CN107345161A - A kind of method for hydrogen cracking of coal tar - Google Patents

Abstract

The invention discloses a kind of method for hydrogen cracking of coal tar.This method includes coal tar raw material after hydrofinishing, is contacted with hydrocracking catalyst and carries out hydrocracking reaction, and obtained isocrackate obtains gasoline fraction and diesel oil distillate through separation；Modified Zeolite Y used, its property are as follows in wherein described hydrocracking catalyst：Relative crystallinity is 110% ~ 150%, SiO₂/Al₂O₃Mol 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 more than the 70% of total pore volume.This method can effectively convert the polycyclic aromatic hydrocarbon heavy constituent in coal tar, the more excellent transportation fuel blend component of the quality of production.

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, particularly one kind to be converted into cleaning vapour by coal tar fraction The method for hydrogen cracking of oil and diesel oil.

Background technology

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 oil 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 produce substantial amounts of sulfide and nitride, cause serious Environmental pollution.Coal tar clean processing and effective utilize become more important.Coal can be effectively removed using hydrogenation technique The impurity such as sulphur, nitrogen in tar, its density is reduced, realizes lighting.

Coal tar hydrogenating processing mainly includes 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, oxygen content is high, water caused by deoxidation is to the active, steady of catalyst Qualitative and intensity produces very detrimental effect, second, colloid, carbon residue content height easily promote catalyst carbon deposit, causes to be catalyzed Agent inactivation and bed block, third, sulphur, nitrogen content are high, it is desirable to which deep hydrogenation denitrogenation, otherwise stability does not reach requirement, fourth, coal Contain substantial amounts of aromatic hydrocarbons in tar, Cetane number is very low in its diesel oil distillate, it is desirable to it is deeply hydrodearomatized, and reducing as far as possible Aromatic hydrocarbons saturation and open loop to greatest extent, makes every effort to improve diesel cetane-number to greatest extent on the premise of chain rupture.

The process that the process of middle coalite tar catalytic hydrogenation clean fuel is also its lighting, cleaned, including protect Shield process (removing heavy metal), unifining process (hetero atom 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 During one of key technology.

CN201010228569.5 discloses group technology and its catalysis of a kind of producing clean fuel oil by hydrogenation of coal tar Agent.This method is to use fixed bed group technology, the active component used in catalyst for hydro-upgrading therein be group VIII and Vib metals oxide NiO, MoO₃、CoO、WO₃In one or more, carrier is the modified kaolin of acid.Due to using Sour modified kaolin is as carrier, its pore volume very little and acid higher, therefore, for the higher coal tar of colloid and asphalt content Oily raw material, resin and asphalt enter less than in catalyst duct, more carbon deposit are formed in catalyst surface, so that catalyst Easily inactivation, service cycle are short；Other hydrogen consumption is higher, and diesel product quality has much room for improvement.

CN102029157A discloses a kind of catalyst for coal tar pitch hydrogenation cracking lighting reaction, with inorganic Porous material is carrier, from one kind in aluminum 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 is loaded on carrier, then constant pressure and dry under nitrogen protection, then it is fired after obtained catalyst.Prepared by this method urges 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, The conversion ratio of coal tar asphalt need further to improve, and catalyst life is shorter.

At present, the molecular sieve in hydrocracking catalyst as cracking active component is using most often Y types molecule Sieve.The method of industrial production Y type molecular sieve is essentially all in USP 3639099 and USP using GRACE companies of the U.S. at present The directing agent method proposed in 4166099, the orifice diameter in the Y type molecular sieve original powder duct of synthesis is 0.74nm × 0.74nm, its Micropore pore volume accounts for more than the 95% of total pore volume.Polycyclic heavy constituent molecular diameter in hydrocracking raw material generally 1nm with On, the cracking reaction for heavy constituent macromolecular, be adapted to its reaction and product diffusion preferable duct pore diameter range be 2nm ~ 10nm macropore range, can be exposed by more accessible acid centre, at the same also the absorption beneficial to 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 The low situation for being unfavorable for wax oil macromolecular reaction is measured, processing generally is modified to Y type molecular sieve original powder, can obtain different ducts The Modified Zeolite Y of structure and acid distribution.

CN201310240740.8 discloses a kind of ultra-steady Y molecular sieve（USY）Method of modifying.The characteristics of this method be Organic acid and inorganic salts dealuminzation reagent are added in modifying process simultaneously, the combination for carrying out organic acid-inorganic salts is modified.Use this The mesopore volume of USY molecular sieve of the total volume less than 50% made from method reality, its crystallinity is below 85%.

The method that CN200610001864.0 discloses a kind of lower Modified NaY molecular sieve of surfactant protection.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 Secondary ammonium exchanges, and by hydro-thermal process twice before being chemically treated, sour dealuminzation is then carried out under the protection of surfactant, is obtained The silica alumina ratio of HY sieve samples（SiO₂/Al₂O₃）For 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 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 ℃；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, reaction 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 by the dry gas of dealumination complement silicon agent saturation, reacts 0.5h ~ 7.0h, obtain crude product；By crude product at 30 ~ 100 DEG C Alkali process 10min ~ 5h, the solid-liquid mass ratio of alkali process is 1 ~ 50：1, obtain the Y molecular sieve that silica alumina ratio is high and second hole is abundant.

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.When reactant molecule size is less than molecular sieve aperture and overcomes molecular sieve crystal surface It energy barrier, can just diffuse into molecular sieve pore passage, specific catalytic reaction occurs, at this moment be adsorbed molecule and pass through molecular sieve crystal Hole and cage diffusion serve it is conclusive.Molecular sieve total pore volume and mesoporous pore volume prepared by conventional method of modifying 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 can handle the raw material that molecule is bigger, oil product is heavier, improve macromolecular conversion probability etc. show it is 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 coal tar.This Hydrocracking catalyst used in inventive method is to use the modification Y types 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 more excellent communications and transportation combustion of the quality of production 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 It is enough effectively to extend Cracking catalyst service life, device length service 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 obtains gasoline fraction and diesel oil distillate through separation；Wherein Hydrocracking catalyst used, including hydrogenation active metal component and carrier, carrier include Modified Zeolite Y, amorphous Sial and aluminum oxide, wherein described Modified Zeolite Y, its property is as follows：Relative crystallinity is 110% ~ 150%, SiO₂/ Al₂O₃Mol ratio is 55 ~ 100, and cell parameter is 2.425 ~ 2.435nm, and total pore volume is 0.55 ~ 1.0mL/g, preferably 0.6 ~ 1.0mL/g, mesoporous pore volume account 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 2 ~ 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 0.1 ~ 0.5mmol/g.

In described Modified Zeolite Y, Na₂O weight content is below 0.15wt%.

In described hydrocracking catalyst, described 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 aluminum oxide contains Measure as 20% ~ 85%, preferably 30% ~ 75%.

For described hydrogenation active metals typically using vib and the metal of group VIII, 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, vib metals（In terms of oxide）Content be 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, include preparation and the load hydrogenation active metal component of carrier, The preparation process of wherein carrier is as follows：By Modified Zeolite Y, amorphous silica-alumina, aluminum oxide mix, shaping, then dry and Roasting, is made the preparation method of catalyst carrier, wherein Modified Zeolite Y, 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 0.20 ~ 0.40MPa, temperature Spend for 600 ~ 800 DEG C, processing time is 0.5 ~ 5.0 hour；

（3）By step（2）Gained Y type molecular sieve carries out hydrothermal crystallizing processing, Ran Houjing under the conditions of existing for organic formwork agent Filter and dry；

（4）By step（3）The Y type molecular sieve of gained is calcined under low temperature oxygen-enriched atmosphere, and the modification Y type molecules of the present invention are made Sieve.

The inventive method step（1）In, the property of NaY type molecular sieves is as follows：

SiO₂/Al₂O₃Mol ratio be 3 ~ 6, preferably 4.5 ~ 5.5, grain size be 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm, relatively Crystallinity is 80% ~ 110%, and cell parameter is 2.465 ~ 2.470nm, Na₂O weight content is 6.0wt% ~ 8.0wt%, compares surface Product 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 for 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 type molecular sieves With（NH₄）₂SiF₆The reaction condition that aqueous solution contact is reacted：Temperature is 80 ~ 150 DEG C, preferably 90 ~ 120 DEG C, during reaction Between be 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, separation point Son sieve and accessory substance, can wash, refilter, dry, preferably dry after gained Y type molecular sieve butt for 60wt% ~ 80wt%.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：0.20 ~ 0.40MPa of gauge pressure, preferably 0.25 ~ 0.40MPa, preferably 600 ~ 800 DEG C of temperature, 610 ~ 750 DEG C, place Manage 0.5 ~ 5.0 hour time, preferably 1.0 ~ 3.0 hours.

The inventive method step（3）In, organic formwork agent is tetraethyl ammonium hydroxide, TMAH, tetrapropyl One or more in ammonium hydroxide.Wherein, by step（2）In after obtained Y type molecular sieve uniformly mixes with organic formwork agent, Hydrothermal crystallizing is carried out, process is as follows：By step（2）In obtained Y type molecular sieve be beaten in the organic formwork agent aqueous solution, liquid is solid Weight ratio is 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%, 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, filtered and drying can use conventional method to carry out, and typically dry condition is as follows：50 ~ 1 ~ 10h is dried at 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, 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.Roasting is general Using the method being calcined under temperature programming again constant temperature, heating rate is preferably 1 ~ 2 DEG C/min.

In the method for hydrogen cracking of the present invention, using one-stage serial technological process, it is necessary to enter before hydrocracking reaction Row hydrofinishing, its used Hydrobon catalyst can use conventional Hydrobon catalyst or be hydrocracked pre- place Catalyst is managed, typically using alumina-based supports, using vib and group VIII metal as hydrogenation active metal component, VI B 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 Group vib metal（In terms of oxide）Content be 15.0% ~ 30.0%, group VIII metal（In terms of oxide）Content be 4.0% ~8.0%。

Described coal tar fraction, its property are as follows：Density（20℃）For 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 more than 90wt%.

The method for hydrogen cracking of the present invention uses two-stage method technological process, and operating condition is as follows used by hydrofinishing： Reaction stagnation pressure is 12.0 ~ 20.0MPa, and volume space velocity is 0.1 ~ 0.5h during liquid^-1, hydrogen to oil volume ratio 1000：1~2000：1, reaction Temperature is 370 ~ 435 DEG C.Operating condition is as follows used by being hydrocracked：Reaction stagnation pressure is 10.0 ~ 20.0MPa, volume during liquid Air speed is 0.1 ~ 0.5h^-1, hydrogen to oil volume ratio 1000：1~2000：1, reaction temperature is 350 ~ 450 DEG C.

Hydrocracking catalyst used by the inventive method, wherein Y type molecular sieve are to use（NH₄）₂SiF₆To NaY points Son sieve is modified processing, while modulation molecular sieve silica alumina ratio is realized, can take off the sodium ion in NaY molecular sieve together Go out, hydrothermal crystallizing then is carried out to the molecular sieve after hydro-thermal process in the presence of organic formwork agent, can so make part silicon atom Enter framework of molecular sieve structure under organic formwork agent effect with aluminium atom, in bone that is further stable and improving modified molecular screen While frame structure, caused non-skeleton structure in zeolite-water heat treatment process, unimpeded pore passage structure, the organic mould in part are eliminated Plate agent can be also entered in the duct of molecular sieve, coordinate follow-up oxygen-enriched low-temperature treatment, can be by the organic formwork in molecular sieve The controllable removing in order of agent, so as to produce a large amount of ordered mesopore structures, and pore size distribution is more concentrated.

Y type molecular sieve is acid suitably in hydrogen Cracking catalyst used by the inventive method, crystallinity is high, mesoporous institute's accounting Example is high, pore-size distribution is more concentrated.Because the Y type molecular sieve has bigger pore volume and mesopore volume, in more acidity The heart is exposed, and is advantageous to raw material heavy oil macromolecular and is cracked, but also with more preferably pore size distribution range, can be effective Ground controls the cracking degree of reactant, and is advantageous to product and is diffused in duct, so in cracking reaction, relative can increase Add activated centre, and heavy oil macromolecular can be made to carry out the cracking reaction of suitable degree, both improve 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, the polycyclic aromatic hydrocarbon heavy constituent in coal tar can be effectively converted, produced The more excellent transportation fuel blend component of quality, 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 length service cycle.

The process of coal tar hydrocracking production lightweight transportation fuel of the present invention, effective and reasonable can utilize coal tar The consumption of petroleum resources can be reduced by obtaining the energy fuel of alternative oil, be national energy security power-assisted, improved coal tar and added Work utilization ratio, increases substantially economic benefit.

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 use 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 up 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 can be prepared by coprecipitation or grafting copolymerization process in catalyst carrier of the present invention, by document It is prepared by middle conventional method.In obtained amorphous silica-alumina, SiO₂Weight content be 10% ~ 60%, preferably 20% ~ 55%, The pore volume of amorphous silica-alumina is 0.6 ~ 1.1mL/g, preferably 0.8 ~ 1.0mL/g, and specific surface area is 300 ~ 500m²/ g, preferably For 350 ~ 500m²/g。

Detailed process prepared by catalyst carrier for hydrgenating of the present invention is as follows：By Modified Zeolite Y, amorphous silica-alumina, oxygen Change aluminium mixing, shaping, then dry and be calcined, be 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 calcined 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 by conventional methods（Vib and 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 containing required active component Agent carrier, carrier after dipping are then small in 450 DEG C ~ 550 DEG C roastings 2.5 ~ 6.0 in 100 DEG C ~ 150 DEG C dryings 1 ~ 12 hour When, final catalyst is made.

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 this The scope 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 uses XRF methods（X ray fluorescence spectrometry）Measure, molecular sieve Grain size use SEM（SEM）Mode determine.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 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 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

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）₂SiF₆ The aqueous solution, it is 72g/L's that 307mL solution concentrations were uniformly added dropwise at 60 minutes（NH₄）₂SiF₆Solution, constant temperature stirs after completion of dropwise addition 2 hours, constant temperature was filtered and dried after terminating, and the butt of molecular sieve is 65.3wt% after drying；By above-mentioned dried molecule Sieve is added in hydrothermal treatment device, in gauge pressure 0.25MPa, 610 DEG C of temperature, under the conditions of 1.0 hours processing times molecular sieve is entered Water-filling is heat-treated；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetraethyl ammonium hydroxide that 520mL mass concentrations are 5.3% In the aqueous solution, constant temperature is stirred 4 hours under the conditions of 80 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydrothermal crystallizing, 90 DEG C, gauge pressure 0.1MPa of crystallization temperature, crystallization time 10 hours, crystallization is filtered after terminating and drying process；Hydro-thermal is brilliant To change obtained drying sample to be calcined under oxygen-enriched state, oxygen content is 70v% in calcination atmosphere, and heating rate is 1 DEG C/min, 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-1, molecular sieve Property is 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 55g/L's that 182mL solution concentrations were uniformly added dropwise at 60 minutes（NH₄）₂SiF₆Solution, constant temperature after completion of dropwise addition Stirring 2 hours, constant temperature is filtered and dried after terminating, and the butt of molecular sieve is 68.0wt% after drying；Will be above-mentioned dried Molecular sieve is added in hydrothermal treatment device, gauge pressure 0.30MPa, 670 DEG C of temperature, under the conditions of 2.0 hours processing times to point Son sieve carries out hydro-thermal process；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetrapropyl hydrogen that 910mL mass concentrations are 7.5% Aoxidize in aqueous ammonium, constant temperature is stirred 4 hours under the conditions of 90 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydro-thermal Crystallization, 110 DEG C, gauge pressure 0.1MPa of crystallization temperature, crystallization time 10 hours, crystallization is filtered after terminating and drying process；Will The drying sample that hydrothermal crystallizing obtains is calcined under oxygen-enriched state, and oxygen content is 65v% in calcination atmosphere, heating rate 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 is listed in table 1.

Embodiment 3

Take NaY original powder 278g to be put into 1000mL water purification, be warming up to 100 DEG C, start to be added dropwise into molecular sieve pulp（NH₄）₂SiF₆The aqueous solution, it is 85g/L's that 417mL solution concentrations were uniformly added dropwise at 60 minutes（NH₄）₂SiF₆Solution, constant temperature after completion of dropwise addition Stirring 3 hours, constant temperature is filtered and dried after terminating, and the butt of molecular sieve is 67.2wt% after drying；Will be above-mentioned dried Molecular sieve is added in hydrothermal treatment device, gauge pressure 0.35MPa, 700 DEG C of temperature, under the conditions of 3.0 hours processing times to molecule Sieve carries out hydro-thermal process；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetraethyl hydrogen-oxygen that 1040mL mass concentrations are 3.5% Change in aqueous ammonium, constant temperature is stirred 3 hours under the conditions of 85 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydro-thermal crystalline substance Change, 80 DEG C, gauge pressure 0.1MPa of crystallization temperature, crystallization time 5 hours, crystallization is filtered after terminating and drying process；By hydro-thermal The drying sample that crystallization obtains is calcined under oxygen-enriched state, and oxygen content is 75v% in calcination atmosphere, and heating rate is 1 DEG C/ Min, constant temperature calcining temperature are 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, point Son sieve property is listed in table 1.

Embodiment 4

Take NaY original powder 278g to be put into 1400mL water purification, be warming up to 95 DEG C, start to be added dropwise into molecular sieve pulp（NH₄）₂SiF₆The aqueous solution, it is 60g/L's that 200mL solution concentrations were uniformly added dropwise at 60 minutes（NH₄）₂SiF₆Solution, constant temperature after completion of dropwise addition Stirring 2 hours, constant temperature is filtered and dried after terminating, and the butt of molecular sieve is 68.1wt% after drying；Will be above-mentioned dried Molecular sieve is added in hydrothermal treatment device, gauge pressure 0.30MPa, 750 DEG C of temperature, under the conditions of 2.0 hours processing times to point Son sieve carries out hydro-thermal process；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetrapropyl hydrogen that 520mL mass concentrations are 6.8% Aoxidize in aqueous ammonium, constant temperature is stirred 3 hours under the conditions of 90 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydro-thermal Crystallization, 95 DEG C, gauge pressure 0.1MPa of crystallization temperature, crystallization time 8 hours, crystallization is filtered after terminating and drying process；By water The drying sample that thermal crystallisation obtains is calcined under oxygen-enriched state, and oxygen content is 70v% in calcination atmosphere, and heating rate is 1 DEG C/ Min, constant temperature calcining temperature are 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 is 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 stirring 2 hours, constant temperature was filtered, washed and dried after terminating, and the butt of molecular sieve is 63.8wt% after drying；Temperature programming will divide Son sieve is calcined 3 hours at 600 DEG C；Then repeat an ammonium to exchange, and filter and dry；After taking second of ammonium of 100g to exchange Molecular sieve be put into 650mL mass concentrations be 7.5% the tetraethyl ammonium hydroxide aqueous solution in, constant temperature stirs under the conditions of 80 DEG C Mix 2 hours, then mixed material is transferred in crystallizing kettle and carries out crystallization, 100 DEG C, gauge pressure 0.1MPa of crystallization temperature, crystallization 8 hours time, 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, obtain 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 stirring 2 hours, constant temperature divides after terminating to be filtered, washed and dried, and the butt of molecular sieve is 63.8wt% after drying；Temperature programming will Molecular sieve is calcined 3 hours at 600 DEG C；Then repeat an ammonium to exchange, and filter and dry；Second of ammonium of 100g is taken to exchange Molecular sieve afterwards 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, constant temperature Filtered after end and drying process；Above-mentioned dried molecular sieve is added in hydrothermal treatment device, in gauge pressure 0.30MPa, 670 DEG C of temperature, molecular sieve is obtained to molecular sieve progress hydro-thermal process under the conditions of 2.0 hours processing times；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 property row are prepared using the method for embodiment in CN201510147788.3 1 In table 1.

The property of the Y type molecular sieve of table 1

Production code member	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/Al2O3Mol ratio	73.6.3	62.3	81.9	65.8
					Mesoporous pore volume（Bore dia 2nm ~ 10nm）Account 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

Production code member	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/Al2O3Mol ratio	7.5	33.5	8.6
				Mesoporous pore volume（Bore dia 2nm ~ 10nm）Account 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-aluminas（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 area 400m²/ g, butt 70wt%）, 200 grams of adhesives（The mol ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4）It is put into stone roller Mixed grind in press, adds water, is rolled into paste, extrusion, and extrusion bar is dried 4 hours at 110 DEG C, is then calcined 4 hours at 550 DEG C, Obtain carrier ZS-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 roastings 4 of temperature programming 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-aluminas（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 area 400m²/ g, do Base 70wt%）, 200 grams of adhesives（The mol ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4）It is put into roller and mixes Grind, add water, be 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 ZS- 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 roastings 4 of temperature programming Hour, catalyst HC-2 is obtained, carrier and corresponding catalyst property are shown in Table 2.

Embodiment 7 ~ 8

As described in Example 5, change LAY-1 into LAY-2, LAY-3 respectively, carrier ZS-3, ZS-4 and catalyst HC- is made 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 inventive method, and hydrocracking catalyst HC-1, HC-2, HC-3 and HC-4 is respectively adopted.Using Two-stage method technological process, Hydrobon catalyst use 3936 catalyst, tested on fixed bed hydrogenation experimental rig, behaviour It is as condition：Refining stage reaction stagnation pressure is 18.0MPa, and volume space velocity is 0.2h during liquid^-1, hydrogen to oil volume ratio 1500：1.Cracking Duan Fanying stagnation pressures are 16.0MPa, and volume space velocity is 0.3h during liquid^-1, hydrogen to oil volume ratio 1200：1, it is used as raw material using coal tar 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-stage method Technological process, Hydrobon catalyst use 3936 catalyst, tested on fixed bed hydrogenation experimental rig, operating condition For：Refining stage reaction stagnation pressure is 18.0MPa, and volume space velocity is 0.2h during liquid^-1, hydrogen to oil volume ratio 1500：1.Cracking zone reacts Stagnation pressure is 16.0MPa, and volume space velocity is 0.3h during liquid^-1, hydrogen to oil volume ratio 1200：1, it is former using coal tar as feedstock oil Material property is listed in table 3, and evaluation result is listed in table 4.

The physico-chemical property of the catalyst carrier of table 2 and catalyst

Carrier forms and property
					Numbering	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 forms and property
					Numbering	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 forms and property
				Numbering	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 forms and property
				Numbering	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 the coal tar of table 3

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, %	Vestige
		Carbon residue, %	0.83
Flash-point (is remained 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

The comparative evaluation's result of table 4

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 during 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 during 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 during 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 during 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 (14)

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 obtains gasoline fraction and diesel oil distillate through separation；It is wherein described Hydrocracking catalyst, including hydrogenation active metal component and carrier, carrier includes Modified Zeolite Y, amorphous silica-alumina And aluminum oxide, wherein described Modified Zeolite Y, its property is as follows：Relative crystallinity is 110% ~ 150%, SiO₂/Al₂O₃Rub You are than being 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 total hole More than the 70% of 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：Total pore volume For 0.6 ~ 1.0mL/g, 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 μ M, 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 be 0.1 ~ 0.5mmol/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：Compare surface Product is 250 ~ 450m²/ g, pore volume are 0.30 ~ 0.50mL/g.

9. in accordance with the method for claim 1, it is characterised in that：Described hydrogenation active metals are vib and 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, using the content that oxide is counted as 10.0% ~ 30.0%, content of the group VIII metal in terms of oxide is vib metals 4.0% ~ 8.0%, the content of carrier is 62.0% ~ 82.0%.

10. according to the method described in claim 1 or 9, it is characterised in that：Described carrier of hydrocracking catalyst, with carrier Weight on the basis of, the content of Modified Zeolite Y is 10% ~ 50%, and the content of amorphous silica-alumina is 5% ~ 30%, and aluminum oxide contains Measure as 20% ~ 85%, be preferably as follows：The content of Modified Zeolite Y is 15% ~ 45%, and the content of amorphous silica-alumina is 10% ~ 25%, The content of aluminum oxide is 30% ~ 75%.

11. in accordance with the method for claim 1, it is characterised in that：In described amorphous silica-alumina, SiO₂Weight content be 10% ~ 60%, preferably 20% ~ 55%, the property of amorphous silica-alumina are as follows：Pore volume is 0.6 ~ 1.1mL/g, specific surface area is 300 ~ 500m²/ g, is preferably as follows：Pore volume is 0.8 ~ 1.0mL/g, and specific surface area is 350 ~ 500m²/g。

12. in accordance with the method for claim 1, it is characterised in that：The method for hydrogen cracking uses one-stage serial technique stream Hydrobon catalyst is to use alumina-based supports used by journey, wherein hydrofinishing, with vib and group VIII gold It is molybdenum and/or tungsten to belong to for hydrogenation active metal component, vib metals, and group VIII metal is cobalt and/or nickel, with catalyst Weight on the basis of, vib metals are using the content that oxide is counted as 15.0% ~ 30.0%, and group VIII metal is in terms of oxide Content be 4.0% ~ 8.0%.

13. according to the method described in claim 1 or 12, it is characterised in that：The method for hydrogen cracking uses one-stage serial work Skill flow, hydrofinishing operating condition are as follows：Reaction stagnation pressure is 12.0 ~ 20.0MPa, and volume space velocity is 0.1 ~ 0.5h during liquid^-1, hydrogen Oil volume ratio is 1000：1~2000：1, reaction temperature is 370 ~ 435 DEG C；Hydrocracking operation condition is as follows：Reacting stagnation pressure is 10.0 ~ 20.0MPa, volume space velocity is 0.1 ~ 0.5h during liquid^-1, hydrogen to oil volume ratio 1000：1~2000：1, reaction temperature be 350 ~ 450℃。

14. in accordance with the method for claim 1, it is characterised in that：Described coal tar fraction, its property are as follows：20 DEG C close Spend for 0.95 ~ 1.20 g/cm³, initial boiling point be 160 ~ 190 DEG C, the end point of distillation be 450 ~ 480 DEG C, sulfur content be 1.50wt% ~ 3.0wt%, nitrogen content are 10000 ~ 20000 μ g/g, and arene content is more than 90wt%.