CN104667958B - 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, amorphous silicon aluminum 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 amorphous silicon aluminum 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 amorphous silicon aluminum are adopted as cracking components of the catalyst. The prepared catalyst is characterized by producing a clean diesel oil product with a low condensation point with the highest yield, improving properties of hydrogenation tail oil, and the like.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, particularly a kind of high activity, maximum production
Hydrocracking catalyst of low freezing point diesel fuel and preparation method thereof.
Background technology
Hydrocracking technology has that adaptability to raw material is strong, products scheme flexibility is big, purpose product selectivity is high, product matter
Measure, the features such as added value is high, various heavys, inferior raw material can directly be converted the industrial chemicals of clean fuel oil and high-quality,
As one of modern times oil refining and the most important heavy oil deep processing technique of petro chemical industry, obtain increasingly extensive in countries in the world
Application.Because crude quality is deteriorated year by year, sour crude is significantly increased, environmental protection to oil refining process in itself and petroleum product-quality
It is required that increasingly strict, market is continuously increased to clean fuel oil and industrial chemicals demand.Therefore, hydrocracking technology will also be obtained
More it is widely applied, while also itself proposes requirement higher to hydrocracking technology.
Hydrocracking technology core is catalyst, and the key component mostly Y types point of cracking are played in such catalyst
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, its double 6 yuan of rings unit bug hole structure for being mainly characterized by two 4 yuan of rings and four 5 yuan of rings belong 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
There is effect well in cracking reaction to the fracture of chain hydrocarbon-selective, 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, two linear channels are mutually orthogonal and perpendicular to [001] direction in three cross one another pore canal systems, and pore size is
0.57 nm × 0.75 nm, the 3rd twelve-ring pore canal system, parallel to [001] direction, is non-linear channels, pore size
It is 0.56 nm × 0.65 nm；The complete beta-molecular sieve framework silicon-aluminum structure of crystallization there is also diversity, 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 molecular sieve in addition
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 the solution with phosphorus-containing compound solution and containing transistion metal compound carries out dipping to molecular sieve and is modified, the β for obtaining
Molecular sieve has the relative crystallinity of specific surface area and Geng Gao higher, 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 by certain density acid（Inorganic acid）Treatment, acid treatment process can be by molecular sieve
The abjection of part framework aluminum, the modified beta molecular sieve for obtaining has silica alumina ratio higher.The standby modified molecules sifter device of these patent systems
There is poor acid distribution and calculation density, prepared catalyst has poor purpose product selectivity and general product matter
Amount.
US 4,820,402 discloses a kind of hydrocracking catalyst of high selectivity to middle distillates, is characterized in using a kind of high
The molecular sieve of silica alumina ratio such as ZSM-20, Y and β, molecular sieve silica alumina ratio are at least 50:1, preferably 200:More than 1.The method will not
Middle distillates oil selectivity most preferably ZSM-20 when being used for hydrocracking catalyst with high silica alumina ratio molecular sieve, next to that β.Because this is urged
The silica alumina ratio of molecular sieve used by agent is too high, makes the active relatively low of catalyst, and middle distillates oil selectivity is nor very high.
CN 97122139.1 describes a kind of amorphous silicon Al catalysts.The catalyst is with amorphous silica-alumina and aluminum oxide
It is carrier, is hydrogenation active metals component with tungsten, nickel, is prepared by the specific process for carrying out hydro-thermal process after being molded using carrier again.
Although the activity and the middle distillates oil selectivity amorphous silicon Al catalysts more conventional than its of the catalyst are significantly improved, with most
The characteristics of a large amount of production low-coagulation diesel oils, but reaction temperature is still higher, and operating flexibility is poor, it is difficult to meet manufacturer's increase
The need for device disposal ability, further increasing output of diesel oil.
CN1362362A discloses a kind of method of modifying of beta-molecular sieve.The method process is as follows：（1）The complete β of crystallization points
Son sieve directly carries out ammonium salt exchange；（2）Beta-molecular sieve after ammonium salt is exchanged is filtered, washed, being dried and being calcined；（3）Roasting is de-
Beta-molecular sieve after ammonium carries out acid treatment, filtering, and the acid for being used 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 treatment.In the method, acid treatment first is carried out to β zeolites, then carried out again
Hydro-thermal process, is using mineral acid treatment, due to using inorganic acid concentration higher, 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, the acid of influence modified molecular screen is distributed and acid strength, in addition, also having carried out high temperature after acid treatment
Hydro-thermal process, can also 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 the pore structure and Acidity of molecular sieve, molecule
The acid distribution and the change of Acidity of sieve will directly affect thus molecular sieve as the performance of the catalyst of Cracking Component, especially
Influence is hydrocracked production of diesel oil 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 uses 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 Cracking Component, with the low condensation point cleaning diesel product of maximum and improvement hydrogenation tail oil property etc.
Feature.
Hydrocracking catalyst of the present invention, comprising carrier and hydrogenation active metals component, carrier includes that beta-molecular sieve, nothing are fixed
Shape sial, aluminum oxide, wherein the property of described beta-molecular sieve is as follows：Specific surface area is 400m2/g~800m2/ g, preferably 500 ~
750m2/ g, total pore volume is 0.4ml/g ~ 0.55mL/g, SiO2/Al2O3Mol ratio is 30 ~ 60, preferably 35 ~ 55, relative crystallization
It is 120% ~ 140% to spend, and meleic acid amount is 0.55 ~ 1.0mmol/g, and 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 beta-molecular sieve of the invention, total aluminium refers to the summation of the aluminium in aluminium and non-framework aluminum in molecular sieve middle skeleton aluminium.
Non-framework aluminum refers to the aluminium existed with hexa-coordinate structure type in molecular sieve.Framework aluminum refers to four-coordination structure shape in molecular sieve
The aluminium that formula is present.
Described hydrogenation active metals are vib He the metal of ∕ or group VIII, vib metals are preferably Mu He ∕
Or tungsten, the metal of group VIII is preferably Gu He ∕ or nickel.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 for 4.0% ~
8.0%。
Amorphous silica-alumina used can be prepared by coprecipitation or grafting copolymerization process in catalyst of the present invention, by normal in document
It is prepared by rule method.SiO in obtained amorphous silica-alumina2Weight content be 5% ~ 40%, preferably 7% ~ 30%, amorphous silicon
The pore volume of aluminium is 0.6 ~ 1.1mL/g, and preferably 0.8 ~ 1.0mL/g, specific surface area is 300 ~ 500m2/ g, preferably 350 ~ 500m2/
g.Amorphous silica-alumina weight content in the carrier is preferably 25% ~ 55%.
Described carrier of hydrocracking catalyst, on the basis of the weight of carrier, the content of beta-molecular sieve is 3% ~ 20%, nothing
The content of amorphous silicon-alumina is 10% ~ 70%, and the content of aluminum oxide is 15% ~ 70%.
Hydrocracking catalyst property of the present invention is as follows：Specific surface area is 200 ~ 400m2/ g, pore volume is 0.35 ~ 0.60mL/
g。
The preparation method of hydrocracking catalyst of the present invention, including：The preparation of carrier and load hydrogenation active metals component,
The preparation process of wherein carrier is as follows：By beta-molecular sieve, amorphous silica-alumina, aluminum oxide mechanical mixture, shaping, then dry and roast
Burn, be made 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 dries, and obtains 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 can typically be steamed in normal pressure, the treatment of dynamic water vapour condition using the water of flowing
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 treatment
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
Only, then dried 3 ~ 6 hours under conditions of 100 ~ 120 DEG C.
The inventive method processes molecular screen primary powder using normal pressure, Dynamic Hydrothermal first, 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 selectivity, 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 effect ground, forms unimpeded pore structure, and make a small amount of OH-Adsorb the skeleton structure in molecular sieve
On, be conducive to improving the acid strength and sour density of molecular sieve, be conducive to improving the isomery performance of catalyst.Relative to existing method
The method of middle use 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+
In the presence of that can be non-selectivity abjection to the framework aluminum in molecular sieve and non-framework aluminum structure, part non-framework aluminum knot can be both deviate from
Structure, can also deviate from part skeleton constructed of aluminium, framework of molecular sieve silicon-aluminum structure and acidic zeolite matter be had a strong impact on, in addition, in acid
High-temperature water heat treatment is carried out after change again, it is also possible to produce non-framework aluminum structure again in this modification procedure, further influence
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 influence
To Cracking catalyst purpose product selectivity and product property.
Catalyst of the present invention adds suitable amorphous silica-alumina as acidic components, especially with special modified beta-molecular sieve
It is the second Cracking Component, that is, has given full play to its respective performance characteristics, preferable concerted catalysis effect is generated again, makes thus
The hydrocracking catalyst of preparation while activity is improved, and with good selective opening of cyclic paraffins, alkane isomery
Change, heavy distillat is moderately hydrocracked, aromatic hydrocarbons saturation and hetero atom remove performance.There is prepared hydrocracking catalyst to live
Property it is high, can maximum production low freezing point diesel fuel, while can and produce high-quality hydrogenation tail oil.
Beta-molecular sieve of the present invention has that silica alumina ratio suitable, bigger serface, crystallinity is high, acid suitable, pore structure rationally and
The characteristics of non-framework aluminum content is low, especially has suitable splitting action to long chain alkane and aromatic hydrocarbons, the long side chain n- alkyl of cycloalkane
Very strong isomerization, enables hydrocracking catalyst prepared therefrom 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.
When being used for heavy oil hydrocracking by hydrocracking catalyst of the present invention, particularly in condition of high voltage（12~20MPa）
With treatment wax slop（VGO, CGO and DAO）With catalysis activity very high and intermediate oil selectivity, and diesel oil distillate
Condensation point reduction amplitude is reached, and the product property of intermediate oil is improved, and can be met refinery's increase operating flexibility, be increased device
The need for disposal ability, further increasing output of diesel oil.
Specific embodiment
Aluminum oxide can be using oxygen used in conventional hydrocracking catalyst in carrier of hydrocracking catalyst of the present invention
Change aluminium, such as macroporous aluminium oxide and ∕ or small 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 small 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, specific preparation method is 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；
The beta-molecular sieve original powder that the present invention is synthesized using hydrothermal crystallizing.The chemical SiO of used beta-molecular sieve original powder2/Al2O3
Mol ratio 20.0 ~ 25.0, Na2O content is less than 0.2wt%, relative crystallinity more than 95%；
The hydrothermal conditions used in the present invention are that water vapour is 100wt% water vapours, and water vapour presses every kilogram of beta molecule
20 ~ 100L/h of sieve passes through beta-molecular sieve.In order that molecular sieve treatment is evenly, preferably molecular sieve is placed in rotary container, water
Steam is gone out from the other end of container again after passing into molecular sieve from one end of container.Pressure in container keeps normal pressure shape
State, treatment temperature is 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 dries；
Highly basic weak solution, wherein highly basic weak solution concentration are added in return-flow system and 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, filtering, washing were washed untill the close neutrality of cleaning solution pH value, and 100 ~ 120
Dried 3 ~ 6 hours under conditions of DEG C, obtain beta-molecular sieve of the invention.Wherein highly basic weak solution can be lithium hydroxide, hydroxide
One or more in sodium, potassium hydroxide of the aqueous solution.
Detailed process prepared by hydrocracking catalyst of the present invention is：
Beta-molecular sieve, amorphous silica-alumina, aluminum oxide are mixed, then extruded moulding is dried and is calcined, and is prepared into load
Body, described drying can be carried out 3 ~ 6 hours at a temperature of 80 DEG C to 150 DEG C, roasting be 500 DEG C ~ 600 DEG C be calcined 2.5 ~
6.0 hour.
The load of catalyst activity metal of the present invention, can use carrying method conventional in the prior art, preferably infusion process,
Can be saturation leaching, excessive leaching or complexing leaching, i.e., with the solution impregnated catalyst carrier of the active component containing needed for, after dipping
Then carrier is calcined 2.5 ~ 6.0 hours in 100 DEG C ~ 150 DEG C dryings 1 ~ 12 hour at 450 DEG C ~ 550 DEG C, and final catalysis is obtained
Agent.
The following examples are used to illustrate 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 use low temperature liquid nitrogen physisorphtion, silica alumina ratio useization
Method, meleic acid amount uses Pyridine adsorption IR spectra method, and the acid amount and total acid content of middle strong acid are by NH3- TPD methods are determined（It is logical
Cross NH3- TPD methods are determined：150 ~ 250 DEG C of corresponding acid are weak acid, and 250 ~ 400 DEG C of corresponding acid are 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 uses 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 as to 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 use 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 seconds relaxation delay.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 being 22.68, sodium oxide content
It is 0.18wt%.Beta-molecular sieve is fitted into 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 fitted into 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
50g BH-1 molecular sieves are weighed to be put into reflux and concentration 0.04mol/ can be added with closed flask
L NaOH aqueous solution 400ml, the NaOH aqueous solution is 8 with the weight ratio of BH-1 molecular sieves：1, constant temperature stirring 2.0 is small at 95 DEG C
When, filtering, and filter cake is washed with hot deionized water, stop washing close to after 7 with the pH value of cleaning solution.Filter cake in an oven 120
DEG C drying 5 hours, obtains beta molecular sieve of the invention, and its numbering BJ-1, molecular sieve property is shown in Table 1.
Embodiment 4
50g BH-1 molecular sieves are weighed to be put into reflux and concentration 0.1mol/L can be added with closed flask
NaOH aqueous solution 700ml, the NaOH aqueous solution is 14 with the weight ratio of BH-1 molecular sieves：1, constant temperature is stirred 2.5 hours at 90 DEG C,
Filtering, and filter cake is washed with hot deionized water, stop washing close to after 7 with the pH value of cleaning solution.Filter cake is done for 120 DEG C in an oven
Dry 5 hours.Beta molecular sieve of the invention is obtained, its numbering BJ-2, molecular sieve property is shown in Table 1.
Embodiment 5
50g BH-2 molecular sieves are weighed to be put into reflux and concentration 0.15mol/ can be added with closed flask
L KOH aqueous solution 1000ml, the KOH aqueous solution is 20 with the weight ratio of BH-2 molecular sieves：1, constant temperature stirring 2.0 is small at 80 DEG C
When, filtering, and filter cake is washed with hot deionized water, stop washing close to after 7 with the pH value of cleaning solution.Filter cake in an oven 120
DEG C drying 5 hours, obtains beta molecular sieve of the invention, and its numbering BJ-3, molecular sieve property is shown in Table 1.
Embodiment 6
50g BH-2 molecular sieves are weighed to be put into reflux and concentration 0.06mol/ can be added with closed flask
(NaOH+KOH, the two molar ratio is 1 to L：1) the weight ratio of aqueous solution 300ml, NaOH and the KOH aqueous solution and BH-2 molecular sieves
It is 6：1, constant temperature is stirred 3.0 hours at 90 DEG C, filtering, and washs filter cake with hot deionized water, with the pH value of cleaning solution close to 7
Stop washing afterwards.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta molecular sieve of the 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 be 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 filterings, and wet cake carries out second exchange again,
Condition is with for the first time.
（2）Through the beta-molecular sieve that ammonium salt twice is exchanged, washing reaches 6, is then placed in drying box, 110 DEG C of dryings 6 to pH
Hour；
（3）Dried beta-molecular sieve was warming up to 250 DEG C in being put into muffle furnace in 1 hour, and constant temperature 2 hours is then proceeded to
It was warming up to 400 DEG C in 1 hour, then constant temperature 4 hours, 540 DEG C are finally warmed up to, constant temperature 10 hours, material all burns white, carbon residue
≤0.2%；
（4）The beta-molecular sieve of the de- ammonium of high-temperature roasting is size-reduced, sieving, 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）Through the beta-molecular sieve filtration washing of acid treatment, then in 110 DEG C of dryings 6 hours, butt is 85%.
（6）Above-mentioned dry sample 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, stir, be warming up to 95 DEG C, constant temperature stirring 2
Hour, 60 DEG C of filterings are then cooled to, wet cake carries out second exchange again, and condition is with for the first time；
（2）Through the beta-molecular sieve that ammonium salt twice is exchanged, washing reaches 6, is then placed in drying box, 110 DEG C of dryings 6 to pH
Hour；
（3）Dried beta-molecular sieve was warming up to 250 DEG C in being put into muffle furnace in 1 hour, and constant temperature 2 hours is then proceeded to
It was warming up to 400 DEG C in 1 hour, then constant temperature 4 hours, 540 DEG C are finally warmed up to, constant temperature 10 hours, material all burns white, carbon residue
≤0.2%；
（4）Beta-molecular sieve is put into reflux and can add concentration 0.04mol/L NaOH water with closed flask
Solution 400ml, the NaOH aqueous solution is 8 with the solvent and solute weight ratio of molecular sieve：1, constant temperature is stirred 2.0 hours at 95 DEG C, filtering, and
Filter cake is washed with hot deionized water, stops washing close to after 7 with the pH value of cleaning solution.120 DEG C of dryings 5 are small in an oven for filter cake
When, beta-molecular sieve is obtained, its numbering BD-2, molecular sieve property is shown in Table 1.
Comparative example 3
Using beta-molecular sieve original powder with embodiment 1.Above-mentioned molecular sieve 1000g is taken, is fitted into closed hydro-thermal process stove, used
The method of temperature programming（Heating rate is 100 DEG C/h）, 620 DEG C of hydro-thermal process temperature, hydro-thermal process pressure is 0.2MPa.
Alkali process are being carried out using raw material, is using concentration to be processed for the NaOH solution of 0.04mol/L, NaOH solution is being consolidated 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, washing is stopped with the pH value of cleaning solution close to after 7.120 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 the embodiment of table 1 and comparative example gained molecular sieve
Continued 1
Embodiment 7
By 15.6 grams of BJ-2 molecular sieves（Butt 90wt%）, 114.3 grams of amorphous silica-aluminas（SiO2Content 20wt%, pore volume
0.85ml/g, specific surface area 370m2/ g, butt 70wt%）, 94.3 grams of macroporous aluminium oxides（Pore volume 1.0ml/g, specific surface area
400m2/ g, butt 70wt%）, 133.3 grams of adhesives（Butt 30wt%, nitric acid is 0.4 with the mol ratio of small porous aluminum oxide）It is put into
Mixed grind in roller, adds water, and is rolled into paste, extrusion, and extrusion bar is then small in 550 DEG C of roastings 4 in 110 DEG C of dryings 4 hours
When, carrier HS-1 is obtained, property is 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 HC-1 is obtained, corresponding catalyst property is shown in Table 2.
Embodiment 8
By 33.3 grams of BJ-2 molecular sieves（Butt 90wt%）, 85.7 grams of amorphous silica-aluminas（SiO2Content 20wt%, pore volume
0.85ml/g, specific surface area 370m2/ g, butt 70wt%）, 100.0 grams of macroporous aluminium oxides（Pore volume 1.0ml/g, specific surface area
400m2/ g, butt 70wt%）, 133.3 grams of adhesives（Butt 30wt%, nitric acid is 0.4 with the mol ratio of small porous aluminum oxide）It is put into
Mixed grind in roller, adds water, and is rolled into paste, extrusion, and extrusion bar is then small in 550 DEG C of roastings 4 in 110 DEG C of dryings 4 hours
When, carrier HS-2 is obtained, property is 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 HC-2 is obtained, corresponding catalyst property is shown in Table 2.
Embodiment 9
By 22.2 grams of BJ-4 molecular sieves（Butt 90wt%）, 71.4 grams of amorphous silica-aluminas（SiO2Content 20wt%, pore volume
0.85ml/g, specific surface area 370m2/ g, butt 70wt%）, 128.6 grams of macroporous aluminium oxides（Pore volume 1.0ml/g, specific surface area
400m2/ g, butt 70wt%）, 133.3 grams of adhesives（Butt 30wt%, nitric acid is 0.4 with the mol ratio of small porous aluminum oxide）It is put into
Mixed grind in roller, adds water, and is rolled into paste, extrusion, and extrusion bar is then small in 550 DEG C of roastings 4 in 110 DEG C of dryings 4 hours
When, carrier HS-3 is obtained, property is 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 HC-3 is obtained, corresponding catalyst property is shown in Table 2.
Embodiment 10
By 44.4 grams of BJ-4 molecular sieves（Butt 90wt%）, 142.9 grams of amorphous silica-aluminas（SiO2Content 20wt%, pore volume
0.85ml/g, specific surface area 370m2/ g, butt 70wt%）, 28.6 grams of macroporous aluminium oxides（Pore volume 1.0ml/g, specific surface area
400m2/ g, butt 70wt%）, 133.3 grams of adhesives（Butt 30wt%, nitric acid is 0.4 with the mol ratio of small porous aluminum oxide）It is put into
Mixed grind in roller, adds water, and is rolled into paste, extrusion, and extrusion bar is then small in 550 DEG C of roastings 4 in 110 DEG C of dryings 4 hours
When, carrier HS-4 is obtained, property is 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 HC-4 is obtained, corresponding catalyst property is shown in Table 2.
Comparative example 4
By 33.3 grams of BD-1 molecular sieves（Butt 90wt%）, 85.7 grams of amorphous silica-aluminas（SiO2Content 20wt%, pore volume
0.85ml/g, specific surface area 370m2/ g, butt 70wt%）, 100.0 grams of macroporous aluminium oxides（Pore volume 1.0ml/g, specific surface area
400m2/ g, butt 70wt%）, 133.3 grams of adhesives（Butt 30wt%, nitric acid is 0.4 with the mol ratio of small porous aluminum oxide）It is put into
Mixed grind in roller, adds water, and is rolled into paste, extrusion, and extrusion bar is then small in 550 DEG C of roastings 4 in 110 DEG C of dryings 4 hours
When, carrier HDS-1 is obtained, property is 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 HDC-1 is obtained, corresponding catalyst property is shown in Table 2.
Comparative example 5
By 22.2 grams of BD-2 molecular sieves（Butt 90wt%）, 71.4 grams of amorphous silica-aluminas（SiO2Content 20wt%, pore volume
0.85ml/g, specific surface area 370m2/ g, butt 70wt%）, 128.6 grams of macroporous aluminium oxides（Pore volume 1.0ml/g, specific surface area
400m2/ g, butt 70wt%）, 133.3 grams of adhesives（Butt 30wt%, nitric acid is 0.4 with the mol ratio of small porous aluminum oxide）It is put into
Mixed grind in roller, adds water, and is rolled into paste, extrusion, and extrusion bar is then small in 550 DEG C of roastings 4 in 110 DEG C of dryings 4 hours
When, carrier HDS-2 is obtained, property is 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 HDC-2 is obtained, corresponding catalyst property is shown in Table 2.
The physico-chemical property of the catalyst carrier of table 2 and catalyst
| Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative example 4 | Comparative example 5 | |
| Carrier is constituted and property | ||||||
| Numbering | HS-1 | HS-2 | HS-3 | HS-4 | HDS-1 | HDS-2 |
| Beta-molecular sieve, wt% | 7 | 15 | 10 | 20 | 15 | 10 |
| Amorphous silica-alumina, wt% | 40 | 30 | 25 | 50 | 30 | 25 |
| Aluminum oxide | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Pore volume, mL/g | 0.73 | 0.69 | 0.74 | 0.66 | 0.71 | 0.64 |
| Specific surface area, m2/g | 428 | 456 | 418 | 459 | 399 | 386 |
| Catalyst is constituted and property | ||||||
| Numbering | HC-1 | HC-2 | HC-3 | HC-4 | HDC-1 | HCD-2 |
| WO3, wt% | 20.8 | 24.3 | 26.7 | 23.5 | 23.9 | 21.8 |
| NiO, wt% | 5.5 | 6.5 | 7.6 | 6.3 | 6.2 | 5.6 |
| Pore volume, mL/g | 0.53 | 0.46 | 0.48 | 0.47 | 0.48 | 0.44 |
| Specific surface area, m2/g | 315 | 322 | 276 | 336 | 269 | 246 |
Embodiment 11
This embodiment describes the catalyst activity evaluation result prepared by the present invention.On fixed bed hydrogenation experimental rig
Evaluated, appreciation condition is：Reaction stagnation pressure 16.0MPa, hydrogen to oil volume ratio 1500, volume space velocity 0.9h during liquid-1, use decompression
Distillate（VGO）Used as feedstock oil, raw material oil nature is listed in table 3.Catalyst HC-2, HD-1 are commented under identical process conditions
Valency, the evaluation result for obtaining is listed in table 4.
By evaluation result as can be seen that catalyst of the present invention is under identical process conditions, intermediate oil selectivity, receipts
Rate and product quality are superior to reference catalyst.
The raw material oil nature of table 3
| Feedstock oil | Vacuum distillate（VGO） |
| Density (20 DEG C), g/cm3 | 0.9072 |
| Boiling range, DEG C | |
| IBP/10% | 305/361 |
| 30%/50% | 394/417 |
| 70%/90% | 443/481 |
| 95%/EBP | 509/533 |
| Condensation point, DEG C | 34 |
| Sulphur, wt% | 1.98 |
| Nitrogen, μ g/g | 1228 |
| Carbon, wt% | 85.28 |
| Hydrogen, wt% | 12.46 |
| BMCI values | 45.0 |
Table 4 HC-1, HDC-1 and HDC-2 catalyst performance comparative evaluation condition and result
| Catalyst | HC-2 | HDC-1 | HDC-2 |
| Feedstock oil | Vacuum distillate | Vacuum distillate | Vacuum distillate |
| Volume space velocity during liquid, h-1 | 0.9 | 0.9 | 0.9 |
| Reaction stagnation pressure, MPa | 16.0 | 16.0 | 16.0 |
| Hydrogen to oil volume ratio | 1500:1 | 1500:1 | 1500:1 |
| Reaction temperature, DEG C | 390 | 398 | 405 |
| Product yield and property | |||
| Heavy naphtha | |||
| Yield, wt% | 4.6 | 5.7 | 5.9 |
| Virtue is latent, wt% | 58.2 | 51.5 | 50.9 |
| Jet fuel | |||
| Yield, wt% | 18.4 | 20.3 | 19.8 |
| Smoke point, mm | 26 | 25 | 24 |
| Aromatic hydrocarbons, v% | 7.8 | 8.6 | |
| Diesel oil | |||
| Yield, wt% | 47.9 | 43.6 | 42.1 |
| Condensation point, DEG C | -16 | -5 | -6 |
| Cetane number | 50.7 | 47.6 | 46.9 |
| Tail oil | |||
| Yield, wt% | 25.5 | 25.9 | 25.3 |
| Condensation point, DEG C | 12 | 25 | 27 |
| BMCI values | 12.5 | 15.3 | 16.8 |
| Chemical hydrogen consumption, wt% | 2.06 | 2.19 | 2.23 |
Claims (23)
1. a kind of hydrocracking catalyst, comprising hydrogenation active metals component and carrier, wherein carrier is comprising beta-molecular sieve, without fixed
Shape sial and aluminum oxide, the property of the beta-molecular sieve are as follows：Specific surface area is 400m2/g~800m2/ g, total pore volume is 0.4ml/g
~ 0.55mL/g, SiO2/Al2O3Mol ratio be 30 ~ 60, relative crystallinity be 120% ~ 140%, meleic acid amount be 0.55 ~
1.0mmol/g, non-framework aluminum accounts for less than 1%, NH of total aluminium3The middle strong acid that-TPD methods are measured acid amount account for total acid content 70% ~
85%, Na2O≤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 3% ~ 20%, and the content of amorphous silica-alumina is 10% ~ 70%, the content of aluminum oxide for 15% ~
70%。
6. according to the catalyst described in claim 1, it is characterised in that：SiO in described amorphous silica-alumina2Weight content be
5% ~ 40%, the pore volume of amorphous silica-alumina is 0.6 ~ 1.1mL/g, and specific surface area is 300 ~ 500m2/g。
7. according to the catalyst described in claim 1, it is characterised in that：Described hydrogenation active metals are vib He ∕ or the
The metal of VIII, vib metals be Mu He ∕ or tungsten, the metal of group VIII is Gu He ∕ 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, vib metals with the content that oxide is counted be 10.0% ~ 30.0%, group VIII metal containing in terms of oxide
Measure is 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 is 0.35 ~ 0.60mL/g.
10. the preparation method of any described catalyst of claim 1 ~ 9, including：The preparation of carrier and load hydrogenation activity gold
Category component, the preparation process of wherein carrier is as follows：By beta-molecular sieve, amorphous silica-alumina, aluminum oxide mechanical mixture, it is molded, then
Dry and be calcined, be made 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 dries, and obtains beta-molecular sieve,
In the highly basic weak solution, the concentration of diluted alkaline is with OH-0.01 ~ 0.2mol/L of meter.
11. in accordance with the method for claim 10, it is characterised in that step（1）The property of beta-molecular sieve original powder 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, beta-molecular sieve original powder is placed in container
In, using temperature programming, heating rate is 50 ~ 150 DEG C/h, when rising to 250 ~ 450 DEG C, starts to introduce water vapour, Ran Hou
500 ~ 650 DEG C are warming up to while introducing water vapour, and are processed 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-0.02 ~ 0.15mol/L of meter.
17. 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。
18. 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.
19. 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.
20. 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
Dried 3 ~ 6 hours under part.
21. 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, are then calcined 2.5 ~ 6.0 hours at 450 DEG C ~ 550 DEG C.
22. in accordance with the method for claim 10, it is characterised in that：Described aluminum oxide is using macroporous aluminium oxide He ∕ or small
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。
23. 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 are as follows：In 100 DEG C ~ 150 DEG C dryings 1 ~ 12 hour, then 450 DEG C ~
550 DEG C are calcined 2.5 ~ 6.0 hours.
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