or more.The modified Y molecular sieve can be modified by the conventional method of this field
It arrives.The main function of light aromatic hydrocarbons hydrogenation conversion catalyst is the reaction that selectivity can be carried out for the double ring arene in raw material,
And it is poor to the selectivity of other aromatic hydrocarbons.This hydrogenation conversion catalyst is can be as described above according to the common sense system of this field
Standby exclusive technology catalyst out.
It is the hydrogenation conversion catalyst containing molecular sieve that corresponding mononuclear aromatics, which retains catalyst, the hydro-conversion catalysis
Agent includes hydrogenation active metals, molecular sieve component and alumina support.General hydrogenation conversion catalyst is by Wo, Mo, Co, Ni etc.
Hydrogenation active metal component, molecular sieve component and alumina support etc. are constituted.It is exclusively used in hydrogenation conversion catalyst gold of the invention
Belong to and form preferred Mo-Co, by weight includes MoO35~25wt%, 3~8wt% of CoO, 20~40wt% of molecular sieve and oxidation
30~50wt% of aluminium, the molecular sieve can be Y type molecular sieve.Further, preferred Y type molecular sieve has the property that grain
Diameter is 500~700nm, and 2.438~2.440nm of cell parameter, infrared 0.6~0.7mmol/g of total acid, middle strong acid ratio is 70%
(mmolg-1/mmol·g-1) more than, the ratio of 2-8nm secondary pore Kong Rongzhan total pore volume is 51 ~ 55%.The catalyst is maximum
It is characterized in that the preparation process of molecular sieve, the non-framework aluminum more modification Y that is conducive to mononuclear aromatics reservation moderate using acid strength
Type molecular sieve.Its main function is the mononuclear aromatics that can retain in the transmitting logistics of top, to other components of non-monocycle into
Row selectively reaction.This hydrogenation conversion catalyst is to prepare as described above according to the common sense of this field.
In the present invention, technical term " strong acid " is Conventional wisdom well known to those skilled in the art.Field of catalyst preparation
In, middle strong acid, strong acid are all made of NH3- TPD is analyzed, and 150-250 DEG C of desorption is defined as weak acid, 250-400 DEG C of desorption
It is defined as middle strong acid, 400-500 DEG C of desorption is defined as strong acid.
Above-mentioned three kinds of catalyst will consider the excessive of cracking performance, i.e. the heavy aromatics hydro-conversion at top during gradation
Catalyst touches nitrogenous refined oil, and it is reacted mainly for polycyclic aromatic hydrocarbon, therefore cracking performance need not be excessively high；Its underpart
The light aromatic hydrocarbons hydrogenation conversion catalyst of filling bears the task of production high octane gasoline, while needing to carry out double ring arene anti-
It answers, lytic activity is higher than heavy aromatics hydrogenation conversion catalyst；The effect that the mononuclear aromatics of lowest part retains catalyst is to protect
Mononuclear aromatics is stayed, while low octane rating component being avoided to enter in gasoline fraction, so its lytic activity is also unsuitable excessively high, and again
Aromatic hydrogenation reforming catalyst is close or slightly lower.
Gas-liquid separation described in step c), fractional distillation process are content well-known to those having ordinary skill in the art.Gas-liquid separation is
The separation process of hydroconversion process product generally mainly contains high-low pressure separator, circulation hydrogen system etc.；Fractional distillation process is
The process that the liquid-phase product of gas-liquid separation further refines generally mainly contains stripper, fractionating column, side line tower etc..
Conversion gasoline described in step c) is the gasoline component that hydroconversion process obtains, and general sulfur content < 10 μ g/g is ground
Study carefully method octane number > 85.
Two sections of conventional hydrocracking reactions described in step c) refer to residual after this method produces premium component
Extraction raffinate phase component, since wherein arene content is few, it is possible to directly carry out producing good boat coal or diesel product
Hydrocracking process or as preparing ethylene by steam cracking raw material, this process is content well-known to those having ordinary skill in the art, here
It is not repeated.
Compared with prior art, the method for production premium of the invention has the advantage that
1, the suitable heavy oil feed of selection will after the hydro-conversion of proprietary catalyst selectively saturation and open loop chain rupture
Polycyclic aromatic hydrocarbon in raw material is converted into premium component, and resulting gasoline component has sulfur content low, the high feature of octane number,
Reconciliation production can be carried out, under the conditions of this method, resulting other constitutive properties also have advantage, can be according to specialty oil
It is produced, is perhaps evaporated by being translated into good boat coal, diesel oil or tail oil after chain rupture after conventional hydrocracking open loop
Point.Heavy distillate can be converted as purpose product premium to greatest extent, be the processing of inferior raw material and the life of gasoline
Production has found an economically viable route, has very big practical advantages.
2, mink cell focus hydro-conversion is carried out gradation segmental machining in process flow by the method for the present invention, is produced improving gasoline
On the basis of quality, ideal comprehensive process effect is obtained.In process flow, the method for the present invention is not required to appoint device
What transformation only realizes the purpose of fine quality production by the adjustment of the combination transitivity of catalyst, has and saves equipment, operation
The advantages such as expense is low, reduce investment, are with a wide range of applications.
3, the method for the present invention has made certain limitation in process conditions, has to the reaction depth of refining stage and conversion zone
The requirement of hardness, the purpose is to as far as possible convert mononuclear aromatics for polycyclic aromatic hydrocarbon in heavy raw oil, and be retained in gasoline and evaporate
It in point, while playing and avoiding low octane rating fraction excessive fragmentation, the generation of phenomenon is reduced so as to cause quality of gasoline, cooperation is urged
The gradation of agent is excessive, can fully achieve the purpose of processing heavy raw oil greatly preparing hihg-quality gasoline.
3, according to the method for the present invention, new hydrogenation conversion catalyst is developed, is a gross appearance of technological progress, can be incited somebody to action
The production ways of premium are widened, in addition, according to the height of arene content in raw material to hydro-conversion newly developed
Catalyst has carried out targeted gradation research and development and filling, and this method journey that main reaction carries out in the case where converting operating condition may be implemented
Degree, in the past in process of production, for the hydrogenation process of wax oil raw material, if production light fraction, is only catalytic reforming
Device provides the heavy naphtha raw material of Gao Fangqian, and can not directly produce premium, and uses this method, can be directly by wax
Oily raw material is converted into the gasoline products of the market demand, technically has very big competitive advantage, provides more lifes for enterprise
Flexibility is produced, intuitive economic benefit is brought.
Detailed description of the invention
Fig. 1 is the flow diagram of present invention process method.
Specific embodiment
Combined technical method of the invention is described in detail with reference to the accompanying drawing.Process flow is only listed in Fig. 1
It is main to illustrate, some necessary equipment and container are omitted in schematic diagram.
As shown in Figure 1, process flow of the invention is as follows: anti-into hydrofinishing after heavy charge 1 is mixed with hydrogen 2
Answer area and 3 haptoreaction of Hydrobon catalyst；Reaction effluent 4 enters hydroconversion reactions area and the hydro-conversion of gradation is urged
5,6,7 haptoreaction of agent；Reaction effluent 8 enters the product 10 obtained after separation system 9 and goes successively to fractionating system 11, on
Portion's discharge conversion gasoline 12, remaining logistics 13 can be used as liquid fuel or specialty oil discharge system or enter secondary hydrogenation
Cracking reaction area 14 carries out subsequent reactions.Catalyst 3 be Hydrobon catalyst, 5,6 and 7 be respectively heavy aromatics, light aromatic hydrocarbons and
Mononuclear aromatics retains hydro-conversion class catalyst.
Combined technical method of the invention is further described followed by specific embodiment.
Embodiment 1
Using group technology process shown in FIG. 1, straight-run gas oil is selected to carry out adding hydrogen production gasoline, control one as conversion raw material
Fixed refining depth (nitrogen content 100ppm) and conversion level (yield of gasoline 30%).Catalyst used in embodiment is commodity
Catalyst FF-36 hydrotreating catalyst, special hydrogenation conversion catalyst A, B and C mononuclear aromatics retain hydro-conversion catalysis
Agent.
The property of catalyst A, B and C are shown in Table 1, and the property of feedstock oil is shown in Table 2, and operating condition is shown in Table 3.
Embodiment 2
Using group technology process shown in FIG. 1, straight-run gas oil is selected to carry out adding hydrogen production gasoline, control one as conversion raw material
Fixed purification (nitrogen content 200ppm) and conversion level (yield of gasoline 30%).Catalyst used in embodiment is commercial catalyst
Agent FF-36 hydrotreating catalyst, special hydrogenation conversion catalyst A, B and C mononuclear aromatics retain hydrogenation conversion catalyst.
The property of catalyst A, B and C are shown in Table 1, and the property of feedstock oil is shown in Table 2, and operating condition is shown in Table 3.
Embodiment 3
Using group technology process shown in FIG. 1, straight-run gas oil is selected to carry out adding hydrogen production gasoline, control one as conversion raw material
Fixed purification (nitrogen content 200ppm) and conversion level (yield of gasoline about 20%).Catalyst used in embodiment is urged for commodity
Agent FF-36 hydrotreating catalyst, special hydrogenation conversion catalyst A, B and C mononuclear aromatics retain hydrogenation conversion catalyst.
The property of catalyst A, B and C are shown in Table 1, and the property of feedstock oil is shown in Table 2, and operating condition is shown in Table 3.
Comparative example 1
Comparative example 1 is the hydrocracking process for processing straight-run gas oil, according to conventional hydrofinishing depth and controls naphtha receipts
Rate ~ 20%, contrast product are heavy naphtha, and catalyst used in comparative example is commercial catalyst FF-36 hydrorefining catalyst
Agent, FC-24 hydrocracking catalyst.
The property of feedstock oil is shown in Table 2, and operating condition is shown in Table 3.
Comparative example 2
Comparative example 1 is the hydrocracking process for processing straight-run gas oil, according to conventional hydrofinishing depth and controls naphtha receipts
Rate ~ 30%, contrast product are heavy naphtha, and catalyst used in comparative example is commercial catalyst FF-36 hydrorefining catalyst
Agent, FC-24 hydrocracking catalyst.
The property of feedstock oil is shown in Table 2, and operating condition is shown in Table 3.
The 1 main physico-chemical property of special reforming catalyst of table
2 feedstock oil property list of table
3 reaction condition of table
4 gasoline fraction main character of table
It can compared with comparative example using method processing heavy oil feed of the invention it can be seen from above-mentioned implementation and comparative example
To save the process of catalytic reforming, the directly gasoline products of production high-octane rating, low-sulfur, technically there is advantage.
Claims (17)
1. a kind of method for producing premium, includes the following steps:
A) under the conditions of hydrofining technology, heavy oil feed mixed with hydrogen after by containing Hydrobon catalyst bed
Reaction zone carries out restricted hydrofining reaction；
B) the resulting reaction effluent of step a) is under the conditions of hydroconversion process, by containing gradation wax oil hydrogenation conversion catalyst
The reaction zone of agent bed carries out restricted hydroconversion reactions；
C) reaction effluent obtained by step b) carries out gas-liquid separation, fractionation operation, obtains conversion gasoline, conversion diesel oil and unconverted
Oil.
2. according to the method for claim 1, which is characterized in that total arene content is in 40wt% in the heavy oil feed
More than, preferably 45wt% or more, nitrogen content is in 800mgg-1More than, preferably 1000mgg-1More than.
3. according to the method for claim 2, which is characterized in that the end point of distillation of the heavy oil feed is 450~580 DEG C,
It is preferred that 480~570 DEG C；Density is 0.90g/cm3More than, preferably 0.93g/cm3More than.
4. according to method described in claim 2 or 3, which is characterized in that the heavy raw oil is selected from decompressed wax oil, depitching
One of oil or wax tailings are several.
5. according to the method for claim 1, which is characterized in that Hydrofinishing conditions described in step a) are as follows: reaction pressure
6.0~13.0 MPa, hydrogen to oil volume ratio 200: 1~3000: 1, volume space velocity are 0.1~5.0 h-1, 260 DEG C of reaction temperature~
435℃。
6. according to the method for claim 1, which is characterized in that restricted hydrofinishing described in step a) refers to control step
The nitrogen content of rapid a) gained refined oil is 50 ~ 250mgg-1, preferably 100 ~ 200mgg-1。
7. according to the method for claim 6, which is characterized in that tricyclic in aromatic component in reaction effluent obtained by step a)
And the content of the above component is 1 ~ 20wt%, preferably 2 ~ 15wt%.
8. according to the method for claim 1, which is characterized in that hydroconversion process condition described in step b) are as follows: reaction
6.0~13.0 MPa of pressure, hydrogen to oil volume ratio 300: 1~2000: 1, volume space velocity are 0.1~5.0 h-1, 280 DEG C of reaction temperature
~455 DEG C.
9. according to the method for claim 1, which is characterized in that restricted hydroconversion reactions described in step b) are to accuse
The yield of gasoline fraction is 10~40wt% in output aggregate processed.
10. according to the method for claim 1, which is characterized in that the gradation wax oil hydrogenation reforming catalyst refer to by
Reaction stream direction successively includes that heavy aromatics hydrogenation conversion catalyst, light aromatic hydrocarbons hydrogenation conversion catalyst and mononuclear aromatics retain
Catalyst.
11. according to the method for claim 10, which is characterized in that the heavy aromatics hydrogenation conversion catalyst includes adding hydrogen
Active metal, Y type molecular sieve and alumina support；The heavy aromatics hydrogenation conversion catalyst includes WO by weight3Or MoO3 9
5~10wt% of~29wt%, NiO or CoO, 20~50wt% of 15~45wt% of Y type molecular sieve and aluminium oxide.
12. according to the method for claim 11, which is characterized in that the partial size of the Y type molecular sieve is 400~600nm, red
Outer 0.3~0.7mmol/g of total acid, middle strong acid ratio is 50% or more, 2.435~2.440nm of cell parameter；Hole holds 0.5~0.7
cm3/ g, wherein the ratio of 2-8nm secondary pore Kong Rongzhan total pore volume is 60% or more.
13. according to the method for claim 10, which is characterized in that the light aromatic hydrocarbons hydrogenation conversion catalyst includes adding hydrogen
Active metal, Y type molecular sieve and alumina support；The light aromatic hydrocarbons hydrogenation conversion catalyst includes WO by weight3Or MoO3 5
3~8wt% of~15wt%, NiO or CoO, 5~30wt% of 50~60wt% of Y type molecular sieve and aluminium oxide.
14. according to the method for claim 13, which is characterized in that the cell parameter of the Y type molecular sieve be 2.438~
2.442nm, infrared 0.6~0.8mmol/g of total acid, middle strong acid ratio is 80% or more, the wherein 2-8nm secondary pore hole hole Rong Zhanzong
The ratio of appearance is 50% or more.
15. according to the method for claim 1, which is characterized in that it includes adding hydrogen living that the mononuclear aromatics, which retains catalyst,
Property metal, Y type molecular sieve and alumina support；Catalyst includes MoO by weight35~25wt%, 3~8wt% of CoO, Y type
30~50wt% of 20~40wt% of molecular sieve and aluminium oxide.
16. according to the method for claim 15, which is characterized in that the partial size of the Y type molecular sieve is 500~700nm, brilliant
2.438~2.440nm of born of the same parents' parameter, infrared 0.6~0.7mmol/g of total acid, middle strong acid ratio is in 70% or more, 2-8nm secondary pore hole
The ratio that appearance accounts for total pore volume exists51~55%。
17. according to the method for claim 1, which is characterized in that the conversion diesel oil and unconverted oil is arranged as oil product
Out, or conventional hydrocracking reaction is carried out.
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