CN107345161B - A kind of method for hydrogen cracking of coal tar - Google Patents

A kind of method for hydrogen cracking of coal tar Download PDF

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Publication number
CN107345161B
CN107345161B CN201610289579.7A CN201610289579A CN107345161B CN 107345161 B CN107345161 B CN 107345161B CN 201610289579 A CN201610289579 A CN 201610289579A CN 107345161 B CN107345161 B CN 107345161B
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content
pore volume
modified zeolite
molecular sieve
catalyst
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CN107345161A (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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • 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
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • 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
    • 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
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • 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
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
    • 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

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

Abstract

The invention discloses a kind of method for hydrogen cracking of coal tar.This method includes coal tar raw material after hydrofinishing, contacts with hydrocracking catalyst and carries out hydrocracking reaction, and obtained isocrackate is separated, and obtains gasoline fraction and diesel oil distillate；Wherein Modified Zeolite Y used in the hydrocracking catalyst, property are as follows: relative crystallinity is 110% ~ 150%, SiO2/Al2O3Molar ratio is 55 ~ 100, and cell parameter is 2.425 ~ 2.435nm, and total pore volume is 0.55 ~ 1.0mL/g, and mesoporous pore volume accounts for 70% of total pore volume or more.This method can effectively convert the polycyclic aromatic hydrocarbon heavy constituent in coal tar, the quality of production more preferably transportation fuel blend component.

Description

A kind of method for hydrogen cracking of coal tar
Technical field
The present invention relates to a kind of method for hydrogen cracking of coal tar, especially a kind of to convert cleaning vapour for coal tar fraction The method for hydrogen cracking of oil and diesel oil.
Background technique
Coal tar is an important byproduct during pyrolysis of coal distillation process, is the complex mixture of many kinds of substance, According to the difference of pyrolysis of coal pyrolysis temperature and process approach, coal tar can be divided into coalite tar and high temperature coal-tar.
Compared with petroleum heavy distillat, coal tar raw material has the content of heteroatoms such as sulphur, nitrogen high, and ash content is high, and polycyclic aromatic hydrocarbon contains The features such as amount is high, resin and asphalt content is high.Therefore directly burning can generate a large amount of sulfide and nitride, cause serious Environmental pollution.Coal tar clean processing and effective use become more important.Coal can be effectively removed using hydrogenation technique The impurity such as sulphur, nitrogen in tar reduce its density, realize lighting.
Coal tar hydrogenating processing includes mainly hydrofinishing and hydro-upgrading, and hydrofinishing main purpose is to remove coal The hetero atoms such as sulphur, nitrogen, oxygen in tar improve product quality；The main purpose of hydro-upgrading is to further change coal tar The molecular structure of each component in oil, such as aromatic hydrogenation saturation, polycyclic aromatic hydrocarbon open loop.Compared with distillate hydrogenation, coal tar adds Hydrogen modifying catalyst faces the challenge in terms of following four: first is that high oxygen content, the water that deoxidation generates is to the active, steady of catalyst Qualitative and intensity generates very detrimental effect, second is that colloid, carbon residue content height are easy to promote catalyst carbon deposit, causes to be catalyzed Agent inactivation and bed blocking, third is that sulphur, nitrogen content are high, it is desirable that deep hydrogenation denitrogenation, otherwise stability does not reach requirement, fourth is that coal Contain a large amount of aromatic hydrocarbons in tar, Cetane number is very low in diesel oil distillate, it is desirable that it is deeply hydrodearomatized, and reducing to the greatest extent Maximum aromatic hydrocarbons saturation and open loop, make every effort to improve diesel cetane-number to greatest extent under the premise of chain rupture.
The process that the process of middle coalite tar catalytic hydrogenation clean fuel is also its lighting, cleans, including protect Shield process (removing heavy metal), unifining process (hetero atoms such as removing nitrogen, sulphur, oxygen), hydrocracking process (alkene saturation, Aromatic hydrocarbons saturation and cracking).Wherein hydrocracking process is the main process that coal tar cleans, and hydrocracking catalyst is this One of key technology in the process.
CN201010228569.5 discloses group technology and its catalysis of a kind of producing clean fuel oil by hydrogenation of coal tar Agent.This method be using fixed bed group technology, active component used in catalyst for hydro-upgrading therein be group VIII and Vib metals oxide NiO, MoO3、CoO、WO3One or more of, carrier is the modified kaolin of acid.Due to using Sour modified kaolin is as carrier, and hole holds very little and acidity is higher, therefore, for colloid and the higher coal tar of asphalt content Oily raw material, resin and asphalt enter less than in catalyst duct, more carbon deposit are formed in catalyst surface, to make catalyst It is easy inactivation, operation cycle is short；In addition hydrogen consumption is higher, and diesel product quality is to be improved.
CN102029157A discloses a kind of catalyst for coal tar pitch hydrogenation cracking lighting reaction, with inorganic Porous material is carrier, selects one of aluminium oxide, salic silica gel, MCM-41 or SBA-15, passes through vacuum impregnation Method, by one or both of metallic element Fe, Ni, Co, Mo of active component with the shape of metal oxide or metal sulfide Formula loads on carrier, then constant pressure and dry under nitrogen protection, then catalyst is made after being fired.This method preparation is urged Agent activity is poor, and reaction coking is more, and cracking yield of light oil is low, and the conversion per pass of coal tar asphalt reaches 35% or so, It still needs further improvement for the conversion ratio of coal tar asphalt, and catalyst life is shorter.
Currently, as the molecular sieve of cracking active component using most often Y type molecule in hydrocracking catalyst Sieve.The method of industrial production Y type molecular sieve is essentially all using GRACE company, the U.S. in USP 3639099 and USP at present The directing agent method proposed in 4166099, the orifice diameter in the Y type molecular sieve original powder duct of synthesis are 0.74nm × 0.74nm, Micropore pore volume accounts for about 95% of total pore volume or more.Polycyclic heavy constituent molecular diameter in hydrocracking raw material usually 1nm with On, the cracking reaction for heavy constituent macromolecular, be suitble to its react and product diffusion ideal duct pore diameter range be 2nm ~ The macropore range of 10nm, can be exposed by more accessible acid centre, at the same also conducive to the absorption of raw material macromolecular and Reaction and desorption and the diffusion of purpose product improve molecular sieve cracking selectivity.Contain to improve the mesoporous pore volume of Y type molecular sieve Low the case where being unfavorable for wax oil macromolecular reaction is measured, processing usually is modified to Y type molecular sieve original powder, different ducts can be obtained The Modified Zeolite Y of structure and acid distribution.
CN201310240740.8 discloses a kind of method of modifying of ultra-steady Y molecular sieve (USY).The characteristics of this method be Organic acid and inorganic salts dealuminzation reagent is added in modifying process simultaneously, it is modified to carry out the combination of organic acid-inorganic salts.Use this The mesopore volume of USY molecular sieve made from method reality of the total volume 50% hereinafter, its crystallinity below 85%.
CN200610001864.0 discloses a kind of method that surfactant protects lower Modified NaY molecular sieve.This method The characteristics of be that surfactant is added in sour dealumination process, i.e., using industrial NaY molecular sieve as raw material, two are carried out before hydro-thermal process Then secondary ammonium exchange carries out sour dealuminzation under the protection of surfactant, obtains by hydro-thermal process twice before being chemically treated Silica alumina ratio (the SiO of HY sieve sample2/Al2O3) be 9 ~ 18, while keep 75% ~ 95% crystallinity, the mesoporous ratio of molecular sieve compared with Industrial NaY molecular sieve has a certain amount of raising.
CN201510147788.3 discloses that a kind of silica alumina ratio is high and second hole Y molecular sieve abundant and preparation method thereof. This method comprises: obtaining dry Y type molecular sieve, being cooled to 200 ~ 600 Y type molecular sieve in 300 DEG C ~ 600 DEG C 1 ~ 5h of processing ℃；In dried over anhydrous environment, it is passed through the dry gas being saturated by dealumination complement silicon agent into dry Y type molecular sieve, reacts 0.5h ~ 7.0h, or in dried over anhydrous environment, while temperature to be at the uniform velocity warming up to 500 ~ 700 DEG C into dry y-type zeolite It is passed through the dry gas being saturated by dealumination complement silicon agent, 0.5h ~ 7.0h is reacted, obtains crude product；By crude product at 30 ~ 100 DEG C Alkali process 10min ~ 5h, the solid-liquid mass ratio of alkali process are 1 ~ 50:1, obtain silica alumina ratio height and second hole Y molecular sieve abundant.
From the point of view of application of the molecular sieve with cracking function during Industrial Catalysis, performance depends primarily on following Two aspects: selective absorption and reaction.When reactant molecule size is less than molecular sieve aperture and overcomes molecular sieve crystal surface Energy barrier can just diffuse into molecular sieve pore passage, and specific catalysis reaction occurs, is at this moment adsorbed molecule across molecular sieve crystal Hole and cage diffusion serve it is conclusive.The molecular sieve total pore volume and mesoporous pore volume of conventional method of modifying preparation It is less than normal, it is unfavorable for the conversion of raw material macromolecular, therefore the modification point that pore structure is open, mesoporous content is high and acid site exposure is more Son sieve is capable of handling the raw material that molecule is bigger, oil product is heavier, and raising macromolecular conversion probability etc. shows more superior Performance, to promote the level of hydrocracking catalyst.
Summary of the invention
Place in order to overcome the shortcomings in the prior art, the present invention provides a kind of method for hydrogen cracking of coal tar.This Hydrocracking catalyst used in inventive method is using the modification Y type point more concentrated rich in meso-hole structure, effective pore sife distribution Son sieve is Cracking Component, can effectively convert the polycyclic aromatic hydrocarbon heavy constituent in coal tar, the quality of production more preferably fire by communications and transportation Expect blend component, wherein diesel product arene content is low, and the Cetane number increase rate of diesel product is big；Meanwhile this method energy Enough effectively to extend Cracking catalyst service life, device is long operation cycle.
The method for hydrogen cracking of coal tar of the present invention, including coal tar raw material are urged after hydrofinishing with being hydrocracked Agent contact carries out hydrocracking reaction, and obtained isocrackate is separated, and obtains gasoline fraction and diesel oil distillate；Wherein Hydrocracking catalyst used, including hydrogenation active metal component and carrier, carrier include Modified Zeolite Y, amorphous Sial and aluminium oxide, wherein the Modified Zeolite Y, property are as follows: relative crystallinity is 110% ~ 150%, SiO2/ Al2O3Molar ratio be 55 ~ 100, cell parameter be 2.425 ~ 2.435nm, total pore volume be 0.55 ~ 1.0mL/g, preferably 0.6 ~ 1.0mL/g, mesoporous pore volume account for 70% of total pore volume or more, preferably 80% ~ 95%.
The grain size of the Modified Zeolite Y is 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm.
In the Modified Zeolite Y, mesoporous bore dia is 2 ~ 10nm.
The specific surface area of the Modified Zeolite Y is 650 ~ 1000m2/ g, preferably 750 ~ 1000m2/g。
The infrared total acid content of the Modified Zeolite Y is 0.1 ~ 0.5mmol/g.
In the Modified Zeolite Y, Na2The weight content of O is 0.15wt% or less.
In the hydrocracking catalyst, the carrier, on the basis of the weight of carrier, Modified Zeolite Y Content is 10% ~ 50%, preferably 15% ~ 45%, and the content of amorphous silica-alumina is 5% ~ 30%, preferably 10% ~ 25%, and aluminium oxide contains Amount is 20% ~ 85%, preferably 30% ~ 75%.
The hydrogenation active metals generally use the metal of group VIB and group VIII, and vib metals are preferably molybdenum And/or tungsten, group VIII metal are preferably cobalt and/or nickel.In hydrocracking catalyst catalyst of the present invention, with the weight of catalyst On the basis of amount, the content of vib metals (in terms of oxide) is 10.0% ~ 30.0%, group VIII metal (in terms of oxide) Content be 4.0% ~ 8.0%, the content of carrier is 62.0% ~ 86.0%.
The property of hydrocracking catalyst of the present invention is as follows: specific surface area is 250 ~ 450m2/ g, pore volume be 0.30 ~ 0.50mL/g。
The preparation method of hydrocracking catalyst of the present invention, preparation and load hydrogenation active metal component including carrier, Wherein the preparation process of carrier is as follows: Modified Zeolite Y, amorphous silica-alumina, aluminium oxide are mixed, molding, it is then dry and Roasting, is made catalyst carrier, wherein the preparation method of Modified Zeolite Y, includes the following steps:
(1) NaY type molecular sieve and (NH4)2SiF6Aqueous solution contact is reacted, and is filtered and is dried after reaction；
(2) hydro-thermal process is carried out to Y type molecular sieve obtained by step (1)；Hydrothermal conditions: gauge pressure be 0.20 ~ 0.40MPa, temperature are 600 ~ 800 DEG C, and the processing time is 0.5 ~ 5.0 hour；
(3) hydrothermal crystallizing processing is carried out under the conditions of by Y type molecular sieve obtained by step (2) existing for the organic formwork agent, so By filtering and drying；
(4) step (3) resulting Y type molecular sieve is roasted under low temperature oxygen-enriched atmosphere, modification Y type point of the invention is made Son sieve.
In the method for the present invention step (1), the property of NaY type molecular sieve is as follows:
SiO2/Al2O3Molar ratio be 3 ~ 6, preferably 4.5 ~ 5.5, grain size be 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm, Relative crystallinity is 80% ~ 110%, and cell parameter is 2.465 ~ 2.470nm, Na2The weight content of O is 6.0wt% ~ 8.0wt%, than Surface area is 600 ~ 900m2/ g, total pore volume are 0.3 ~ 0.4 mL/g, and micropore pore volume accounts for 75% of total pore volume or more.
In the method for the present invention step (1), (NH4)2SiF6Additional amount be NaY type molecular sieve dry weight 5wt% ~ 20wt%。
In the method for the present invention step (1), (NH4)2SiF6The mass concentration of aqueous solution is 50 ~ 100g/L.NaY type molecular sieve With (NH4)2SiF6Aqueous solution contacts the reaction condition that is reacted: temperature is 80 ~ 150 DEG C, preferably 90 ~ 120 DEG C, when reaction Between be 0.1 ~ 5.0 hour, preferably 1.0 ~ 3.0 hours.
In the method for the present invention step (1), NaY type molecular sieve and (NH4)2SiF6After aqueous solution contact is reacted, separation point Son sieve and by-product, can wash, refilter, dry, it is preferably dry after resulting Y type molecular sieve butt be 60wt% ~ 80wt%.Dry condition is usually 0.5 ~ 5.0 hour dry at 50 ~ 95 DEG C.
In the method for the present invention step (2), hydro-thermal process is the molecular sieve obtained in saturated steam processing step (1), Treatment conditions: 0.20 ~ 0.40MPa of gauge pressure, preferably 0.25 ~ 0.40MPa, 600 ~ 800 DEG C of temperature, preferably 610 ~ 750 DEG C, place The reason time 0.5 ~ 5.0 hour, preferably 1.0 ~ 3.0 hours.
In the method for the present invention step (3), organic formwork agent is tetraethyl ammonium hydroxide, tetramethylammonium hydroxide, tetrapropyl One or more of ammonium hydroxide.Wherein, after evenly mixing by Y type molecular sieve obtained in step (2) and organic formwork agent, Hydrothermal crystallizing is carried out, process is as follows: Y type molecular sieve obtained in step (2) being beaten in organic formwork agent aqueous solution, liquid is solid Weight ratio is 3:1 ~ 8:1, and temperature is 70 ~ 90 DEG C, and the time is 0.5 ~ 5.0 hour, and the mass concentration of organic formwork agent aqueous solution is 3% ~ 10%, mixed material is then placed in crystallization in crystallizing kettle, crystallization temperature is 80 ~ 120 DEG C, and crystallization time is 4 ~ 10h, gauge pressure For 0.1 ~ 0.2MPa.After crystallization, being filtered and being dried can be carried out using conventional method, and generally dry condition is as follows: 50 ~ Dry 1 ~ 10h at 110 DEG C.
In the method for the present invention, step (4) is roast under low temperature oxygen-enriched atmosphere by the Y type molecular sieve that step (3) obtains, Wherein oxygen-enriched atmosphere refers to that oxygen content is greater than 50v%, and maturing temperature is 300 ~ 450 DEG C, and calcining time is 5 ~ 10h.Roasting is general Using the method roasted under temperature programming again constant temperature, heating rate is preferably 1 ~ 2 DEG C/min.
In method for hydrogen cracking of the invention, using one-stage serial process flow, before hydrocracking reaction, need into Row hydrofinishing, used Hydrobon catalyst can be used conventional Hydrobon catalyst or be hydrocracked pre- place Catalyst is managed, alumina-based supports, using group VIB and group VIII metal as hydrogenation active metal component, Section VI B are generally used Race's metal is 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, the The content of group vib metal (in terms of oxide) is 15.0% ~ 30.0%, and the content of group VIII metal (in terms of oxide) is 4.0% ~8.0%。
The coal tar fraction, property are as follows: (20 DEG C) of density are 0.95 ~ 1.20 g/cm3, initial boiling point be 160 ~ 190 DEG C, the end point of distillation is 450 ~ 480 DEG C, and sulfur content is 1.50wt% ~ 3.0wt%, and nitrogen content is 10000 ~ 20000 μ g/g, and aromatic hydrocarbons contains Amount is greater than 90wt%.
Method for hydrogen cracking of the invention uses two-stage method process flow, and operating condition used by hydrofinishing is as follows: Reaction stagnation pressure is 12.0 ~ 20.0MPa, and volume space velocity is 0.1 ~ 0.5h when liquid-1, hydrogen to oil volume ratio is 1000:1 ~ 2000:1, reaction Temperature is 370 ~ 435 DEG C.Operating condition used by being hydrocracked is as follows: reaction stagnation pressure is 10.0 ~ 20.0MPa, volume when liquid Air speed is 0.1 ~ 0.5h-1, hydrogen to oil volume ratio is 1000:1 ~ 2000:1, and reaction temperature is 350 ~ 450 DEG C.
Hydrocracking catalyst used by the method for the present invention, wherein Y type molecular sieve is using (NH4)2SiF6To NaY points Son sieve is modified processing, while realizing modulation molecular sieve silica alumina ratio, can take off together the sodium ion in NaY molecular sieve Out, hydrothermal crystallizing then is carried out to the molecular sieve after hydro-thermal process in the presence of organic formwork agent, part silicon atom can be made in this way Enter framework of molecular sieve structure under organic formwork agent effect with aluminium atom, in the further bone stablized and improve modified molecular screen While frame structure, the non-skeleton structure generated in zeolite-water heat treatment process, unimpeded cellular structure, the organic mould in part are eliminated Plate agent is also able to enter in the duct of molecular sieve, cooperates subsequent oxygen-enriched low-temperature treatment, can be by the organic formwork in molecular sieve Agent controllably orderly removes, to generate a large amount of ordered mesopore structures, and pore size distribution is more concentrated.
Y type molecular sieve acidity is suitable in hydrogen Cracking catalyst used by the method for the present invention, crystallinity is high, mesoporous institute's accounting Example is high, pore-size distribution is more concentrated.Since the Y type molecular sieve has bigger pore volume and mesopore volume, more in acidity The heart is exposed, and is conducive to raw material heavy oil macromolecular and is cracked, but also has more preferably pore size distribution range, can be effective Ground controls the cracking degree of reactant, and is conducive to product and is diffused in duct, in this way in cracking reaction, opposite can increase Add activated centre, and heavy oil macromolecular can be made to carry out the cracking reaction of suitable degree, both improves the cracking capability of heavy oil, simultaneously Coke yield is reduced, catalyst can show good cracking activity and product selectivity.
The method of coal tar hydrocracking of the present invention can effectively convert the polycyclic aromatic hydrocarbon heavy constituent in coal tar, production Quality more preferably transportation fuel blend component, wherein diesel product arene content is low, and the Cetane number of diesel product improves Amplitude is big；Meanwhile this method can effectively extend Cracking catalyst service life, device is long operation cycle.
The process of coal tar hydrocracking production lightweight transportation fuel of the present invention effective and reasonable can utilize coal tar The energy fuel for obtaining alternative petroleum can reduce the consumption of petroleum resources, be national energy security power-assisted, improve coal tar and add Work utilization efficiency, increases substantially economic benefit.
Detailed description of the invention
Fig. 1 is the SEM electromicroscopic photograph of 1 gained Modified Zeolite Y of embodiment；
Fig. 2 is the SEM electromicroscopic photograph of 1 gained Modified Zeolite Y of comparative example；
Fig. 3 is the XRD diffraction pattern of 1 gained Modified Zeolite Y of embodiment.
Specific embodiment
Aluminium oxide can be using oxygen used in conventional hydrocracking catalyst in carrier of hydrocracking catalyst of the present invention Change aluminium, such as macroporous aluminium oxide and small porous aluminum oxide, the mass ratio of general macroporous aluminium oxide and small porous aluminum oxide is 1:8 ~ 8:1.Institute The property for the macroporous aluminium oxide stated is as follows: pore volume is 0.6 ~ 1.3mL/g, and specific surface area is 300 ~ 450m2/g。
Adhesive therefor of the present invention is made of small porous aluminum oxide and inorganic acid and/or organic acid.Aperture oxidation used Aluminium pore volume is 0.3 ~ 0.5mL/g, and specific surface area is 200 ~ 400m2/g。
Amorphous silica-alumina used in catalyst carrier of the present invention can be prepared by coprecipitation or grafting copolymerization process, by document Middle conventional method preparation.In amorphous silica-alumina obtained, SiO2Weight content be 10% ~ 60%, preferably 20% ~ 55%, The pore volume of amorphous silica-alumina is 0.6 ~ 1.1mL/g, and preferably 0.8 ~ 1.0mL/g, specific surface area is 300 ~ 500m2/ g, preferably For 350 ~ 500m2/g。
Detailed process is as follows for catalyst carrier for hydrgenating preparation of the present invention: by Modified Zeolite Y, amorphous silica-alumina, oxygen Change aluminium mixing, molding, then dry and roasting is prepared into carrier；It is small that drying can dry 3 ~ 6 at a temperature of 80 DEG C ~ 150 DEG C When, roasting is roasted 2.5 ~ 6.0 hours at 500 DEG C ~ 600 DEG C.
Carrier of hydrocracking catalyst of the present invention loads hydrogenation active metal component (group VIB and by conventional methods Group VIII metal component such as Co, Ni, Mo, W etc.), it is prepared into hydrocracking catalyst.Using load side conventional in the prior art Method, preferably infusion process can be saturation leaching, excessive leaching or complexing leaching, i.e., with the solution impregnation catalyst for containing required active component Agent carrier, carrier after dipping 100 DEG C ~ 150 DEG C drying 1 ~ 12 hour, it is then small in 450 DEG C ~ 550 DEG C roastings 2.5 ~ 6.0 When, final catalyst is made.
The following examples are for being described in more detail technical solution of the present invention, but the scope of the present invention is not limited solely to this The range of a little 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, relatively Crystallinity and cell parameter use x-ray diffraction method, and silica alumina ratio is measured using XRF method (x ray fluorescence spectrometry), molecular sieve Grain size using SEM(scanning electron microscope) by the way of measure.Meleic acid amount uses Pyridine adsorption IR spectra method, sodium Content uses plasma emission spectrometry.
NaY molecular sieve original powder employed in the embodiment of the present invention and comparative example be it is industrially prepared, property is as follows: SiO2/ Al2O3Molar ratio is 5.1, and grain size is ~ 1.7 μm, relative crystallinity 95%, cell parameter 2.468nm, Na2The weight content of O For 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
It takes NaY original powder 278g to be put into 800mL water purification, is warming up to 95 DEG C, start that (NH is added dropwise into molecular sieve pulp4)2SiF6Aqueous solution dropped evenly the (NH that 307mL solution concentration is 72g/L at 60 minutes4)2SiF6Solution, constant temperature after completion of dropwise addition Stirring 2 hours, is filtered and is dried after constant temperature, and the butt of molecular sieve is 65.3wt% after drying；After above-mentioned drying Molecular sieve is added in hydrothermal treatment device, to molecule under the conditions of gauge pressure 0.25MPa, 610 DEG C of temperature, processing the time 1.0 hours Sieve carries out hydro-thermal process；Molecular sieve after taking 130g hydro-thermal process is put into the tetraethyl hydrogen-oxygen that 520mL mass concentration is 5.3% Change in aqueous ammonium, constant temperature stirs 4 hours under the conditions of 80 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydro-thermal crystalline substance Change, 90 DEG C of crystallization temperature, gauge pressure 0.1MPa crystallization time 10 hours, is filtered and is dried after crystallization；By hydro-thermal The drying sample that crystallization obtains roasts under oxygen-enriched state, in calcination atmosphere oxygen content be 70v%, heating rate be 1 DEG C/ Min, constant temperature calcining temperature are 420 DEG C, and the constant temperature calcining time is 6 hours, obtain molecular sieve of the present invention.Sample number into spectrum LAY-1, point Son sieve property is listed in table 1.
Embodiment 2
It takes NaY original powder 278g to be put into 800mL water purification, is warming up to 100 DEG C, start to be added dropwise into molecular sieve pulp (NH4)2SiF6Aqueous solution dropped evenly the (NH that 182mL solution concentration is 55g/L at 60 minutes4)2SiF6Solution, completion of dropwise addition Constant temperature stirs 2 hours afterwards, is filtered and dries after constant temperature, and the butt of molecular sieve is 68.0wt% after drying；It will be above-mentioned dry Molecular sieve after dry is added in hydrothermal treatment device, in gauge pressure 0.30MPa, 670 DEG C of temperature, processing 2.0 hours time condition Under to molecular sieve carry out hydro-thermal process；Molecular sieve after taking 130g hydro-thermal process is put into four that 910mL mass concentration is 7.5% In propyl ammonium hydroxide aqueous solution, under the conditions of 90 DEG C constant temperature stir 4 hours, then by mixed material be transferred in crystallizing kettle into Row hydrothermal crystallizing, 110 DEG C of crystallization temperature, gauge pressure 0.1MPa crystallization time 10 hours, is filtered and dries place after crystallization Reason；The drying sample that hydrothermal crystallizing obtains is roasted under oxygen-enriched state, oxygen content is 65v%, heating rate in calcination atmosphere For 1 DEG C/min, 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-2, molecular sieve property are listed in table 1.
Embodiment 3
It takes NaY original powder 278g to be put into 1000mL water purification, is warming up to 100 DEG C, start to be added dropwise into molecular sieve pulp (NH4)2SiF6Aqueous solution dropped evenly the (NH that 417mL solution concentration is 85g/L at 60 minutes4)2SiF6Solution, completion of dropwise addition Constant temperature stirs 3 hours afterwards, is filtered and dries after constant temperature, and the butt of molecular sieve is 67.2wt% after drying；It will be above-mentioned dry Molecular sieve after dry is added in hydrothermal treatment device, under the conditions of gauge pressure 0.35MPa, 700 DEG C of temperature, processing the time 3.0 hours Hydro-thermal process is carried out to molecular sieve；Molecular sieve after taking 130g hydro-thermal process is put into the tetrem that 1040mL mass concentration is 3.5% In base ammonium hydroxide aqueous solution, constant temperature is stirred 3 hours under the conditions of 85 DEG C, and then mixed material is transferred in crystallizing kettle and is carried out Hydrothermal crystallizing, 80 DEG C of crystallization temperature, gauge pressure 0.1MPa crystallization time 5 hours, is filtered and is dried after crystallization； The drying sample that hydrothermal crystallizing obtains is roasted under oxygen-enriched state, oxygen content is 75v%, heating rate 1 in calcination atmosphere DEG C/min, constant temperature calcining temperature is 320 DEG C, and the constant temperature calcining time is 8 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY- 3, molecular sieve property is listed in table 1.
Embodiment 4
It takes NaY original powder 278g to be put into 1400mL water purification, is warming up to 95 DEG C, start to be added dropwise into molecular sieve pulp (NH4)2SiF6Aqueous solution dropped evenly the (NH that 200mL solution concentration is 60g/L at 60 minutes4)2SiF6Solution, completion of dropwise addition Constant temperature stirs 2 hours afterwards, is filtered and dries after constant temperature, and the butt of molecular sieve is 68.1wt% after drying；It will be above-mentioned dry Molecular sieve after dry is added in hydrothermal treatment device, in gauge pressure 0.30MPa, 750 DEG C of temperature, processing 2.0 hours time condition Under to molecular sieve carry out hydro-thermal process；Molecular sieve after taking 130g hydro-thermal process is put into four that 520mL mass concentration is 6.8% In propyl ammonium hydroxide aqueous solution, under the conditions of 90 DEG C constant temperature stir 3 hours, then by mixed material be transferred in crystallizing kettle into Row hydrothermal crystallizing, 95 DEG C of crystallization temperature, gauge pressure 0.1MPa crystallization time 8 hours, is filtered and dries place after crystallization Reason；The drying sample that hydrothermal crystallizing obtains is roasted under oxygen-enriched state, oxygen content is 70v%, heating rate in calcination atmosphere For 1 DEG C/min, constant temperature calcining temperature is 380 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
It takes NaY original powder 278g to be put into the solution that 1000mL ammonium nitrate concn is 1.5mol/L, is warming up to 95 DEG C, constant temperature Stirring 2 hours, is filtered after constant temperature, washs and dries, and the butt of molecular sieve is 63.8wt% after drying；Temperature programming Molecular sieve is roasted 3 hours at 600 DEG C；Then repeat an ammonium exchange, and filtering and drying；Second of ammonium of 100g is taken to hand over Molecular sieve after changing is put into the tetraethyl ammonium hydroxide aqueous solution that 650mL mass concentration is 7.5%, permanent under the conditions of 80 DEG C Mixed material, is then transferred in crystallizing kettle and carries out crystallization by temperature stirring 2 hours, and 100 DEG C of crystallization temperature, gauge pressure 0.1MPa, It crystallization time 8 hours, is filtered and is dried after crystallization；The drying sample that crystallization obtains is roasted under oxygen-enriched state It burns, oxygen content is 60v% in calcination atmosphere, and heating rate is 1 DEG C/min, and constant temperature calcining temperature is 360 DEG C, when constant temperature calcining Between be 8 hours, obtain molecular sieve.Sample number into spectrum LDAY-1, molecular sieve property are listed in table 1.
Comparative example 2
It takes NaY original powder 278g to be put into the solution that 1000mL ammonium nitrate concn is 1.5mol/L, is warming up to 95 DEG C, constant temperature Stirring 2 hours divides after constant temperature and is filtered, washs and dries, and the butt of molecular sieve is 63.8wt% after drying；Program liter Temperature roasts molecular sieve 3 hours at 600 DEG C；Then repeat an ammonium exchange, and filtering and drying；Take second of ammonium of 100g Molecular sieve after exchange is put into the dust technology that 800mL concentration is 0.3mol/L, and constant temperature stirs 2 hours under the conditions of 80 DEG C, It is filtered and is dried after constant temperature；Molecular sieve after above-mentioned drying is added in hydrothermal treatment device, in gauge pressure 0.30MPa, 670 DEG C of temperature obtain molecular sieve to molecular sieve progress hydro-thermal process under the conditions of the 2.0 hours time of processing；Sample is compiled Number LDAY-2, molecular sieve property are listed in table 1.
Comparative example 3
Molecular sieve, sample number into spectrum LDAY-3, molecular sieve are prepared using the method for embodiment 1 in CN201510147788.3 Matter is listed in table 1.
The property of 1 Y type molecular sieve of table
Product number LAY-1 LAY-2 LAY-3 LAY-4
Specific surface area, m2/g 912 887 941 923
Pore volume, cm3/g 0.74 0.69 0.88 0.72
Lattice constant, nm 2.433 2.431 2.428 2.426
Relative crystallinity, % 131 119 140 132
Average crystallite size, μm 1.7 1.7 1.7 1.7
SiO2/Al2O3Molar ratio 73.6.3 62.3 81.9 65.8
Mesoporous pore volume (bore dia 2nm ~ 10nm) accounts for total pore volume ratio, % 86 83 91 87
Infrared total acid content, mmol/g 0.45 0.33 0.30 0.21
Na2O, wt% 0.05 0.06 0.03 0.07
Continued 1
Product number LDAY-1 LDAY-2 LDAY-3
Specific surface area, m2/g 633 703 603
Pore volume, cm3/g 0.44 0.37 0.38
Lattice constant, nm 2.439 2.433 2.449
Relative crystallinity, % 98 103 86
Average crystallite size, μm 1.7 1.7 1.7
SiO2/Al2O3Molar ratio 7.5 33.5 8.6
Mesoporous pore volume (bore dia 2nm ~ 10nm) accounts for total pore volume ratio, % 47 31 37
Infrared total acid content, mmol/g 0.77 0.35 0.71
Na2O, wt% 0.21 0.19 0.45
Embodiment 5
By 100 grams of LAY-1 molecular sieves (butt 90wt%), 64.3 grams of amorphous silica-alumina (SiO2Content 25wt%, pore volume 0.85mL/g, specific surface area 370m2/ g, butt 70wt%), 150 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific surface areas 400m2/ g, butt 70wt%), (molar ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4) to be put into stone roller for 200 grams of adhesives Mixed grind in press, adds water, is rolled into paste, and extrusion, extrusion item is 4 hours dry at 110 DEG C, then roasts 4 hours at 550 DEG C, Obtain carrier ZS-1.
Maceration extract room temperature immersion 2 hours of carrier tungstenic and nickel, 120 DEG C drying 4 hours, 500 DEG C of temperature programming roasting 4 Hour, catalyst HC-1 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 6
By 50 grams of LAY-1 molecular sieves (butt 90wt%), 50 grams of amorphous silica-alumina (SiO2Content 25wt%, pore volume 0.85mL/g, specific surface area 370m2/ g, butt 70wt%), 214.3 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific surface areas 400m2/ g, butt 70wt%), (molar ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4) to be put into stone roller for 200 grams of adhesives Mixed grind in press, adds water, is rolled into paste, and extrusion, extrusion item is 4 hours dry at 110 DEG C, then roasts 4 hours at 550 DEG C, Obtain carrier ZS-2.
Maceration extract room temperature immersion 2 hours of carrier tungstenic and nickel, 120 DEG C drying 4 hours, 500 DEG C of temperature programming roasting 4 Hour, catalyst HC-2 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 7 ~ 8
As described in Example 5, it changes LAY-1 into LAY-2, LAY-3 respectively, carrier ZS-3, ZS-4 and catalysis is made Agent HC-3 and HC-4, carrier and catalyst composition are shown in Table 2.
Comparative example 4 ~ 6
As described in Example 5, change LAY-1 into LDAY-1, LDAY-2, LDAY-2 respectively, be made carrier DZS-1, DZS-2, DZS-3 and catalyst DHC-1, DHC-2 and DHC-3, carrier and catalyst composition are shown in Table 3.
Embodiment 9 ~ 12
This embodiment describes the method for the present invention, and hydrocracking catalyst HC-1, HC-2, HC-3 and HC-4 is respectively adopted. Using two-stage method process flow, Hydrobon catalyst uses 3936 catalyst, is tried on fixed bed hydrogenation experimental rig It tests, operating condition are as follows: it is 18.0MPa that refining stage, which reacts stagnation pressure, and volume space velocity is 0.2h when liquid-1, hydrogen to oil volume ratio 1500:1. It is 16.0MPa that cracking zone, which reacts stagnation pressure, and volume space velocity is 0.3h when liquid-1, hydrogen to oil volume ratio 1200:1, use coal tar as Feedstock oil, feedstock property are 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 and the DHC-3 prepared using comparative example.Using two Section method process flow, Hydrobon catalyst use 3936 catalyst, are tested on fixed bed hydrogenation experimental rig, operate Condition are as follows: it is 18.0MPa that refining stage, which reacts stagnation pressure, and volume space velocity is 0.2h when liquid-1, hydrogen to oil volume ratio 1500:1.Cracking zone Reaction stagnation pressure is 16.0MPa, and volume space velocity is 0.3h when liquid-1, hydrogen to oil volume ratio 1200:1 uses coal tar as raw material Oil, feedstock property are listed in table 3, and evaluation result is listed in table 4.
The physico-chemical property of 2 catalyst carrier of table and catalyst
Carrier composition and property
Number ZS-1 ZS-2 ZS-3 ZS-4
Composition
Modified Zeolite Y, wt% 30.0 15.0 30.0 30.0
Amorphous silica-alumina, wt% 15.0 15.0 15.0 15.0
Macroporous aluminium oxide, wt% 35.0 50.0 35.0 35.0
Adhesive, wt% Surplus Surplus Surplus Surplus
Property
Pore volume, mL/g 0.65 0.70 0.67 0.69
Specific surface area, m2/g 529 445 538 521
Catalyst composition and property
Number HC-1 HC-2 HC-3 HC-4
WO3, wt% 22.52 23.52 21.94 23.15
NiO, wt% 5.71 5.98 5.84 5.83
Pore volume, mL/g 0.42 0.45 0.41 0.44
Specific surface area, m2/g 429 386 425 433
Continued 2
Carrier composition and property
Number DZS-1 DZS-2 DZS-3
Composition
Modified Zeolite Y, wt% 30.0 30.0 30.0
Amorphous silica-alumina, wt% 15.0 15.0 15.0
Macroporous aluminium oxide, wt% 35.0 35.0 35.0
Adhesive, wt% Surplus Surplus Surplus
Property
Pore volume, mL/g 0.51 0.50 0.54
Specific surface area, m2/g 422 433 428
Catalyst composition and property
Number DHC-1 DHC-2 DHC-3
WO3, wt% 22.49 22.50 22.56
NiO, wt% 5.81 5.78 5.89
Pore volume, mL/g 0.30 0.30 0.27
Specific surface area, m2/g 322 335 305
The main character of 3 coal tar of table
Analysis project Coal tar
Density (20 DEG C), kg/m3 1130
Sulphur, μ g/g 20584
Nitrogen, μ g/g 12600
Carbon, % 91.00
Hydrogen, % 5.95
Oxygen, %(subtract difference) 1.44
Boiling range/DEG C
IBP/10%/30%/50% 170/230/300/340
70%/90%/95%/EBP 370/410/435/460
Viscosity (100 DEG C), mm2/s 2.408
Ash, % 0.002
Moisture content, % Trace
Carbon residue, % 0.83
Flash-point (silent), DEG C 98
Four components, %
Saturation point 0.5
Fragrance point 66.0
Colloid 32.9
Asphalitine 0.6
Metal, μ g/g
Ni 0.024
V 0
Fe 1.518
Na 0
4 comparative evaluation's result of table
Hydrocracking catalyst HC-1 HC-2 HC-3 HC-4
Feedstock oil Coal tar Coal tar Coal tar Coal tar
Operating condition
Volume space velocity when refining stage liquid, h-1 0.2 0.2 0.2 0.2
Refining stage hydrogen to oil volume ratio 1500:1 1500:1 1500:1 1500:1
Refining stage reacts stagnation pressure, MPa 18.0 18.0 18.0 18.0
Refining stage reaction temperature, DEG C 386 386 386 386
Volume space velocity when cracking zone liquid, h-1 0.3 0.3 0.3 0.3
Cracking zone hydrogen to oil volume ratio 1200:1 1200:1 1200:1 1200:1
Cracking zone reacts stagnation pressure, MPa 16.0 16.0 16.0 16.0
Cracking zone reaction temperature, DEG C 381 385 388 391
Product yield and property
Heavy naphtha
Yield, wt% 26.49 23.47 32.12 30.36
Research octane number (RON) RON 85.2 84.3 84.1 83.2
Sulphur, μ g/g 9 8 8 6
Nitrogen, μ g/g 1.2 1.1 1.0 1.0
Diesel oil
Yield, wt% 65.51 68.51 58.88 60.66
Aromatic hydrocarbons, wt% 33.5 35.4 31.0 30.1
Cetane number 33.2 29.3 34.8 35.3
Liquid is received, wt% 99.56 99.47 99.12 99.03
Continued 4
Hydrocracking catalyst DHC-1 DHC-2 DHC-3
Feedstock oil Coal tar Coal tar Coal tar
Operating condition
Volume space velocity when refining stage liquid, h-1 0.2 0.2 0.2
Refining stage hydrogen to oil volume ratio 1500:1 1500:1 1500:1
Refining stage reacts stagnation pressure, MPa 18.0 18.0 18.0
Refining stage reaction temperature, DEG C 386 386 386
Volume space velocity when cracking zone liquid, h-1 0.3 0.3 0.3
Cracking zone hydrogen to oil volume ratio 1200:1 1200:1 1200:1
Cracking zone reacts stagnation pressure, MPa 16.0 16.0 16.0
Cracking zone reaction temperature, DEG C 398 403 405
Product yield and property
Heavy naphtha
Yield, wt% 17.62 18.97 16.74
Research octane number (RON) RON 81.5 82.3 80.7
Sulphur, μ g/g 20 15 18
Nitrogen, μ g/g 9.8 8.9 7.9
Diesel oil
Yield, wt% 72.38 70.03 68.26
Aromatic hydrocarbons, wt% 48.6 59.3 51.4
Cetane number 21.5 18.6 19.1
Liquid is received, wt% 97.65 95.43 94.31

Claims (17)

1. a kind of method for hydrogen cracking of coal tar, including coal tar raw material is after hydrofinishing, with hydrocracking catalyst Contact carries out hydrocracking reaction, and obtained isocrackate is separated, and obtains gasoline fraction and diesel oil distillate；It is wherein described Hydrocracking catalyst, including hydrogenation active metal component and carrier, carrier includes Modified Zeolite Y, amorphous silica-alumina And aluminium oxide, wherein the Modified Zeolite Y, property are as follows: relative crystallinity is 110% ~ 150%, SiO2/Al2O3It rubs , than being 55 ~ 100, cell parameter is 2.425nm ~ 2.435nm for you, and total pore volume is 0.55mL/g ~ 1.0mL/g, mesoporous pore volume Account for 70% or more of total pore volume；
The method for hydrogen cracking uses two sections of series process flows, and hydrofinishing operating condition is as follows: reaction stagnation pressure is 12.0MPa ~ 20.0MPa, volume space velocity is 0.1h when liquid-1~0.5h-1, hydrogen to oil volume ratio is 1000:1 ~ 2000:1, reaction temperature It is 370 DEG C ~ 435 DEG C；Hydrocracking operation condition is as follows: reaction stagnation pressure is 10.0MPa ~ 20.0MPa, and volume space velocity is when liquid 0.1h-1~0.5h-1, hydrogen to oil volume ratio is 1000:1 ~ 2000:1, and reaction temperature is 350 DEG C ~ 450 DEG C.
2. according to the method for claim 1, it is characterised in that: the property of the Modified Zeolite Y is as follows: total pore volume For 0.6mL/g ~ 1.0mL/g, mesoporous pore volume accounts for the 80% ~ 95% of total pore volume.
3. according to the method for claim 1, it is characterised in that: the grain size of the Modified Zeolite Y is 1.0 μm ~ 2.5 μm。
4. according to the method for claim 1, it is characterised in that: the grain size of the Modified Zeolite Y is 1.2 μm ~ 1.8 μm。
5. according to the method for claim 1, it is characterised in that: the mesoporous bore dia of the Modified Zeolite Y is 2nm ~10nm。
6. according to the method for claim 1, it is characterised in that: the specific surface area of the Modified Zeolite Y is 650m2/g~ 1000m2/g。
7. according to the method for claim 1, it is characterised in that: the specific surface area of the Modified Zeolite Y is 750m2/g~ 1000m2/g。
8. according to the method for claim 1, it is characterised in that: the infrared total acid content of the Modified Zeolite Y is 0.1mmol/g~0.5mmol/g。
9. according to the method for claim 1, it is characterised in that: in the Modified Zeolite Y, Na2The weight content of O is 0.15wt% or less.
10. according to the method for claim 1, it is characterised in that: the property of the hydrocracking catalyst is as follows: specific surface Product is 250m2/g~450m2/ g, pore volume are 0.30mL/g ~ 0.50mL/g.
11. according to the method for claim 1, it is characterised in that: the hydrogenation active metals are group VIB and Section VIII The metal of race, vib metals are molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel；Using the weight of catalyst as base Standard, content of the vib metals in terms of oxide are 10.0% ~ 30.0%, and content of the group VIII metal in terms of oxide is 4.0% ~ 8.0%, the content of carrier is 62.0% ~ 82.0%.
12. according to method described in claim 1 or 11, it is characterised in that: the carrier of hydrocracking catalyst, to carry On the basis of the weight of body, the content of Modified Zeolite Y is 10% ~ 50%, and the content of amorphous silica-alumina is 5% ~ 30%, aluminium oxide Content is 20% ~ 85%.
13. according to method described in claim 1 or 11, it is characterised in that: the carrier of hydrocracking catalyst, with carrier Weight on the basis of, the content of Modified Zeolite Y is 15% ~ 45%, and the content of amorphous silica-alumina is 10% ~ 25%, aluminium oxide Content is 30% ~ 75%.
14. according to the method for claim 1, it is characterised in that: in the amorphous silica-alumina, SiO2Weight content be 10% ~ 60%, the property of amorphous silica-alumina is as follows: pore volume is 0.6mL/g ~ 1.1mL/g, specific surface area 300m2/g~500m2/ g。
15. according to the method for claim 1, it is characterised in that: in the amorphous silica-alumina, SiO2Weight content be 20% ~ 55%, the property of amorphous silica-alumina is as follows: pore volume is 0.8mL/g ~ 1.0mL/g, specific surface area 350m2/g~500m2/ g。
16. according to the method for claim 1, it is characterised in that: Hydrobon catalyst used by the hydrofinishing It is using alumina-based supports, using group VIB and group VIII metal as hydrogenation active metal component, vib metals are molybdenum And/or tungsten, group VIII metal are cobalt and/or nickel, on the basis of the weight of catalyst, vib metals are in terms of oxide Content is 15.0% ~ 30.0%, and content of the group VIII metal in terms of oxide is 4.0% ~ 8.0%.
17. according to the method for claim 1, it is characterised in that: the coal tar fraction, property are as follows: 20 DEG C close Degree is 0.95g/cm3~1.20g/cm3, initial boiling point is 160 DEG C ~ 190 DEG C, and the end point of distillation is 450 DEG C ~ 480 DEG C, and sulfur content is 1.50wt% ~ 3.0wt%, nitrogen content are the 10000 μ g/g of μ g/g ~ 20000, and arene content is greater than 90wt%.
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