CN104667969B - A hydrocracking catalyst and a preparing method thereof - Google Patents
A hydrocracking catalyst and a preparing method thereof Download PDFInfo
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Abstract
A hydrocracking catalyst and a preparing method thereof are disclosed. The catalyst comprises metal components with hydrogenation activity and a carrier comprising a beta molecular sieve, a Y type molecular sieve and aluminum oxide, wherein properties of the beta molecular sieve are as follows: the specific surface area is 400-800 m2/g, the total pore volume is 0.4-0.55 mL/g, the SiO2/Al2O3 mole ratio is 30-60, the relative crystallinity is 120-140%, the infrared acid content is 0.55-1.0 mmol/g, the non-framework aluminum accounts for less than 1% of the total aluminum, the amount of medium-strong acids which is measured by a NH3-TPD method accounts for 70-85% of the total acid amount, and the percent of Na2O is not more than 0.15 wt%. The preparing method includes mixing the beta molecular sieve, the Y type molecular sieve and the aluminum oxide, kneading and forming to prepare the carrier; and loading the metal components with hydrogenation activity by a conventional method. The beta molecular sieve which is proper in silicon aluminum ratio, large in specific surface area, proper in acidity, reasonable in pore structure and low in content of non-framework aluminum, and the and the Y type molecular sieve are adopted as cracking components of the catalyst. The prepared catalyst can be used for increasing the yield of diesel oil with a low condensation point and improving properties of chemical raw materials.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, especially with beta-molecular sieve and Y type molecules
Sieve as predominant cracking component, with very high catalytic activity and be capable of high-output qulified intermediate oil hydrocracking catalyst and its
Preparation method.
Background technology
In recent years, countries in the world refined products market constantly increases always to the demand of high-quality middle cut oil product, with
Developing rapidly for economy, this imbalance between supply and demand seems more prominent.Hydrocracking technology is with its exclusive advantage into attaching most importance to
Oily deep processing production high-quality cleans the best means of intermediate oil.At present, oil type hydrocracking catalyst in countries in the world
Activity be not very high, the condensation point of gained diesel oil is also higher, it is difficult to meet refinery existing apparatus are transformed or increase process
Measure to reach the purpose for further increasing production intermediate oil.
Be hydrocracked the intermediate oil that raises productivity and improves the quality it is critical only that exploitation and using suitable catalyst.Containing single molecule
Although the hydrocracking catalyst of screen banks point has very high activity, but its middle distillates oil selectivity is poor, the catalysis containing composite molecular screen
Agent but shows to improve activity and can improve selective synergy.
Hydrocracking technology core is catalyst, and the key component for playing cracking in such catalyst mostly is Y types point
Son sieve and beta-molecular sieve.Relative to Y type molecular sieve, beta-molecular sieve has three-dimensional twelve-ring pore structure, but without as Y type molecular sieve
Such supercage structure, which is mainly characterized by double 6 yuan of rings unit bug hole structures of two 4 yuan of rings and four 5 yuan of rings, belongs to cube
Crystallographic system, main channel diameter is in 0.56-0.75nm.Beta-molecular sieve with topological structure and stereoscopic three-dimensional duct feature cause it
To the fracture of chain hydrocarbon-selective with effect well in cracking reaction, and with very strong isomery performance, as cracking component
Can be used for Low Freezing Point middle oil fraction, be industrially widely used.
The various and complexity of beta-molecular sieve silicon-aluminum structure.The skeleton structure of beta-molecular sieve is more multiple compared to Y type molecular sieve
Miscellaneous, in three cross one another pore canal systems, two linear channels are mutually orthogonal and perpendicular to [001] direction, and pore size is
0.57 nm × 0.75 nm, the 3rd twelve-ring pore canal system, parallel to [001] direction, are non-linear channels, pore size
For 0.56 nm × 0.65 nm；Completely beta-molecular sieve framework silicon-aluminum structure there is also diversity to crystallization, and framework silicon-aluminum structure is four
Coordination structure and this structure account for the main body of sial existence form total in molecular sieve, also exist a small amount of six in addition in molecular sieve
The non-framework aluminum of coordination；There are different changes in follow-up different modifying process in these various sial existing ways and content
Change, so as to different catalytic performances will be produced.
A kind of method of modifying of beta-molecular sieve is disclosed in CN101450318A.The method is by sodium form beta-molecular sieve and ammonium salt
Exchange, then dipping is carried out to molecular sieve with phosphorus-containing compound solution and the solution containing transistion metal compound be modified, the β for obtaining
Molecular sieve has the relative crystallinity of higher specific surface area and Geng Gao, further can generate low-carbon alkene by shape slective cracking.
EP95304, EP488867, US4554065 disclose beta-molecular sieve method of modifying, are mainly removed using three sections of alternating temperatures
Remove template（De- ammonium process）, then through certain density acid（Inorganic acid）Process, acid treatment process can be by molecular sieve
The abjection of part framework aluminum, the modified beta molecular sieve for obtaining has higher silica alumina ratio.The standby modified molecules sifter device of these patent systems
There is poor acid distribution and calculate density, prepared catalyst has poor purpose product selectivity and general product matter
Amount.
CN1393521A discloses a kind of middle oil type hydrocracking catalyst and preparation method thereof, and catalyst used carrier is
The complex type molecular sieve of amorphous silica-alumina, aluminum oxide and Y and β.Wherein composite molecular screen is by beta-molecular sieve original powder burning-off template
After mixing with modified Y molecular sieve afterwards, then Jing H+And NH4 +Mixed solution is processed and is obtained.The method is by beta-molecular sieve original powder elder generation burning-off
Template, so to the degree of crystallinity of molecular sieve is greatly lowered, is also affected the acidity of molecular sieve, is engaged with other components, should
The catalysis activity of catalyst is not high, and the product quality of the intermediate oil of navigate coal and diesel oil is general, further need to improve.
US 5,350,501, US 5,447,623, US 5,279,726, US 5,536,687 describe a kind of zeolite containing β
With the catalyst of Y zeolites.For producing during intermediate oil, consisting of：Y molecular sieve（1~15w%）, beta-molecular sieve（1~
15w%）, decentralized sial, aluminum oxide, metal W and Ni.Beta-molecular sieve wherein used is that Jing ion exchanges and roasting remove template
The mode of agent obtains Hydrogen beta-molecular sieve.The catalyst reaction activity and middle distillates oil selectivity are all not bery high, it is difficult to meet manufacturer
Aggrandizement apparatus disposal ability, further increases production the needs of intermediate oil.
CN1362362A discloses a kind of method of modifying of beta-molecular sieve.The method process is as follows：（1）Completely β point of crystallization
Son sieve directly carries out ammonium salt exchange；（2）Beta-molecular sieve after ammonium salt is exchanged carries out filtering, washes, is dried and roasting；（3）Roasting takes off
Beta-molecular sieve after ammonium carries out acid treatment, filtration, and the acid for being adopted is generally inorganic acid, can be nitric acid, hydrochloric acid or sulfuric acid etc.；
（4）The complete beta-molecular sieve of acid treatment carries out pressurized thermal water process.In the method, acid treatment is carried out to β zeolites first, then carried out again
Hydro-thermal process, is using mineral acid treatment, due to higher using inorganic acid concentration, in this course during acid treatment
The skeleton structure of moieties sieve will be destroyed, molecular sieve crystallinity declines, and the non-skeleton structure for forming bulk stays in molecular sieve
In duct, it is difficult to be removed, acid distribution and the acid strength of modified molecular screen are affected, in addition, also having carried out high temperature after acid treatment
Hydro-thermal process, also can form a certain amount of non-framework aluminum in molecular sieve, and these non-framework aluminum structures will block molecular sieve pore passage,
And the acid site in part mask molecule sieve skeleton structure, this will directly affect pore structure and the Acidity of molecular sieve, molecule
The acid distribution of sieve and the change of Acidity will directly affect thus performance of the molecular sieve as the catalyst of Cracking Component, especially
Impact is hydrocracked midbarrel oil yield and quality.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of hydrocracking catalyst and its preparation side
Method.The hydrocracking catalyst adopts a kind of suitable silica alumina ratio, bigger serface, acid suitable, pore structure rationally and non-skeleton
The low beta-molecular sieve of aluminium content, is acted synergistically with Y type molecular sieve, the active high and high-output qulified centre of prepared catalyst
The features such as distillate.
Hydrocracking catalyst of the present invention, comprising carrier and hydrogenation active metals component, carrier includes beta-molecular sieve, Y types point
Son sieve and aluminum oxide, wherein described beta-molecular sieve, its property are as follows：Specific surface area is 400m2/g~800m2/ g, preferably 500 ~
750m2/ g, total pore volume are 0.4ml/g ~ 0.55mL/g, SiO2/Al2O3Mol ratio is 30 ~ 60, preferably 35 ~ 55, relative to crystallize
Spend for 120% ~ 140%, meleic acid amount is 0.55 ~ 1.0mmol/g, non-framework aluminum accounts for less than 1%, NH of total aluminium3- TPD methods are measured
Middle strong acid acid amount account for the 70% ~ 85% of total acid content, preferably 75% ~ 85%, Na2O≤0.15wt%, preferably≤0.10wt%.
In the beta-molecular sieve of the present invention, total aluminium refers to the summation of the aluminium in aluminium and non-framework aluminum in molecular sieve middle skeleton aluminium.
The aluminium that non-framework aluminum is present with hexa-coordinate version in referring to molecular sieve.Framework aluminum is referred in molecular sieve with four-coordination structure shape
The aluminium that formula is present.
Described hydrocracking catalyst, in terms of the weight of carrier, the content of beta-molecular sieve is 5% ~ 20%, Y type molecular sieve
Content be 10% ~ 40%, the content of aluminum oxide is 40% ~ 85%.
Described hydrogenation active metals are the metal of vib and/or group VIII, vib metals be preferably molybdenum and
Or tungsten, metal preferably cobalt and/or the nickel of group VIII.In catalyst of the present invention, on the basis of the weight of catalyst, VIB
Race's metal（In terms of oxide）Content be 10.0% ~ 30.0%, group VIII metal（In terms of oxide）Content be 4.0% ~
8.0%。
Described Y type molecular sieve, its property are as follows：Specific surface area is 850m2/g~950m2/ g, total pore volume 0.43mL/g ~
0.55mL/g, relative crystallinity 90% ~ 130%, silica alumina ratio 20 ~ 150,2.425 ~ 2.433nm of cell parameter, meleic acid amount
0.1~0.4mmol/g.The Y type molecular sieve can be prepared using prior art.
Hydrocracking catalyst property of the present invention is as follows：Specific surface area is 200 ~ 450m2/ g, pore volume are 0.35 ~ 0.60mL/
g。
The preparation method of hydrocracking catalyst of the present invention, the preparation and load hydrogenation active metals component including carrier,
The preparation process of wherein carrier is as follows：By beta-molecular sieve, Y type molecular sieve, aluminum oxide mechanical mixture, shaping, then it is dried and roasts
Burn, make catalyst carrier；Wherein described beta-molecular sieve, including following preparation process：
（1）Beta-molecular sieve original powder is processed under the conditions of normal pressure, dynamic water vapour, treatment temperature is 500 ~ 650
DEG C, process time is 5 ~ 10 hours；
（2）With highly basic weak solution process step（1）The beta-molecular sieve of gained, then filters, washes and is dried, obtain beta molecule
Sieve.
Step（1）Beta-molecular sieve original powder is synthesized using hydrothermal crystallization method, its SiO2/Al2O3Mol ratio 20.0 ~ 25.0,
Na2O content is less than 0.2wt%.
Step（1）Beta-molecular sieve original powder typically can be steamed using the water of flowing in normal pressure, the process of dynamic water vapour condition
Vapour is carried out, using 100wt% water vapours.Water vapour passes through beta-molecular sieve by every kilogram of 20 ~ 100L/h of beta-molecular sieve.
Step（2）In, in the highly basic weak solution, the concentration of diluted alkaline（With OH-Meter）0.01 ~ 0.2mol/L, preferably 0.02 ~
0.15mol/L.The highly basic weak solution can be added to the water using highly basic and be formulated, and highly basic can be lithium hydroxide, hydrogen-oxygen
Change one or more in sodium, potassium hydroxide.Highly basic weak solution is 5 with the weight ratio of beta-molecular sieve:1~20:1.Described process
Condition：40 ~ 120 DEG C of temperature, preferably 70 ~ 100 DEG C, the time is 1.0 ~ 8.0 hours, preferably 2.0 ~ 4.0 hours.Described washing
Condition：50 ~ 90 DEG C of washing temperature, preferably 60 ~ 80, washing time 0.5 ~ 1.0 hour until cleaning solution pH value is close to neutrality is
Only, then it is dried 3 ~ 6 hours under conditions of 100 ~ 120 DEG C.
The inventive method processes molecular screen primary powder initially with normal pressure, Dynamic Hydrothermal, in the effect of dynamic high temperature water vapour
Under can realize that molecular sieve takes off ammonium（Template removal）Framework aluminum activation energy is reduced with selective, and is avoided to framework of molecular sieve knot
The destruction of structure, and the homogeneity of framework of molecular sieve structure is kept, it is engaged with follow-up highly basic weak solution modifying process, Neng Gouyou
Non-framework aluminum is uniformly deviate from by effect ground, forms unimpeded pore structure, and makes a small amount of OH-Adsorb the skeleton structure in molecular sieve
On, be conducive to improving the acid strength of molecular sieve and sour density, be conducive to improving the isomery performance of catalyst.Relative to existing method
The method of middle employing acid treatment and rear hydro-thermal process carries out the modified of molecular sieve, due to there is substantial amounts of H in strong acid acidization+
It can be non-selectivity abjection to the framework aluminum in molecular sieve and non-framework aluminum structure to exist, and can both deviate from part non-framework aluminum knot
Structure, can also deviate from part skeleton constructed of aluminium, have a strong impact on framework of molecular sieve silicon-aluminum structure and acidic zeolite matter, in addition, in acid
High-temperature water heat treatment is carried out again after change, it is also possible to produce non-framework aluminum structure in this modification procedure again, further affect
The Acidity of molecular sieve, a large amount of non-framework aluminum structures are present in the hole of Severe blockage molecular sieve in the duct of modified molecular sieve
Acid site in structure, but also meeting masked portion framework of molecular sieve, largely effects on the performance of modified molecular sieve, and then affects
To Cracking catalyst purpose product selectivity and product property.
The b molecular sieves that the present invention is selected have suitable cracking to make to long chain alkane and aromatic hydrocarbons, the long side chain n- alkyl of cycloalkane
With with good isomerization, enable prepared hydrocracking catalyst while high diesel yield is kept, by a relatively large margin
The condensation point of diesel oil distillate is reduced, the effect of volume increase low-coagulation diesel oil is reached.
Beta-molecular sieve of the present invention had both given full play to which respective with Y type molecular sieve collectively as cracking center
Performance characteristics, can make the concerted catalysis effect that two kinds of molecular sieves are produced again, i.e., beta-molecular sieve is to the long side on alkane or aromatic hydrocarbons
Chain has good isomerization, can effectively reduce the condensation point of product, while Y type molecular sieve has very high open loop to select to aromatic hydrocarbons
Property, improve the product property of purpose product.The active height of hydrocracking catalyst prepared by the present invention, can high-output qulified centre
Cut oil product（Boat coal+diesel oil）, while the hydrogenation tail oil of high-quality can and be produced.
When hydrocracking catalyst of the present invention is used for heavy oil hydrocracking, particularly in condition of high voltage（12~20MPa）With
Process wax slop（VGO, CGO and DAO）And/or poor ignition quality fuel（Coker gas oil and catalytic diesel oil etc.）Miscella, urges with very high
Change activity and intermediate oil selectivity, and the condensation point of diesel oil distillate reduces amplitude greatly, the product property of intermediate oil is obtained
To improvement, refinery's increase operating flexibility, the needs for increasing device disposal ability, further increasing production intermediate oil can be met.
Specific embodiment
In carrier of hydrocracking catalyst of the present invention, aluminum oxide can be using oxygen used in conventional hydrocracking catalyst
Change aluminium, such as macroporous aluminium oxide and/or little porous aluminum oxide.0.7 ~ the 1.0mL/g of pore volume of macroporous aluminium oxide used, specific surface area
200~500m2/g.The pore volume of little porous aluminum oxide used is 0.3 ~ 0.5mL/g, and specific surface area is 200 ~ 400m2/g。
The such as peptization acid of conventional shaping assistant, extrusion aid can also be added in catalyst carrier preparation process of the present invention
Deng.
Beta-molecular sieve in hydrocracking catalyst of the present invention, concrete preparation method are as follows：
（1）Beta-molecular sieve original powder is processed under the conditions of normal pressure, dynamic water vapour, treatment temperature is 500 ~ 650
DEG C, process time is 5 ~ 10 hours；
Beta-molecular sieve original powder of the present invention using hydrothermal crystallizing synthesis.The chemical SiO of adopted beta-molecular sieve original powder2/Al2O3
Mol ratio 20.0 ~ 25.0, Na2O content is less than 0.2wt%, relative crystallinity more than 95%；
It is 100wt% water vapours that the hydrothermal conditions adopted in the present invention are water vapours, and water vapour is by every kilogram of beta molecule
20 ~ 100L/h of sieve passes through beta-molecular sieve.In order that molecular sieve is processed evenly, preferably molecular sieve is placed in rotary container, water
Steam is passed into from one end of container and gone out from the other end of container after molecular sieve again.Pressure in container keeps normal pressure shape
State, treatment temperature are maintained at 500 ~ 650 DEG C, and process time is 5 ~ 10 hours；
In the inventive method, beta-molecular sieve original powder is placed in container such as tube furnace, and using temperature programming, heating rate is
50 ~ 150 DEG C/h, when being preferably raised to 250 ~ 450 DEG C, further preferably start to introduce water vapour at 250 ~ 400 DEG C, then
500 ~ 650 DEG C are warming up to while water vapour is introduced, and are processed 5 ~ 10 hours at this temperature；
（2）With highly basic weak solution process step（3）The beta-molecular sieve of gained, then filters, washes and is dried；
Highly basic weak solution, wherein highly basic weak solution concentration is added in return-flow system closed container（With OH-
Meter）0.01 ~ 0.2mol/L, preferably 0.02 ~ 0.15mol/L, stir and are warmed up to 40 ~ 120 DEG C, preferably 70 ~ 100 DEG C, then
It is 5 by the weight ratio of highly basic weak solution and molecular sieve:1~20:1, add step（3）The molecular sieve of acquisition, constant temperature stirring 1.0 ~
8.0 hours, preferably 2.0 ~ 4.0 hours, filter, washing, wash till cleaning solution pH value is close to neutrality, and 100 ~ 120
It is dried 3 ~ 6 hours under conditions of DEG C, obtains the beta-molecular sieve of the present invention.Wherein highly basic weak solution can be lithium hydroxide, hydroxide
The aqueous solution of one or more in sodium, potassium hydroxide.
Detailed process prepared by hydrocracking catalyst of the present invention is：
Then beta-molecular sieve, Y type molecular sieve, aluminum oxide mixing, extruded moulding are dried and roasting, load is prepared into
Body, described drying can be carried out at a temperature of 80 DEG C to 150 DEG C 3 ~ 6 hours, roasting be 500 DEG C ~ 600 DEG C roastings 2.5 ~
6 hours.
The load of catalyst activity metal of the present invention, can adopt the carrying method of routine in prior art, preferably infusion process,
Can be saturation leaching, excessive leaching or complexing leaching, i.e., with the solution impregnated catalyst carrier containing required active component, after dipping
Carrier is obtained final catalysis in 100 DEG C ~ 150 DEG C dryings 1 ~ 12 hour then in 450 DEG C ~ 550 DEG C roastings 2.5 ~ 6.0 hours
Agent.
The following examples are used for illustrating in greater detail the present invention, but the scope of the present invention is not limited solely to these embodiments
Scope.In the present invention, wt% is mass fraction.
Analysis method of the present invention：Specific surface area and pore volume adopt low temperature liquid nitrogen physisorphtion, silica alumina ratio employingization
Method, meleic acid amount adopt Pyridine adsorption IR spectra method, and the acid amount of middle strong acid and total acid content are by NH3- TPD methods are determined（It is logical
Cross NH3- TPD methods are determined：150 ~ 250 DEG C it is corresponding acid be weak acid, 250 ~ 400 DEG C it is corresponding acid be middle strong acid, 400 ~ 500 DEG C
Corresponding acid is strong acid；Weak acid, middle strong acid and strong acid acid amount and be total acid content）, sodium content adopts plasma emission spectrometry,
Relative crystallinity is determined using XRD method.
In the present invention, using nuclear magnetic resonance spectroscopy（NMR methods）Measure27Al MAS NMR spectras, so that obtain framework aluminum
And the ratio of non-framework aluminum, in terms of aluminium atom.Nuclear magnetic resonance spectroscopy（NMR methods）It is using Bruker AVANCE III 500
Type nuclear magnetic resonance spectrometer, wherein software adopt Topspin 2.0.Surveying27During Al MAS NMR spectras, accepted standard material is
Alchlor, resonant frequency is 133MHz, experiment condition：4-6 microsecond pulse widths, 60-120 second relaxation delays.Gained27Al
In MAS NMR spectras, the corresponding chemical shift of framework aluminum be 40 ~ 65ppm, the corresponding chemical shift of non-framework aluminum be -10 ~
10ppm。
Embodiment 1
Take beta-molecular sieve original powder about 3500g, its chemical sial SiO2/Al2O3（Mol ratio）Than for 22.68, sodium oxide content
For 0.18wt%.Beta-molecular sieve is loaded in tube furnace, using the method for temperature programming（Heating rate is 100 DEG C/h）, in pipe
Formula furnace temperature starts to introduce the water vapour of 100wt% when being raised to 300 DEG C, and water vapour passes through beta molecule by every kilogram of beta-molecular sieve 40L/h
Sieve, by diamond heating to 550 DEG C, constant temperature time is 8 hours.Gained molecular sieve numbering is BH-1, and property is shown in Table 1.
Embodiment 2
Beta-molecular sieve original powder about 3500g is taken, with embodiment 1.Molecular sieve is loaded in tube furnace, using the side of temperature programming
Method（Heating rate is 100 DEG C/h）, start to introduce the water vapour of 100wt%, water vapour when tubular type furnace temperature is raised to 300 DEG C
By every kilogram of beta-molecular sieve 70L/h by beta-molecular sieve, by diamond heating to 620 DEG C, constant temperature time is 8 hours.Gained molecule
Sieve numbering is BH-2, and property is shown in Table 1.
Embodiment 3
Weigh 50g BH-1 molecular sieves to be put into reflux and can be, in closed flask, to add concentration 0.04mol/
L NaOH aqueous solution 400ml, the NaOH aqueous solution are 8 with the weight ratio of BH-1 molecular sieves：1, at 95 DEG C, constant temperature stirring 2.0 is little
When, filter, and filter cake is washed with hot deionized water, stop washing after being close to 7 with the pH value of cleaning solution.Filter cake in an oven 120
DEG C drying 5 hours, obtains the beta molecular sieve of the present invention, and its numbering BJ-1, molecular sieve property are shown in Table 1.
Embodiment 4
Weigh 50g BH-1 molecular sieves to be put into reflux and can be, in closed flask, to add concentration 0.1mol/L
NaOH aqueous solution 700ml, the NaOH aqueous solution are 14 with the weight ratio of BH-1 molecular sieves：1, at 90 DEG C, constant temperature is stirred 2.5 hours,
Filter, and filter cake is washed with hot deionized water, stop washing after being close to 7 with the pH value of cleaning solution.Filter cake is done for 120 DEG C in an oven
Dry 5 hours.The beta molecular sieve of the present invention is obtained, its numbering BJ-2, molecular sieve property are shown in Table 1.
Embodiment 5
Weigh 50g BH-2 molecular sieves to be put into reflux and can be, in closed flask, to add concentration 0.15mol/
L KOH aqueous solution 1000ml, the KOH aqueous solution are 20 with the weight ratio of BH-2 molecular sieves：1, at 80 DEG C, constant temperature stirring 2.0 is little
When, filter, and filter cake is washed with hot deionized water, stop washing after being close to 7 with the pH value of cleaning solution.Filter cake in an oven 120
DEG C drying 5 hours, obtains the beta molecular sieve of the present invention, and its numbering BJ-3, molecular sieve property are shown in Table 1.
Embodiment 6
Weigh 50g BH-2 molecular sieves to be put into reflux and can be, in closed flask, to add concentration 0.06mol/
(NaOH+KOH, the two molar ratio are 1 to L：1) the weight ratio of aqueous solution 300ml, NaOH the and KOH aqueous solution and BH-2 molecular sieves
For 6：1, at 90 DEG C, constant temperature is stirred 3.0 hours, is filtered, and is washed filter cake with hot deionized water, is close to 7 with the pH value of cleaning solution
Stop washing afterwards.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain the beta molecular sieve of the present invention, its numbering BJ-4, molecular sieve
Property is shown in Table 1.
Comparative example 1
Modified molecular screen is prepared using the method in CN01106042.5.Gained molecular sieve is BD-1, and property is shown in Table 1, tool
Body process is as follows：
（1）Molecular screen primary powder 300g in Example 1, with 2.0M ammonium nitrate solutions with liquid-solid ratio as 10:1 is handed over
Change, be warming up to 90 ~ 95 DEG C, constant temperature is stirred 2 hours, is then cooled to 50 ~ 60 DEG C of filtrations, and wet cake carries out second exchange again,
Condition is with for the first time.
（2）The Jing beta-molecular sieves that ammonium salt is exchanged twice, wash to pH and reach 6, be then placed in drying box, 110 DEG C of dryings 6
Hour；
（3）Dried beta-molecular sieve was warming up to 250 DEG C in 1 hour in being put into muffle furnace, and constant temperature 2 hours is then proceeded to
400 DEG C are warming up in 1 hour, then constant temperature 4 hours, 540 DEG C are finally warmed up to, constant temperature 10 hours, material all burn white, carbon residue
≤0.2%；
（4）The beta-molecular sieve of the de- ammonium of high-temperature roasting is size-reduced, sieve, and weighs 400g, adds 0.4M HCl 4000ml, stirring
80 DEG C are warming up to, constant temperature is stirred 2 hours, cold filtration washing.
（5）The beta-molecular sieve filtration washing of Jing acid treatments, then in 110 DEG C of dryings 6 hours, butt is 85%.
（6）The sample of above-mentioned drying is placed in closed hydro-thermal process stove, 0.4 is uniformly sprayed（Kg water/kg drying samples）
Water purification, it is then closed, heat up, control pressure 300KPa, 600 DEG C of temperature, programming rate be 500 DEG C/h, constant temperature and pressure roasting
Burn 3 hours, then Temperature fall, that is, obtain comparative example modified molecular screen.
Comparative example 2
（1）Take commercial synthesis SiO2/Al2O3 24.35, Na2Slurries during the Na beta-molecular sieves of O 3.75wt% after crystallization
1000ml, 300g containing solid phase（In terms of butt）, 2M ammonium chloride solution 2000mL are added, stirred, be warming up to 95 DEG C, constant temperature stirring 2
Hour, 60 DEG C of filtrations are then cooled to, wet cake carries out second exchange again, and condition is with for the first time；
（2）The Jing beta-molecular sieves that ammonium salt is exchanged twice, wash to pH and reach 6, be then placed in drying box, 110 DEG C of dryings 6
Hour；
（3）Dried beta-molecular sieve was warming up to 250 DEG C in 1 hour in being put into muffle furnace, and constant temperature 2 hours is then proceeded to
400 DEG C are warming up in 1 hour, then constant temperature 4 hours, 540 DEG C are finally warmed up to, constant temperature 10 hours, material all burn white, carbon residue
≤0.2%；
（4）Beta-molecular sieve is put into reflux and can be, in closed flask, to add concentration 0.04mol/L NaOH water
Solution 400ml, the NaOH aqueous solution is 8 with the solvent and solute weight ratio of molecular sieve：1, at 95 DEG C, constant temperature is stirred 2.0 hours, is filtered, and
Filter cake is washed with hot deionized water, stops washing after 7 being close to the pH value of cleaning solution.120 DEG C of dryings 5 are little in an oven for filter cake
When, beta-molecular sieve is obtained, its numbering BD-2, molecular sieve property are shown in Table 1.
Comparative example 3
Using beta-molecular sieve original powder with embodiment 1.Above-mentioned molecular sieve 1000g is taken, is loaded in closed hydro-thermal process stove, is adopted
The method of temperature programming（Heating rate is 100 DEG C/h）, 620 DEG C of hydro-thermal process temperature, hydro-thermal process pressure are 0.2MPa.
Alkali process are being carried out using raw material, concentration is being adopted and is processed for the NaOH solution of 0.04mol/L, NaOH solution is solid with the liquid of molecular sieve
Weight ratio is 8：1, treatment temperature be 95 DEG C, process time be 2.0 hours, after constant temperature terminates, slurries are filtered, and with heat go from
Sub- water washing filter cake, stops washing after being close to 7 with the pH value of cleaning solution.120 DEG C of dryings 5 hours, obtain beta molecule in an oven
Sieve, numbering is BD-3, and physico-chemical property is listed in table 1.
The property of 1 embodiment of table and molecular sieve obtained by comparative example
Continued 1
Embodiment 7
By 22.22 grams of BJ-1 molecular sieves（Butt 90wt%）, 44.44 grams of Y type molecular sieves（SiO2/Al2O3=50, lattice constant
2.431nm, pore volume 0.45ml/g, specific surface area 900m2/ g, butt 90wt%）, 157.1 grams of macroporous aluminium oxides（Pore volume 1.0ml/
G, specific surface area 400m2/ g, butt 70wt%）, 100 grams of adhesives（Butt 30wt%, nitric acid with the mol ratio of little porous aluminum oxide is
0.4）Mixed grind in roller is put into, is added water, be rolled into paste, extrusion extrudes bar in 110 DEG C of dryings 4 hours, then at 550 DEG C
Roasting 4 hours, obtains 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 Z C-1 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 8
By 33.33 grams of BJ-1 molecular sieves（Butt 90wt%）, 44.44 grams of Y type molecular sieves（SiO2/Al2O3=43.5, structure cell is normal
Number 2.432nm, pore volume 0.48ml/g, specific surface area 890m2/ g, butt 90wt%）, 142.86 grams of macroporous aluminium oxides（Pore volume
1.0ml/g, specific surface area 400m2/ g, butt 70wt%）, 100 grams of adhesives（Butt 30wt%, nitric acid are rubbed with little porous aluminum oxide
You are than being 0.4）Mixed grind in roller is put into, is added water, be rolled into paste, extrusion extrudes bar in 110 DEG C of dryings 4 hours, Ran Hou
550 DEG C of roastings 4 hours, obtain 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 Z C-2 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 9
By 11.11 grams of BJ-4 molecular sieves（Butt 90wt%）, 66.67 grams of Y type molecular sieves（SiO2/Al2O3=85.3, structure cell is normal
Number 2.430nm, pore volume 0.45ml/g, specific surface area 917m2/ g, butt 90wt%）, 142.86 grams of macroporous aluminium oxides（Pore volume
1.0ml/g, specific surface area 400m2/ g, butt 70wt%）, 100 grams of adhesives（Butt 30wt%, nitric acid are rubbed with little porous aluminum oxide
You are than being 0.4）Mixed grind in roller is put into, is added water, be rolled into paste, extrusion extrudes bar in 110 DEG C of dryings 4 hours, Ran Hou
550 DEG C of roastings 4 hours, obtain carrier ZS-3.
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 Z C-3 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 10
By 44.44 grams of BJ-4 molecular sieves（Butt 90wt%）, 55.56 grams of Y type molecular sieves（SiO2/Al2O3=36.7, structure cell is normal
Number 2.433nm, pore volume 0.42ml/g, specific surface area 886m2/ g, butt 90wt%）, 88.89 grams of macroporous aluminium oxides（Pore volume
1.0ml/g, specific surface area 400m2/ g, butt 70wt%）, 100 grams of adhesives（Butt 30wt%, nitric acid are rubbed with little porous aluminum oxide
You are than being 0.4）Mixed grind in roller is put into, is added water, be rolled into paste, extrusion extrudes bar in 110 DEG C of dryings 4 hours, Ran Hou
550 DEG C of roastings 4 hours, obtain carrier ZS-4.
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 Z C-4 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Comparative example 4
By 33.33 grams of BD-1 molecular sieves（Butt 90wt%）, 44.44 grams of Y type molecular sieves（SiO2/Al2O3=43.5, structure cell is normal
Number 2.432nm, pore volume 0.48ml/g, specific surface area 890m2/ g, butt 90wt%）, 142.86 grams of macroporous aluminium oxides（Pore volume
1.0ml/g, specific surface area 400m2/ g, butt 70wt%）, 100 grams of adhesives（Butt 30wt%, nitric acid are rubbed with little porous aluminum oxide
You are than being 0.4）Mixed grind in roller is put into, is added water, be rolled into paste, extrusion extrudes bar in 110 DEG C of dryings 4 hours, Ran Hou
550 DEG C of roastings 4 hours, obtain carrier ZDS-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 Z DC-1 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Comparative example 5
By 11.11 grams of BD-1 molecular sieves（Butt 90wt%）, 66.67 grams of Y type molecular sieves（SiO2/Al2O3=50, lattice constant
2.431nm, pore volume 0.45ml/g, specific surface area 900m2/ g, butt 90wt%）, 142.86 grams of macroporous aluminium oxides（Pore volume 1.0ml/
G, specific surface area 400m2/ g, butt 70wt%）, 100 grams of adhesives（Butt 30wt%, nitric acid with the mol ratio of little porous aluminum oxide is
0.4）Mixed grind in roller is put into, is added water, be rolled into paste, extrusion extrudes bar in 110 DEG C of dryings 4 hours, then at 550 DEG C
Roasting 4 hours, obtains carrier ZDS-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 Z DC-2 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Comparative example 6
This comparative example is to change the BJ-1 molecular sieves in embodiment 8 into BD-3 molecular sieves, and other prepare carrier with embodiment 8
ZDS-3, property are shown in Table 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 Z DC-3 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 11
This embodiment describes by preparing catalyst activity evaluation result carrier of the present invention more.Fill in fixed bed hydrogenation test
Put and evaluated, appreciation condition is：Reaction stagnation pressure 15.0MPa, hydrogen to oil volume ratio 1250：1, volume space velocity 1.5h-1, adopt one
Section series connection once passes through technological process, using vacuum distillate（VGO）Used as feedstock oil, raw material oil nature is listed in table 3.Will catalysis
Agent ZC-2, ZDC-1 and ZDC-3 are evaluated under identical process conditions, and the evaluation result for obtaining is listed in table 4.
By evaluation result as can be seen that prepared catalyst of the present invention is under identical process conditions, midbarrel grease separation
Selecting property, yield and product quality are superior to reference catalyst.
The physico-chemical property of 2 catalyst carrier of table and catalyst
3 raw material oil nature of table
4 ZC-2, ZDC-1 and ZDC-3 catalyst performance comparative evaluation's result of table
Claims (24)
1. a kind of hydrocracking catalyst, comprising hydrogenation active metals component and carrier, wherein carrier includes beta-molecular sieve, Y types point
Son sieve and aluminum oxide, the property of the beta-molecular sieve are as follows：Specific surface area is 400m2/g~800m2/ g, total pore volume be 0.4ml/g ~
0.55mL/g, SiO2/Al2O3Mol ratio is 30 ~ 60, and relative crystallinity is 120% ~ 140%, and meleic acid amount is 0.55 ~ 1.0mmol/
G, non-framework aluminum account for less than 1%, NH of total aluminium3The acid amount of the middle strong acid that-TPD methods are measured accounts for 70% ~ 85%, Na of total acid content2O≤
0.15wt%。
2. according to the catalyst described in claim 1, it is characterised in that the specific surface area of the beta-molecular sieve is 500 ~ 750m2/ g,
Total pore volume is 0.4ml/g ~ 0.55mL/g.
3. according to the catalyst described in claim 1, it is characterised in that the SiO of the beta-molecular sieve2/Al2O3Mol ratio be 35 ~
55。
4. according to the catalyst described in claim 1, it is characterised in that in the beta-molecular sieve, NH3- TPD methods are strong in measuring
The acid amount of acid accounts for the 75% ~ 85% of total acid content.
5. according to the catalyst described in claim 1, it is characterised in that：Described carrier of hydrocracking catalyst, with carrier
On the basis of weight, the content of beta-molecular sieve is 5% ~ 20%, and the content of Y type molecular sieve is 10% ~ 40%, the content of aluminum oxide is 40% ~
85%。
6. according to the catalyst described in claim 1, it is characterised in that：Described Y type molecular sieve, its property are as follows：Specific surface
Product is 850m2/g~950m2/ g, total pore volume be 0.43mL/g ~ 0.55mL/g, relative crystallinity 90% ~ 130%, SiO2/Al2O3Mole
Than for 20 ~ 150, cell parameter is 2.425 ~ 2.433nm, meleic acid 0.1 ~ 0.4mmol/g of amount.
7. according to the catalyst described in claim 1, it is characterised in that：Described hydrogenation active metals are vib and/or the
The metal of VIII, vib metals are molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel.
8. according to the catalyst described in claim 7, it is characterised in that：Described hydrocracking catalyst, with the weight of catalyst
On the basis of amount, the content that vib metals are counted with oxide as 10.0% ~ 30.0%, group VIII metal containing in terms of oxide
Measure as 4.0% ~ 8.0%.
9. according to the catalyst described in claim 1, it is characterised in that：Described catalyst property is as follows：Specific surface area is 200
~400m2/ g, pore volume are 0.35 ~ 0.60mL/g.
10. the preparation method of the arbitrary described catalyst of claim 1 ~ 9, including：The preparation of carrier and load hydrogenation activity gold
Category component, the preparation process of wherein carrier are as follows：By beta-molecular sieve, Y type molecular sieve, aluminum oxide mechanical mixture, it is molded, Ran Hougan
Dry and roasting, makes catalyst carrier；The wherein preparation method of beta-molecular sieve, including：
（1）Beta-molecular sieve original powder is processed under the conditions of normal pressure, dynamic water vapour, treatment temperature is 500 ~ 650 DEG C, place
The reason time is 5 ~ 10 hours；
（2）With highly basic weak solution process step（1）The beta-molecular sieve of gained, then filters, washes and is dried, obtain beta-molecular sieve.
11. in accordance with the method for claim 10, it is characterised in that step（1）Beta-molecular sieve original mealiness matter is as follows：SiO2/
Al2O3Mol ratio 20.0 ~ 25.0, Na2O content is less than 0.2wt%.
12. in accordance with the method for claim 10, it is characterised in that step（1）Using the 100wt% steam treatments of flowing.
13. according to the method described in claim 10 or 12, it is characterised in that step（1）In, water vapour presses every kilogram of beta-molecular sieve
20 ~ 100L/h passes through beta-molecular sieve.
14. according to the method described in claim 10 or 12, it is characterised in that step（1）In, step（1）In, beta-molecular sieve original powder
It is placed in container, using temperature programming, heating rate is 50 ~ 150 DEG C/h, when rising to 250 ~ 450 DEG C, starts to introduce water steaming
Vapour, is then warming up to 500 ~ 650 DEG C while water vapour is introduced, and processes 5 ~ 10 hours at this temperature.
15. in accordance with the method for claim 10, it is characterised in that the highly basic is lithium hydroxide, NaOH, hydroxide
One or more in potassium.
16. according to the method described in claim 10 or 15, it is characterised in that step（2）In, in the highly basic weak solution, diluted alkaline
Concentration with OH-0.01 ~ 0.2mol/L of meter.
17. according to the method described in claim 10 or 15, it is characterised in that step（2）In, in the highly basic weak solution, diluted alkaline
Concentration with OH-0.02 ~ 0.15mol/L of meter.
18. in accordance with the method for claim 10, it is characterised in that the highly basic weak solution is 5 with the weight ratio of beta-molecular sieve:
1~20:1。
19. in accordance with the method for claim 10, it is characterised in that step（2）Described treatment conditions：40 ~ 120 DEG C of temperature,
Time is 1.0 ~ 8.0 hours.
20. in accordance with the method for claim 10, it is characterised in that step（2）Described treatment conditions：70 ~ 100 DEG C of temperature,
Time is 2.0 ~ 4.0 hours.
21. in accordance with the method for claim 10, it is characterised in that step（2）Described drying is the bar at 100 ~ 120 DEG C
It is dried 3 ~ 6 hours under part.
22. in accordance with the method for claim 10, it is characterised in that：The drying of carrier and roasting condition are as follows：100 DEG C ~
150 DEG C of dryings 1 ~ 12 hour, then in 450 DEG C ~ 550 DEG C roastings 2.5 ~ 6.0 hours.
23. in accordance with the method for claim 10, it is characterised in that：Described aluminum oxide adopts macroporous aluminium oxide and/or little
Porous aluminum oxide, the 0.7 ~ 1.0mL/g of pore volume, 200 ~ 500m of specific surface area of macroporous aluminium oxide used2/ g, aperture oxidation used
The pore volume of aluminium is 0.3 ~ 0.5mL/g, and specific surface area is 200 ~ 400m2/g。
24. in accordance with the method for claim 10, it is characterised in that：Hydrogenation active metals component is loaded to using infusion process urges
On agent carrier, the drying and roasting condition after dipping is as follows：In 100 DEG C ~ 150 DEG C dryings 1 ~ 12 hour, then 450 DEG C ~
550 DEG C of roastings 2.5 ~ 6.0 hours.
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| CN107344119B (en) * | 2016-05-05 | 2019-12-13 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier and preparation method thereof |
| CN107345154B (en) * | 2016-05-05 | 2019-04-12 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking of poor ignition quality fuel |
| CN110404581A (en) * | 2018-04-28 | 2019-11-05 | 中国石油天然气股份有限公司 | Preparation method of hydrocracking catalyst and poor/heavy diesel oil hydrocracking method |
| CN116060115B (en) * | 2021-10-29 | 2024-07-02 | 中国石油化工股份有限公司 | Hydrodewaxing catalyst and its preparation method and application |
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| CN1351120A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | High-activity high-or medium-oilness hydrocracking catalyst and its preparing process |
| CN1712134A (en) * | 2004-06-21 | 2005-12-28 | 中国石油化工股份有限公司 | Hydrogenation catalyst carrier and production thereof |
| CN103100417A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
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| CN1351120A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | High-activity high-or medium-oilness hydrocracking catalyst and its preparing process |
| CN1712134A (en) * | 2004-06-21 | 2005-12-28 | 中国石油化工股份有限公司 | Hydrogenation catalyst carrier and production thereof |
| CN103100417A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
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