CN107345154A - A kind of method for hydrogen cracking of poor ignition quality fuel - Google Patents

A kind of method for hydrogen cracking of poor ignition quality fuel Download PDF

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Publication number
CN107345154A
CN107345154A CN201610289577.8A CN201610289577A CN107345154A CN 107345154 A CN107345154 A CN 107345154A CN 201610289577 A CN201610289577 A CN 201610289577A CN 107345154 A CN107345154 A CN 107345154A
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content
pore volume
molecular sieve
accordance
modified zeolite
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CN107345154B (en
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刘昶
王凤来
关明华
杜艳泽
黄薇
赵红
郝文月
曹均丰
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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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    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/146—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • 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
    • C10G2400/04—Diesel oil

Abstract

The invention discloses a kind of method for hydrogen cracking of poor ignition quality fuel.This method contacts including poor ignition quality fuel raw material with hydrocracking catalyst carries out hydrocracking reaction, and obtained isocrackate obtains gasoline fraction and diesel oil distillate through separation；The Modified Zeolite Y that hydrocracking catalyst wherein used uses, its property are as follows：Relative crystallinity is 110% ~ 150%, SiO2/Al2O3Mol ratio is 10 ~ 50, and cell parameter is 2.436 ~ 2.445nm, and total pore volume is 0.55 ~ 1.0mL/g, and mesoporous pore volume accounts for more than the 70% of total pore volume.This method can effectively convert poor-quality diesel-oil by cut fraction, the more excellent gasoline of the quality of production and high-quality diesel product.

Description

A kind of method for hydrogen cracking of poor ignition quality fuel
Technical field
The present invention relates to a kind of method being hydrocracked, particularly a kind of method for hydrogen cracking of catalytic diesel oil hydrogenation production high-knock rating gasoline inferior.
Background technology
Catalytic cracking（FCC）Technology is one of main technique means of heavy oil lighting, and important status is all occupied in the oil refining enterprise of countries in the world.And catalytic cracking process technology is mainly characterized by cracking the alkane in charging and cycloalkane, do not possess the ability of broken ring substantially to aromatic hydrocarbons, therefore a large amount of condensed-nuclei aromatics are generally enriched in catalytic cracking diesel oil.The sulfur content and arene content of catalytic cracking diesel oil are high, engine ignition poor performance, belong to diesel oil blending component inferior, are mainly used in mediation fuel oil, non-derv fuel and heating oil etc. abroad.And in China, in short supply due to petroleum resources, catalytic diesel oil is also mainly to be used for blended diesel product after hydrofinishing or hydro-upgrading.
In recent years, with the increasingly heaviness of processed crude quality, the raw material that catalytic cracking is processed also heaviness and in poor quality increasingly, in addition many enterprises improve the purpose of quality of gasoline or propylene enhancing to reach, to catalytic cracking unit transform or improve the operating severity of catalytic cracking unit, cause the quality of catalytic cracking diesel oil more to deteriorate.At present; the arene content for the catalytic diesel oil that Chinese oil refining enterprise is produced would generally reach 60%~80%; Cetane number is 20 or so; the quality for being difficult to make catalytic diesel oil using the hydrofinishing and hydro-upgrading means of routine meets existing more strict product specification requirement, and the product quality pressure for upgrading that enterprise is faced increasingly increases.
Can there are Y types, β types and ZSM type molecular sieves etc. as the molecular sieve of cracking active component in hydrocracking heavy oil field, wherein Y type molecular sieve application is the most universal.The method of industrial production Y type molecular sieve is essentially all the directing agent method proposed using GRACE companies of the U.S. in USP 3639099 and USP 4166099 at present, the orifice diameter in the Y type molecular sieve original powder duct of synthesis is 0.74nm × 0.74nm, and its micropore pore volume accounts for more than the 95% of total pore volume.Polycyclic heavy constituent molecular diameter in wax oil hydrogenation cracked stock is generally in more than 1nm, cracking reaction for heavy constituent macromolecular, it is adapted to the macropore range that the preferable duct pore diameter range of its reaction and product diffusion is 2nm ~ 10nm, can be exposed by more accessible acid centre, also the desorption and diffusion of the absorption beneficial to raw material macromolecular and reaction and purpose product, raising molecular sieve cracking are selective simultaneously.To improve the low situation for being unfavorable for wax oil macromolecular reaction of the mesoporous pore volume content of Y type molecular sieve, processing generally is modified to Y type molecular sieve original powder, can obtain the Modified Zeolite Y of different pore passage structures and acid distribution.
CN201310240740.8 discloses a kind of ultra-steady Y molecular sieve（USY）Method of modifying.The characteristics of this method, is in modifying process while adds organic acid and inorganic salts dealuminzation reagent, and the combination for carrying out organic acid-inorganic salts is modified.Using the mesopore volume of USY molecular sieve made from this method reality of the total volume less than 50%, its crystallinity is below 85%.
CN201510147788.3 discloses Y molecular sieve that a kind of silica alumina ratio is high and second hole is abundant and preparation method thereof.This method includes：Y type molecular sieve is handled into 1 ~ 5h at 300 DEG C ~ 600 DEG C, dry Y type molecular sieve is obtained, is cooled to 200 ~ 600 DEG C；In dried over anhydrous environment, it is passed through into dry Y type molecular sieve by the dry gas of dealumination complement silicon agent saturation, react 0.5h ~ 7.0h, or in dried over anhydrous environment, it is passed through while temperature to be at the uniform velocity warming up to 500 ~ 700 DEG C into dry y-type zeolite by the dry gas of dealumination complement silicon agent saturation, 0.5h ~ 7.0h is reacted, obtains crude product；By crude product, alkali process 10min ~ 5h, the solid-liquid mass ratio of alkali process are 1 ~ 50 at 30 ~ 100 DEG C：1, obtain the Y molecular sieve that silica alumina ratio is high and second hole is abundant.
CN02144548.6 discloses a kind of and united middle pressure hydrocracking technique of FCC apparatus, intermediate oil is obtained for treatment of heavy hydrocarbon material and the material of hydro-upgrading is provided for FCC apparatus, a kind of LCO of offer is be provided and is recycled back to the mode that hydrofining reactor is re-refined and then circulation cracks, realizes LCO inferior hydrogenation and selective splitting conversion.On the one hand LCO is maintained in diesel boiling range by the technique, improve intermediate oil selectivity, while the cut quality greatly improves, and meets new finished diesel fuel standard, meets the demand that market adjusts to product quality and products scheme.
CN96120988.7 describes a kind of catalyst for hydrocracking diesel oil, the characteristics of catalyst, is to select a kind of molecular sieve of special pore structure, its vehicle group turns into aluminum oxide, amorphous silica-alumina and molecular sieve, this method makes catalyst have good hydrothermal stability and anti-nitrogen poisoning capability by adjusting the content of each component in catalyst carrier, the diesel yield ＞ 95% when handling LCO, with the desulfurization similar to general Hydrobon catalyst, denitrification percent and degumming mass-energy power, while the Cetane number of product can be improved.Its shortcoming is that Cetane number increase rate is small, and product Cetane number still needs to further improve when handling sulphur, nitrogen and gum level higher raw material.
From the molecular sieve with cracking function from the point of view of the application during Industrial Catalysis, its performance depends primarily on following two aspects：Selective absorption and reaction.Molecular sieve aperture and overcome molecular sieve crystal surface energy barrier when reactant molecule size is less than, can just diffuse into molecular sieve pore passage, specific catalytic reaction occurs, be at this moment adsorbed molecule serve through the diffusion in the hole of molecular sieve crystal and cage it is conclusive.Molecular sieve total pore volume and mesoporous pore volume prepared by conventional method of modifying is less than normal, it is unfavorable for the conversion of raw material macromolecular, therefore the modified molecular screen that pore structure is open, mesoporous content is high and acid site exposure is more can handle the raw material that molecule is bigger, oil product is heavier, improve macromolecular conversion probability etc. and show more superior performance, so as to lift the level of hydrocracking catalyst.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of method for hydrogen cracking of poor ignition quality fuel.Hydrocracking catalyst used in the inventive method is to use a kind of Y type molecular sieve more concentrated rich in meso-hole structure, effective pore sife distribution effectively to convert poor-quality diesel-oil by cut fraction, the more excellent gasoline of the quality of production and high-quality diesel product for Cracking Component.
The method for hydrogen cracking of the present invention, including poor ignition quality fuel raw material contact with hydrocracking catalyst and carry out hydrocracking reaction, and obtained isocrackate obtains gasoline fraction and diesel oil distillate through separation；Hydrocracking catalyst wherein used, including hydrogenation active metal component and carrier, carrier include Modified Zeolite Y and aluminum oxide, wherein described Modified Zeolite Y, its property is as follows：Relative crystallinity is 110% ~ 150%, SiO2/Al2O3Mol ratio is 10 ~ 50, preferably 15 ~ 50, and cell parameter is 2.436 ~ 2.445nm, and total pore volume is 0.55 ~ 1.0mL/g, preferably 0.6 ~ 1.0mL/g, and mesoporous pore volume accounts for more than the 70% of total pore volume, preferably 80% ~ 95%.
The grain size of described Modified Zeolite Y is 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm.
In described Modified Zeolite Y, mesoporous bore dia is 2nm ~ 10nm.
The specific surface area of described Modified Zeolite Y is 650 ~ 1000m2/ g, preferably 750 ~ 1000m2/g。
The infrared total acid content of described Modified Zeolite Y is 0.5 ~ 1.0mmol/g.
In described Modified Zeolite Y, Na2O weight content is below 0.15wt%.
The property of hydrocracking catalyst of the present invention is as follows：Specific surface area is 330 ~ 500m2/ g, pore volume are 0.35 ~ 0.55mL/g.
Hydrogenation active metals of the present invention are the metal of vib and group VIII, and vib metals are preferably molybdenum and/or tungsten, and the metal of group VIII is preferably cobalt and/or nickel.On the basis of the weight of catalyst, vib metals（In terms of oxide）Content be 15.0% ~ 30.0%, group VIII metal（In terms of oxide）Content be 4.0% ~ 8.0%, the content of carrier is 62.0% ~ 81.0%.
Described carrier of hydrocracking catalyst, on the basis of the weight of carrier, the content of Modified Zeolite Y is 45% ~ 70%, preferably 50% ~ 70%, and the content of aluminum oxide is 30% ~ 55%, preferably 30% ~ 50%.
The preparation method of hydrocracking catalyst of the present invention, include preparation and the load hydrogenation active metal component of carrier, the preparation process of wherein carrier is as follows：Modified Zeolite Y, aluminum oxide are mixed, shaping, then dries and is calcined, the preparation method of catalyst carrier, wherein Modified Zeolite Y is made, comprises the following steps：
（1）NaY types molecular sieve with（NH4）2SiF6Aqueous solution contact is reacted, through filtering and drying after reaction；
（2）To step（1）Gained Y type molecular sieve carries out hydro-thermal process；Hydrothermal conditions：Gauge pressure is 0.05 ~ 0.20MPa, and temperature is 400 ~ 600 DEG C, and processing time is 0.5 ~ 5.0 hour；
（3）By step（2）Gained Y type molecular sieve carries out hydrothermal crystallizing processing under the conditions of existing for organic formwork agent, then filtered and dry；
（4）By step（3）The Y type molecular sieve of gained is calcined under low temperature oxygen-enriched atmosphere, and the Y type molecular sieve of the present invention is made.
In the preparation process of Modified Zeolite Y used in the present invention, step（1）The property of described NaY type molecular sieves is as follows：
SiO2/Al2O3Mol ratio is 3 ~ 6, preferably 4.5 ~ 5.5, and grain size is 1.0 ~ 2.5 μm, and preferably 1.2 ~ 1.8 μm, relative crystallinity is 80% ~ 110%, and cell parameter is 2.465 ~ 2.470nm, Na2O weight content is 6.0wt% ~ 8.0wt%, and specific surface area is 600 ~ 900m2/ g, total pore volume are 0.3 ~ 0.4 mL/g, and micropore pore volume accounts for more than the 75% of total pore volume.
The inventive method step（1）In,（NH4）2SiF6Addition be NaY type molecular sieve butt weight 5wt% ~ 20wt%.
The inventive method step（1）In,（NH4）2SiF6The mass concentration of the aqueous solution is 50 ~ 100g/L.NaY types molecular sieve with（NH4）2SiF6The reaction condition that aqueous solution contact is reacted：Temperature is 80 ~ 150 DEG C, and preferably 90 ~ 120 DEG C, the reaction time is 0.1 ~ 5.0 hour, preferably 1.0 ~ 3.0 hours.
The inventive method step（1）In, NaY types molecular sieve with（NH4）2SiF6After aqueous solution contact is reacted, molecular sieve and accessory substance are separated, can be washed, refiltered, dry, the butt of the Y type molecular sieve of gained is 60wt% ~ 80wt% after preferably drying.Dry condition is usually to be dried 0.5 ~ 5.0 hour at 50 ~ 95 DEG C.
The inventive method step（2）In, hydro-thermal process is to use saturated steam processing step（1）In obtained molecular sieve, treatment conditions：0.05 ~ 0.20MPa of gauge pressure, preferably 0.10 ~ 0.20MPa, preferably 400 ~ 600 DEG C of temperature, 450 ~ 600 DEG C, preferably 0.5 ~ 5.0 hour processing time, 1.0 ~ 3.0 hours.
The inventive method step（3）In, organic formwork agent is the one or more in tetraethyl ammonium hydroxide, TMAH, TPAOH.Wherein, by step（2）In after obtained Y type molecular sieve uniformly mixes with organic formwork agent, carry out hydrothermal crystallizing, process is as follows：By step（2）In obtained Y type molecular sieve be beaten in the organic formwork agent aqueous solution, solvent and solute weight ratio 3：1~8：1, temperature is 70 ~ 90 DEG C, and the time is 0.5 ~ 5.0 hour, and the mass concentration of the organic formwork agent aqueous solution is 3% ~ 10%, and mixed material then is placed in into crystallization in crystallizing kettle, and crystallization temperature is 80 ~ 120 DEG C, and crystallization time is 4 ~ 10h, and gauge pressure is 0.1 ~ 0.2MPa.After crystallization, filtered and drying can use conventional method to carry out, and typically dry condition is as follows：1 ~ 10h is dried at 50 ~ 110 DEG C.
In the inventive method, step（4）It is by step（3）Obtained Y type molecular sieve be calcined under low temperature oxygen-enriched atmosphere, and wherein oxygen-enriched atmosphere refers to that oxygen content is more than 50v%, and sintering temperature is 300 ~ 450 DEG C, and roasting time is 5 ~ 10h.Typically using the method being calcined under temperature programming again constant temperature, heating rate is preferably 1 ~ 2 DEG C/min for roasting.
The property for the poor ignition quality fuel that the method for hydrogen cracking of the present invention is processed is as follows：Density（20℃）For 0.9 ~ 1.0g/cm3, initial boiling point is 200 ~ 250 DEG C, is done as 350 ~ 380 DEG C, sulfur content is 0.5 wt% ~ 2.0wt%, and nitrogen content is 800 ~ 2000 μ g/g.
The inventive method is applied to catalytic diesel oil hydro-conversion inferior production high-knock rating gasoline process, using one-stage serial technical process, before hydrocracking reaction, need to carry out hydrofinishing, its used Hydrobon catalyst can use conventional Hydrobon catalyst or pretreating catalyst by hydrocracking, typically use alumina-based supports, using vib and group VIII metal as hydrogenation active metal component, vib metals are preferably molybdenum and/or tungsten, and the metal of group VIII is preferably cobalt and/or nickel.On the basis of the weight of catalyst, vib metals（In terms of oxide）Content be 15.0% ~ 30.0%, group VIII metal（In terms of oxide）Content be 4.0% ~ 8.0%.
The inventive method, used hydrocracking operation condition are as follows：Reaction temperature is 350~450 DEG C, reacts 8.0~15.0MPa of stagnation pressure, hydrogen to oil volume ratio 600~1500,0.6~2.5h of volume space velocity during liquid-1。
In hydrocracking catalyst used in the inventive method, Modified Zeolite Y is to use（NH4）2SiF6Processing is modified to NaY molecular sieve, while modulation molecular sieve silica alumina ratio is realized, sodium ion in NaY molecular sieve can be deviate from together, then hydrothermal crystallizing is carried out to the molecular sieve after hydro-thermal process in the presence of organic formwork agent, part silicon atom and aluminium atom can be so set to enter framework of molecular sieve structure under organic formwork agent effect, while further stablizing and improving the skeleton structure of modified molecular screen, eliminate caused non-skeleton structure in zeolite-water heat treatment process, unimpeded pore passage structure, part organic formwork agent can be also entered in the duct of molecular sieve, coordinate follow-up oxygen-enriched low-temperature treatment, can be by the controllable removing in order of the organic formwork agent in molecular sieve, so as to produce a large amount of ordered mesopore structures, and pore structure is more concentrated.
In hydrocracking catalyst used in the inventive method, Modified Zeolite Y, acidity is suitable, crystallinity is high, mesoporous proportion is high, pore-size distribution is more concentrated, suitably as Cracking Component.Because the Y type molecular sieve has bigger pore volume and mesopore volume, more acid centres are exposed, be advantageous to raw material heavy oil macromolecular to be cracked, but also with more preferably pore size distribution range, the cracking degree of reactant can be efficiently controlled, and be advantageous to product and be diffused in duct, so in cracking reaction, can relative increase activated centre, and the cracking reaction of the macromolecular progress suitable degree in catalytic diesel oil inferior can be made, both the ability of the cracking production gasoline of catalytic diesel oil inferior had been improved, reduce coke yield simultaneously, catalyst can show good cracking activity and product selectivity.
Brief description of the drawings
Fig. 1 is the SEM electromicroscopic photographs of the gained Modified Zeolite Y of embodiment 1；
Fig. 2 is the SEM electromicroscopic photographs of the gained Modified Zeolite Y of comparative example 1；
Fig. 3 is the XRD diffraction patterns of the gained Modified Zeolite Y of embodiment 1.
Embodiment
Aluminum oxide can include macroporous aluminium oxide and small porous aluminum oxide in carrier of hydrocracking catalyst of the present invention, and wherein aperture alumina part or whole is used as adhesive.On the basis of the weight of carrier：Macroporous aluminium oxide content is 20% ~ 50%, preferably 20% ~ 40%, and aperture alumina content is 5% ~ 25%, preferably 10% ~ 25%.
Macroporous aluminium oxide used in the present invention, its pore volume are 0.6 ~ 1.3mL/g, preferably 0.7 ~ 1.1mL/g, and specific surface area is 300 ~ 450m2/g。
Adhesive therefor of the present invention is made up of small porous aluminum oxide and inorganic acid and/or organic acid.Aperture alumina pore volume used is 0.3 ~ 0.5mL/g, and specific surface area is 200 ~ 400m2/g。
Detailed process prepared by carrier of hydrocracking catalyst of the present invention is：
Modified Zeolite Y, aluminum oxide are mixed, shaping, is then dried and is calcined, be prepared into carrier, described drying can be carried out 3 ~ 6 hours at a temperature of 80 DEG C ~ 150 DEG C, and roasting is calcined 2.5 ~ 6.0 hours at 500 DEG C ~ 600 DEG C.
In hydrocracking catalyst of the present invention, the load of active metal can use carrying method conventional in the prior art, it is preferred that infusion process, can be saturation leaching, excessive leaching or complexing leaching, i.e. with the solution impregnated catalyst carrier containing required active component, then carrier after dipping is calcined 2.5 ~ 6.0 hours at 450 DEG C ~ 550 DEG C, final catalyst is made in 100 DEG C ~ 150 DEG C dryings 1 ~ 12 hour.
The following examples are used to technical scheme be described in more detail, but the scope of the present invention is not limited solely to the scope of these embodiments.In the present invention, wt% is mass fraction.
Analysis method of the present invention：Specific surface area, pore volume, mesoporous pore volume use low temperature liquid nitrogen determination of adsorption method, and relative crystallinity and cell parameter use x-ray diffraction method, and silica alumina ratio uses XRF methods（X ray fluorescence spectrometry）Measure, the grain size of molecular sieve use SEM（SEM）Mode determine.Meleic acid amount uses Pyridine adsorption IR spectra method, and sodium content uses plasma emission spectrometry.
NaY molecular sieve original powder employed in the embodiment of the present invention and comparative example is industrially prepared, and property is as follows：SiO2/Al2O3Mol ratio is 5.1, and grain size is ~ 1.7 μm, relative crystallinity 95%, cell parameter 2.468nm, Na2O weight content is 6.5wt%, specific surface area 856m2/ g, total pore volume 0.32mL/g, micropore pore volume account for the 81.3% of total pore volume, butt 72.0wt%.
Embodiment 1
Take NaY original powder 278g to be put into 800mL water purification, be warming up to 95 DEG C, start to be added dropwise into molecular sieve pulp（NH4）2SiF6The aqueous solution, it is 78g/L's that 410mL solution concentrations were uniformly added dropwise at 60 minutes（NH4）2SiF6Solution, constant temperature is stirred 2 hours after completion of dropwise addition, and constant temperature is filtered and dried after terminating, and the butt of molecular sieve is 63.8wt% after drying；Above-mentioned dried molecular sieve is added in hydrothermal treatment device, gauge pressure 0.15MPa, 530 DEG C of temperature, under conditions of 1.5 hours processing times to molecular sieve carry out hydro-thermal process；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetraethyl ammonium hydroxide aqueous solution that 650mL mass concentrations are 7.5%, constant temperature stirs 2 hours under the conditions of 80 DEG C, then mixed material is transferred in crystallizing kettle and carries out hydrothermal crystallizing, 100 DEG C of crystallization temperature, gauge pressure 0.1MPa, crystallization time 8 hours, crystallization is filtered after terminating and drying process；The drying sample that crystallization obtains is calcined under oxygen-enriched state, oxygen content is 60v% in calcination atmosphere, and heating rate is 1 DEG C/min, and constant temperature calcining temperature is 360 DEG C, and the constant temperature calcining time is 8 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-1, molecular sieve property are listed in table 1.
Embodiment 2
Take NaY original powder 278g to be put into 800mL water purification, be warming up to 100 DEG C, start to be added dropwise into molecular sieve pulp（NH4）2SiF6The aqueous solution, it is 58g/L's that 256mL solution concentrations were uniformly added dropwise at 60 minutes（NH4）2SiF6Solution, constant temperature is stirred 2 hours after completion of dropwise addition, and constant temperature is filtered and dried after terminating, and the butt of molecular sieve is 65.0wt% after drying；Above-mentioned dried molecular sieve is added in hydrothermal treatment device, gauge pressure 0.10MPa, 450 DEG C of temperature, under the conditions of 2.0 hours processing times to molecular sieve carry out hydro-thermal process；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetraethyl ammonium hydroxide aqueous solution that 369mL mass concentrations are 4.8%, constant temperature stirs 2 hours under the conditions of 85 DEG C, then mixed material is transferred in crystallizing kettle and carries out hydrothermal crystallizing, 110 DEG C of crystallization temperature, gauge pressure 0.1MPa, crystallization time 10 hours, crystallization is filtered after terminating and drying process；The drying sample that hydrothermal crystallizing obtains is calcined under oxygen-enriched state, oxygen content is 65v% in calcination atmosphere, and heating rate is 1 DEG C/min, and constant temperature calcining temperature is 390 DEG C, and the constant temperature calcining time is 8 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-2, molecular sieve property are listed in table 1.
Embodiment 3
Take NaY original powder 278g to be put into 800mL water purification, be warming up to 95 DEG C, start to be added dropwise in molecular sieve pulp（NH4）2SiF6The aqueous solution, it is 78g/L's that 410mL solution concentrations were uniformly added dropwise at 60 minutes（NH4）2SiF6Solution, constant temperature is stirred 2 hours after completion of dropwise addition, and constant temperature is filtered and dried after terminating, and the butt of molecular sieve is 63.8wt% after drying；Above-mentioned dried molecular sieve is added in hydrothermal treatment device, gauge pressure 0.15MPa, 480 DEG C of temperature, under the conditions of 1.0 hours processing times to molecular sieve carry out hydro-thermal process；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetraethyl ammonium hydroxide aqueous solution that 520mL mass concentrations are 5.3%, constant temperature stirs 4 hours under the conditions of 80 DEG C, then mixed material is transferred in crystallizing kettle and carries out hydrothermal crystallizing, 90 DEG C of crystallization temperature, gauge pressure 0.1MPa, crystallization time 10 hours, crystallization is filtered after terminating and drying process；The drying sample that hydrothermal crystallizing obtains is calcined under oxygen-enriched state, oxygen content is 70v% in calcination atmosphere, and heating rate is 1 DEG C/min, and constant temperature calcining temperature is 420 DEG C, and the constant temperature calcining time is 6 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-3, molecular sieve property are listed in table 1.
Embodiment 4
Take NaY original powder 278g to be put into 800mL water purification, be warming up to 100 DEG C, start to be added dropwise into molecular sieve pulp（NH4）2SiF6The aqueous solution, it is 55g/L's that 182mL solution concentrations were uniformly added dropwise at 60 minutes（NH4）2SiF6Solution, constant temperature is stirred 2 hours after completion of dropwise addition, and constant temperature divides after terminating to be filtered and dried, and the butt of molecular sieve is 68.0wt% after drying；Above-mentioned dried molecular sieve is added in hydrothermal treatment device, gauge pressure 0.10MPa, 580 DEG C of temperature, under the conditions of 2.0 hours processing times to molecular sieve carry out hydro-thermal process；The molecular sieve after 130g hydro-thermal process is taken to be put into the TPAOH aqueous solution that 910mL mass concentrations are 7.5%, constant temperature stirs 4 hours under the conditions of 90 DEG C, then mixed material is transferred in crystallizing kettle and carries out hydrothermal crystallizing, 110 DEG C of crystallization temperature, gauge pressure 0.1MPa, crystallization time 10 hours, crystallization is filtered after terminating and drying process；The drying sample that hydrothermal crystallizing obtains is calcined under oxygen-enriched state, oxygen content is 65v% in calcination atmosphere, and heating rate is 1 DEG C/min, and constant temperature calcining temperature is 360 DEG C, and the constant temperature calcining time is 10 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-4, molecular sieve property are listed in table 1.
Comparative example 1
Take NaY original powder 278g to be put into the solution that 1000mL ammonium nitrate concns are 1.5mol/L, be warming up to 95 DEG C, constant temperature is stirred 2 hours, and constant temperature is filtered, washed and dried after terminating, and the butt of molecular sieve is 63.8wt% after drying；Molecular sieve is calcined 3 hours by temperature programming at 600 DEG C；Then repeat an ammonium to exchange, and filter and dry；The molecular sieve after second of ammonium exchange of 100g is taken to be put into the tetraethyl ammonium hydroxide aqueous solution that 650mL mass concentrations are 7.5%, constant temperature stirs 2 hours under the conditions of 80 DEG C, then mixed material is transferred in crystallizing kettle and carries out crystallization, 100 DEG C of crystallization temperature, gauge pressure is 0.1MPa, crystallization time 8 hours, crystallization is filtered after terminating and drying process；The drying sample that crystallization obtains is calcined under oxygen-enriched state, oxygen content is 60v% in calcination atmosphere, and heating rate is 1 DEG C/min, and constant temperature calcining temperature is 360 DEG C, and the constant temperature calcining time is 8 hours, obtains molecular sieve.Sample number into spectrum LDAY-1, molecular sieve property are listed in table 1.
Comparative example 2
Take NaY original powder 278g to be put into the solution that 1000mL ammonium nitrate concns are 1.5mol/L, be warming up to 95 DEG C, constant temperature is stirred 2 hours, and constant temperature divides after terminating to be filtered, washed and dried, and the butt of molecular sieve is 63.8wt% after drying；Molecular sieve is calcined 3 hours by temperature programming at 600 DEG C；Then repeat an ammonium to exchange, and filter and dry；The molecular sieve after second of ammonium exchange of 100g is taken to be put into the dust technology that 800mL concentration is 0.3mol/L, constant temperature stirs 2 hours under the conditions of 80 DEG C, and constant temperature is filtered after terminating and drying process；Above-mentioned dried molecular sieve is added in hydrothermal treatment device, gauge pressure 0.20MPa, 530 DEG C of temperature, under the conditions of 2.0 hours processing times to molecular sieve carry out hydro-thermal process obtain molecular sieve；Sample number into spectrum LDAY-2, molecular sieve property are listed in table 1.
Comparative example 3
Molecular sieve, sample number into spectrum LDAY-3 are prepared using the method for embodiment in CN201510147788.3 1, molecular sieve property is listed in table 1.
Table 1 The property of Y type molecular sieve
Production code member LAY-1 LAY-2 LAY-3 LAY-4
Specific surface area, m2/g 896 859 890 902
Pore volume, cm3/g 0.69 0.60 0.73 0.78
Lattice constant, nm 2.441 2.444 2.442 2.436
Relative crystallinity, % 123 134 129 122
Average crystallite size, μm 1.7 1.7 1.7 1.7
SiO2/Al2O3Mol ratio 48.6 28.6 33.5 17.3
Mesoporous pore volume（Bore dia 2nm ~ 10nm）Account for total pore volume ratio, % 82 89 86 90
Infrared total acid content, mmol/g 0.84 0.88 0.71 0.62
Na2O, wt% 0.05 0.06 0.06 0.08
Continued 1
Production code member LDAY-1 LDAY-2 LDAY-3
Specific surface area, m2/g 633 712 603
Pore volume, cm3/g 0.44 0.38 0.38
Lattice constant, nm 2.439 2.436 2.449
Relative crystallinity, % 98 103 86
Average crystallite size, μm 2.1 2.1 2.1
SiO2/Al2O3Mol ratio 7.5 33.5 8.6
Mesoporous pore volume（Bore dia 2nm ~ 10nm）Account for total pore volume ratio, % 47 34 37
Infrared total acid content, mmol/g 0.77 0.41 0.71
Na2O, wt% 0.21 0.19 0.45
Embodiment 5
By 111.0 grams of LAY-1 molecular sieves（Butt 90wt%）, 100.0 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%）, 100.0 grams of adhesives（The mol ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4）Mixed grind in roller is put into, adds water, is rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, is then calcined 4 hours at 550 DEG C, obtains carrier FHS-1.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of temperature programming is calcined 4 hours, obtains catalyst FHC-1, carrier and corresponding catalyst composition and property is shown in Table 2.
Embodiment 6
By 144.4 grams of LAY-2 molecular sieves（Butt 90wt%）, 57.1 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%）, 100.0 grams of adhesives（The mol ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4）Mixed grind in roller is put into, adds water, is rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, is then calcined 4 hours at 550 DEG C, obtains carrier FHS-2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of temperature programming is calcined 4 hours, obtains catalyst FHC-2, carrier and corresponding catalyst composition and property is shown in Table 2.
Embodiment 7 ~ 8
According to the method for embodiment 5, LAY-1 being changed into LAY-3, LAY-4 respectively, carrier FHS-3, FHS-4 and catalyst FHC-3, FHC-4 being made, carrier and corresponding catalyst composition and property are shown in Table 2.
Comparative example 4 ~ 6
According to the method for embodiment 5, LAY-1 being changed into LDAY-1, LDAY-2, LDAY-3 respectively, carrier DHS-1, DHS-2, DHS-3 and catalyst DHC-1, DHC-2, DHC-3 being made, carrier and corresponding catalyst composition and property are shown in Table 2.
Embodiment 9 ~ 12
This embodiment describes the inventive method, and hydrocracking catalyst FHC-1, FHC-2, FHC-3, FHC-4 is respectively adopted and is tested.Evaluated on fixed bed hydrogenation experimental rig, using one-stage serial technological process, wherein Hydrobon catalyst is 3936 catalyst for refining, and operating condition is：React stagnation pressure 10.0MPa, hydrogen to oil volume ratio 1000:1, volume space velocity 1.50h during liquid-1；Feedstock oil is catalytic diesel oil, and property is listed in table 3, and evaluation result is listed in table 4.
Comparative example 7 ~ 9
This comparative example describes hydrocracking catalyst DHC-1, DHC-2, the DHC-3 prepared using comparative example.Evaluated on fixed bed hydrogenation experimental rig, using one-stage serial technological process, wherein Hydrobon catalyst is 3936 catalyst for refining, and operating condition is：React stagnation pressure 10.0MPa, hydrogen to oil volume ratio 1000:1, volume space velocity 1.50h during liquid-1；Feedstock oil is catalytic diesel oil, and property is listed in table 3, and evaluation result is listed in table 4.
The composition and property of the catalyst carrier of table 2 and catalyst
Carrier forms and property
Numbering FHS-1 FHS-2 FHS-3 FHS-4
Composition
Modified Zeolite Y, wt% 50.0 65.0 50.0 50.0
Macroporous aluminium oxide, wt% 35.0 20.0 35.0 35.0
Adhesive, wt% Surplus Surplus Surplus Surplus
Property
Pore volume, mL/g 0.65 0.60 0.62 0.68
Specific surface area, m2/g 586 642 571 563
Catalyst forms and property
Numbering FHC-1 FHC-2 FHC-3 FHC-4
WO3, wt% 22.48 22.56 22.49 22.12
NiO, wt% 5.56 5.78 6.01 6.08
Pore volume, mL/g 0.45 0.39 0.47 0.49
Specific surface area, m2/g 444 438 434 423
Continued 2
Carrier forms and property
Numbering DHS-1 DHS-2 DHS-3
Composition
Modified Zeolite Y, wt% 50.0 50.0 50.0
Macroporous aluminium oxide, wt% 35.0 35.0 35.0
Adhesive, wt% Surplus Surplus Surplus
Property
Pore volume, mL/g 0.45 0.44 0.47
Specific surface area, m2/g 530 512 459
Catalyst forms and property
Numbering DHC-1 DHC-2 DHC-3
WO3, wt% 22.15 22.17 22.14
NiO, wt% 6.00 6.05 5.93
Pore volume, mL/g 0.30 0.26 0.28
Specific surface area, m2/g 354 401 346
Table 3 Feedstock oil main character
Feedstock oil title Catalytic diesel oil
Density (20 DEG C) , g/cm3 0.9640
Boiling range, DEG C
IBP/10% 205/227
30%/50% 252/275
70%/90% 303/343
95%/EBP 357/371
Condensation point, DEG C -24
Cetane number ~12
S, wt% 0.81
N, μ g/g 914
Mass spectrum forms, wt%
Alkane 13.4
Total cycloalkanes 8.3
Total aromatic hydrocarbons 78.3
Table 4 Comparative evaluation's result
Hydrocracking catalyst FHC-1 FHC-2 FHC-3 FHC-4
Feedstock oil Catalytic diesel oil Catalytic diesel oil Catalytic diesel oil Catalytic diesel oil
Operating condition
Volume space velocity during liquid, h-1 1.5 1.5 1.0 1.0
React stagnation pressure, MPa 10.0 10.0 10.0 10.0
Hydrogen to oil volume ratio 1000:1 1000:1 1000:1 1000:1
Reaction temperature, DEG C 386 382 389 388
Product yield and property
Gasoline
Yield, wt% 42.0 41.8 45.5 56.9
Research octane number (RON) RON 94.6 93.9 95.1 93.5
S, μ g/g 2 3 2 1
N, μ g/g 1 1 1 1
Diesel oil
Yield, wt% 53.2 54.3 50.9 37.9
Cetane number 36.8 37.5 36.1 38.1
Chemical hydrogen consumption, wt% 2.89 2.92 2.91 3.05
Liquid is received, wt% 95.2 96.1 96.4 94.8
Continued 4
Hydrocracking catalyst DHC-1 DHC-2 DHC-3
Feedstock oil Catalytic diesel oil Catalytic diesel oil Catalytic diesel oil
Operating condition
Volume space velocity during liquid, h-1 1.5 1.5 1.0
React stagnation pressure, MPa 10.0 10.0 10.0
Hydrogen to oil volume ratio 1000:1 1000:1 1000:1
Reaction temperature, DEG C 403 410 415
Product yield and property
Gasoline
Yield, wt% 38.9 37.2 44.9
Research octane number (RON) RON 90.1 89.2 88.6
S, μ g/g 8 9 11
N, μ g/g 5 4 8
Diesel oil
Yield, wt% 51.2 50.4 44.8
Cetane number 26.4 28.1 29.3
Chemical hydrogen consumption, wt% 3.22 3.18 3.34
Liquid is received, wt% 90.1 87.6 89.7
When it can be seen from the result of the test of table 4 using the inventive method and hydrocracking catalyst, the yields of gasoline products, quality etc. are superior to comparative example, and the property of diesel product is also significantly better than comparative example.

Claims (13)

1. a kind of method for hydrogen cracking of poor ignition quality fuel, including poor ignition quality fuel raw material contact with hydrocracking catalyst and carry out hydrocracking reaction, obtained isocrackate obtains gasoline fraction and diesel oil distillate through separation；Hydrocracking catalyst wherein used, including hydrogenation active metal component and carrier, carrier include Modified Zeolite Y and aluminum oxide, wherein described Modified Zeolite Y, its property is as follows：Relative crystallinity is 110% ~ 150%, SiO2/Al2O3Mol ratio is 10 ~ 50, and cell parameter is 2.436 ~ 2.445nm, and total pore volume is 0.55 ~ 1.0mL/g, and mesoporous pore volume accounts for more than the 70% of total pore volume.
2. in accordance with the method for claim 1, it is characterised in that：The property of the Modified Zeolite Y is as follows：SiO2/Al2O3Mol ratio is 15 ~ 50, and total pore volume is 0.6 ~ 1.0mL/g, and mesoporous pore volume accounts for the 80% ~ 95% of total pore volume.
3. in accordance with the method for claim 1, it is characterised in that：The grain size of the Modified Zeolite Y is 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm.
4. in accordance with the method for claim 1, it is characterised in that：The mesoporous bore dia of the Modified Zeolite Y is 2nm ~ 10nm.
5. in accordance with the method for claim 1, it is characterised in that：The specific surface area of the Modified Zeolite Y is 650m2/g~1000m2/ g, preferably 750m2/g~1000m2/g。
6. in accordance with the method for claim 1, it is characterised in that：The infrared total acid content of the Modified Zeolite Y is 0.5 ~ 1.0mmol/g.
7. in accordance with the method for claim 1, it is characterised in that：In the Modified Zeolite Y, Na2O weight content is below 0.15wt%.
8. in accordance with the method for claim 1, it is characterised in that：The property of the hydrocracking catalyst is as follows：Specific surface area is 330 ~ 500m2/ g, pore volume are 0.35 ~ 0.55mL/g.
9. in accordance with the method for claim 1, it is characterised in that：Described hydrogenation active metals are the metal of vib and group VIII, and vib metals are molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel；On the basis of the weight of catalyst, vib metals are using the content that oxide is counted as 15.0% ~ 30.0%, and for group VIII metal using the content that oxide is counted as 4.0% ~ 8.0%, the content of carrier is 62.0% ~ 81.0%.
10. in accordance with the method for claim 1, it is characterised in that：Described carrier of hydrocracking catalyst, on the basis of the weight of carrier, the content of Modified Zeolite Y is 45% ~ 70%, preferably 50% ~ 70%, and the content of aluminum oxide is 30% ~ 55%, preferably 30% ~ 50%.
11. in accordance with the method for claim 1, it is characterised in that：The property of the poor ignition quality fuel is as follows：20 DEG C of density are 0.9 ~ 1.0g/cm3, initial boiling point is 200 ~ 250 DEG C, is done as 350 ~ 380 DEG C, sulfur content is 0.5 wt% ~ 2.0wt%, and nitrogen content is 800 ~ 2000 μ g/g.
12. in accordance with the method for claim 1, it is characterised in that：The method for hydrogen cracking uses one-stage serial technical process, before hydrocracking reaction, need to carry out hydrofinishing, its used Hydrobon catalyst uses alumina-based supports, using vib and group VIII metal as hydrogenation active metal component, vib metals are molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel；On the basis of the weight of catalyst, vib metals are using the content that oxide is counted as 15.0% ~ 30.0%, and group VIII metal is using the content that oxide is counted as 4.0% ~ 8.0%.
13. according to the method described in claim 1 or 12, it is characterised in that：Used hydrocracking operation condition is as follows：Reaction temperature is 350~450 DEG C, reacts 8.0~15.0MPa of stagnation pressure, hydrogen to oil volume ratio 600~1500,0.6~2.5h of volume space velocity during liquid-1。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115261062A (en) * 2021-04-30 2022-11-01 中国石油化工股份有限公司 Method for producing high-octane gasoline by single-stage hydrogenation of diesel oil
CN116064132A (en) * 2021-10-29 2023-05-05 中国石油化工股份有限公司 Diesel catalytic separation method

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CN104667969A (en) * 2013-11-26 2015-06-03 中国石油化工股份有限公司 A hydrocracking catalyst and a preparing method thereof

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CN101987971A (en) * 2009-08-06 2011-03-23 中国石油化工股份有限公司石油化工科学研究院 Method for producing high-octane petrol by inferior diesel
CN104667969A (en) * 2013-11-26 2015-06-03 中国石油化工股份有限公司 A hydrocracking catalyst and a preparing method thereof

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Publication number Priority date Publication date Assignee Title
CN115261062A (en) * 2021-04-30 2022-11-01 中国石油化工股份有限公司 Method for producing high-octane gasoline by single-stage hydrogenation of diesel oil
CN115261062B (en) * 2021-04-30 2024-01-09 中国石油化工股份有限公司 Method for producing high-octane gasoline by single-stage hydrogenation of diesel oil
CN116064132A (en) * 2021-10-29 2023-05-05 中国石油化工股份有限公司 Diesel catalytic separation method
CN116064132B (en) * 2021-10-29 2024-05-07 中国石油化工股份有限公司 Diesel catalytic separation method

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