CN109718837A - Hydrocracking catalyst and its preparation method and application - Google Patents
Hydrocracking catalyst and its preparation method and application Download PDFInfo
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Abstract
This disclosure relates to a kind of hydrocracking catalyst and its preparation method and application, on the basis of the dry weight of catalyst, the catalyst includes with the carrier of 45~90 weight % of dry basis, the first metal component of 1~40 weight % in terms of metal oxide, and the second metal component of 1~15 weight % in terms of metal oxide；The carrier includes phosphorus-contained gamma-type molecular sieve, aluminium oxide and silica, and the weight ratio of the phosphorus-contained gamma-type molecular sieve, aluminium oxide and silica is 1:(0.03~20): (0.03~20)；First metal is the metal selected from group VIB；Second metal component is the metal selected from group VIII；In terms of oxide, the phosphorus content of the phosphorus-contained gamma-type molecular sieve is 0.3~5 weight 0.2~0.95mL/g of %, Kong Rongwei, and the ratio of the infrared B acid of pyridine and L acid is 2~10.Catalyst hydrocracking reaction activity with higher.
Description
Technical field
This disclosure relates to a kind of hydrocracking catalyst and its preparation method and application.
Background technique
Industry is hydrocracked charging 350~540 DEG C of fractions such as including VGO and grinds containing a large amount of polycyclic aromatic hydrocarbon and cycloalkane
Study carefully and show be hydrocracked high conversion region, arene content reduces in heavy end, and naphthene content is higher, this makes out
Ring performance, which becomes, improves tail oil quality, improves the effective means of boat coal smoke point.However since the β key in cycloalkane is being in cycloalkanes just
In the vertical direction of carbon ion sky p track, so that the two is not easily formed coplanar conformation, it is stronger that this needs opening cyclic paraffins
Acidity.Molecular sieve acidity with higher, is widely used in hydrocracking reaction.However common HY molecular sieve structure shakiness
It is fixed, framework dealumination is easy to happen in catalyst preparation and use process, the non-framework aluminum generated during system with molecular sieve for preparing is standby is logical
It is often acid weaker, the acid site B is shielded, catalyst performance reduces.Surpassed by second group of hydro-thermal process, introducing grading mode
Steadyization processing can be with molecular sieves stabilized structure.The second component wherein introduced generally includes alkene local soil type point and phosphorus component.Due to roasting
Phosphorus forms the bigger phosphorus aluminum oxide complex of molecular weight, this species complex with the non-framework aluminum removed in molecular sieve during burning
With higher thermal stability, framework dealumination is conducive to prevent, so that its work that can replace alkene local soil type point to a certain extent
With.
Patent CN1279130A discloses a kind of preparation method of phosphorus-contained gamma-type molecular sieve, and this method includes that will contain 0.5-5
Weight % is (with P2O5Meter) phosphorus, Na2O content is 0.5-6 weight %, the P-NH that lattice constant is 2.460-2.475 nanometers4NaY
Molecular sieve 450-700 DEG C hydrothermal calcine 0.5-4 hours under 100% steam atmosphere in roaster；By the product after roasting
Carry out the reaction of liquid phase aluminium-eliminating and silicon-replenishing；Then it filters, washs.Resulting phosphorous super-stable Y molecular sieves have good product selectivity
With hydrothermal stability and preferable anti-vanadium poisoning performance, the Cracking catalyst containing the molecular sieve is reacted for cracking hydrocarbon
When yield of light oil it is high, coke yield is low, and heavy oil conversion performance is high, and the olefin(e) centent in gasoline is low.
Patent ZL200410071122.6 discloses a kind of phosphorus containing molecular sieve, which contains 85~99.9 weight %'s
Molecular sieve and with P2O5Meter, the phosphorus of 0.1~15 weight %, the molecular sieve31In PMAS-NMR spectrogram, chemical shift be 0 ±
The peak area at the peak 1.0ppm accounts for the percentage of total peak area less than 1%.The preparation method of the molecular sieve is included in molecular sieve
Phosphorus is introduced, and washs the molecular sieve with the aqueous solution containing acid, acid therein is selected from one of water-soluble organic acid, inorganic acid
Or it is several, sour content is 0.0001-10.0 mol/L, and the temperature of washing is -95 DEG C of room temperature.The inventive features are, are drawing
After entering phosphorus, include the steps that a molecular sieve described in acid solution wash, is urged using being hydrocracked for phosphorus containing molecular sieve preparation
Agent has higher hydrogenation cracking activity while keeping highly selective.
The prior art usually post-processes phosphorus containing molecular sieve, to further increase the stability and acidity of molecular sieve.
These post-processing approach generally comprise heat treatment and acid processing.The incorporation way of water includes two kinds of sides in usual hydrothermal treatment process
Formula is passed through water vapour, the water that material autogenous roasting is released in roasting process.In two ways, due to temperature
Raising, water vapor pressure sharply increases, in order to enable existing equipment can bear reaction pressure requirement, generallys use open body
System, this makes powder in water-heat process as water vapour constantly takes system out of, and reaction system is in non-steady state operation, so that producing
Quality is not high, although gained molecular sieve has certain open loop activity, but still is not able to satisfy actual demand.
Summary of the invention
Purpose of this disclosure is to provide a kind of hydrocracking catalyst and its preparation method and application, the catalyst have compared with
High hydrocracking reaction activity.
To achieve the goals above, disclosure first aspect: providing a kind of hydrocracking catalyst, with the butt of catalyst
On the basis of weight, which includes 1~40 with the carrier of 45~90 weight % of dry basis, in terms of metal oxide
The first metal component of weight %, and the second metal component of 1~15 weight % in terms of metal oxide；
The carrier includes phosphorus-contained gamma-type molecular sieve, aluminium oxide and silica, the phosphorus-contained gamma-type molecular sieve, aluminium oxide and oxygen
The weight ratio of SiClx is 1:(0.03~20): (0.03~20)；First metal is the metal selected from group VIB；Described
Two metal components are the metal selected from group VIII；
In terms of oxide, the phosphorus content of the phosphorus-contained gamma-type molecular sieve is 0.3~5 0.2~0.95mL/ of weight %, Kong Rongwei
The ratio of g, the infrared B acid of pyridine and L acid is 2~10.
Optionally, on the basis of the dry weight of catalyst, which includes 55~85 weights with dry basis
The carrier of amount %, the first metal component of 12~35 weight % in terms of metal oxide, and 2~10 in terms of metal oxide
The second metal component of weight %；
The weight ratio of the phosphorus-contained gamma-type molecular sieve, aluminium oxide and silica is 1:(0.1~15): (0.1~15).
Optionally, the Al of the phosphorus-contained gamma-type molecular sieve27In-NMR structure spectrogram, I60ppm/I-1ppmFor 5~40, I-1ppm/
I±6ppmIt is 0.4~2.
Optionally, the phosphorus-contained gamma-type molecular sieve is prepared by a method comprising the following steps to obtain:
A, make phosphorus containing molecular sieve raw material at 350-700 DEG C of temperature, pressure be 0.1-2MPa and in the presence of water vapor into
Row hydro-thermal process 0.5-10h, the molecular sieve material after obtaining hydro-thermal process；In terms of oxide and with the dry of phosphorus containing molecular sieve raw material
On the basis of base weight amount, the phosphorus content of the phosphorus containing molecular sieve raw material is 0.1~15 weight %, and sodium content is 0.5~4.5 weight
Measure %；
B, add water to be beaten the molecular sieve material after the hydro-thermal process that step a is obtained, molecular sieve pulp is obtained, by this
Molecular sieve pulp is heated to 40~95 DEG C, then keeps temperature and acid solution, the acid are continuously added into the molecular sieve pulp
The ratio of sour weight and the dry weight of the phosphorus containing molecular sieve raw material is (0.01-0.6) in solution: 1, with molecule described in 1L
On the basis of screening the pulp liquid, with H+Meter, the addition speed of the acid solution are 0.05-10 mols/hr, isothermal reaction after acid adding
0.5-20h collects solid product.
Optionally, in step a, the phosphorus containing molecular sieve raw material is phosphorous Y type molecular sieve, the phosphorous Y type molecule
The lattice constant of sieve is 2.425~2.47nm, and specific surface area is 250~750m20.2~0.95ml/g of/g, Kong Rongwei.
Optionally, in step a, the water content of the phosphorus containing molecular sieve raw material is 10~40 weight %；
The phosphorus containing molecular sieve raw material is graininess, and particle size range is containing for the phosphorus containing molecular sieve raw material of 1mm~500mm
Amount is 10~100 weight % of phosphorus containing molecular sieve raw material gross weight, and the granularity is in terms of the circumscribed circular diameter of particle.
Optionally, the content for the phosphorus containing molecular sieve raw material that particle size range is 1mm~500mm is phosphorus containing molecular sieve raw material gross weight
30~100 weight % of amount；
Preferably, the content for the phosphorus containing molecular sieve raw material that particle size range is 5mm~100mm is phosphorus containing molecular sieve raw material gross weight
30~100 weight % of amount.
Optionally, in step b, the weight of water and phosphorus containing molecular sieve raw material in the molecular sieve pulp that is obtained after mashing
The ratio of dry weight is (14-5): 1.
Optionally, the preparation step of the phosphorus-contained gamma-type molecular sieve further include: in step b, during acid solution is added
Ammonium salt is added into the molecular sieve pulp, the ammonium salt is selected from least one of ammonium nitrate, ammonium chloride and ammonium sulfate, institute
The ratio for stating the weight of ammonium salt and the dry weight of phosphorus containing molecular sieve raw material is (0.1-2.0): 1.
Optionally, in step b, the acid concentration of the acid solution is 0.01~15.0mol/L, the acid for selected from phosphoric acid,
At least one of sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid and acetic acid.
Optionally, the preparation step of the phosphorus-contained gamma-type molecular sieve further include: solid product is collected, then washes, is dry,
Obtain phosphorus containing molecular sieve；The condition of the drying are as follows: temperature is 50~350 DEG C, preferably 70~200 DEG C；Time be 1~for 24 hours,
Preferably 2~6h.
Optionally, first metal is molybdenum and/or tungsten；Second metal is at least one in iron, nickel and cobalt
Kind.
The disclosure third aspect: providing a kind of method for preparing hydrocracking catalyst described in disclosure first aspect,
It is impregnated this method comprises: contacting the maceration extract containing metal precursor with carrier, the material that then will be obtained after dipping
It is dry.
Optionally, this method further include: by phosphorus-contained gamma-type molecular sieve, aluminium oxide, the precursor of silica, peptizing agent, and
Then optional mix lubricant forms, is dry, roasting obtains the carrier；
The precursor of the silica is Silica hydrogel, the white carbon for being 0 weight of weight %~60 % selected from silica solution, loss on ignition
At least one of black and superfine silicon dioxide.
Optionally, the metal precursor includes the first metal precursor and the second metal precursor, wherein described first
Metal precursor be in the inorganic salts and the first metallo-organic compound of inorganic acid selected from the first metal, the first metal at least
It is a kind of；The inorganic salts are selected from nitrate, carbonate, subcarbonate, hypophosphites, phosphate, sulfate and chloride
At least one of；Organic substituent in first metallo-organic compound is selected from hydroxyl, carboxyl, amido, ketone group, ether
At least one of base, alkyl；
Second metal precursor is to have selected from bimetallic inorganic acid, bimetallic inorganic salts and the second metal
At least one of machine compound；The inorganic salts are selected from nitrate, carbonate, subcarbonate, hypophosphites, phosphoric acid
At least one of salt, sulfate and chloride；Organic substituent in second metallo-organic compound be selected from hydroxyl,
At least one of carboxyl, amido, ketone group, ether, alkyl.
Optionally, also contain organic additive in the maceration extract；The concentration of the organic additive is 2-300g/L；Institute
Stating organic additive is selected from ethylene glycol, glycerine, polyethylene glycol, diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, ammonia
Base triacetic acid, 1,2- cyclohexanediamine tetraacetic acid, citric acid, tartaric acid, malic acid, ethylenediamine, diethylenetriamines, hexamethylene two
At least one of amine tetraacethyl, amion acetic acid, nitrilotriacetic acid, ethylenediamine tetra-acetic acid and ethylenediamine tetra-acetic acid ammonium.
Optionally, the condition of the drying are as follows: temperature is 80-350 DEG C, and the time is 0.5-24 hours.
Optionally, this method further includes the steps that roast after the dry materials after contact, the condition of the roasting
Are as follows: temperature is 350-600 DEG C, and the time is 0.2-12 hours.
The disclosure third aspect: hydrocracking catalyst described in a kind of disclosure first aspect is provided in hydrocarbon raw material
Application in hydrocracking reaction.
Optionally, the hydrocarbon raw material is selected from straight run gas oil, vacuum gas oil (VGO), metal removal oil, reduced crude, de- drip
At least one of green decompression residuum, coker distillate, catalytic cracking distillate oil, shale oil, asphalt sand oil and liquefied coal coil；
The condition of the hydrocracking reaction are as follows: reaction temperature is 200-650 DEG C, preferably 300-510 DEG C；Reaction pressure
For 3-24 megapascal, preferably 4-15 megapascal；Liquid hourly space velocity (LHSV) is 0.1-10 hours-1, preferably 0.2-5 hours-1；Hydrogen to oil volume ratio
For 100-5000, preferably 200-1000.
Through the above technical solutions, the disclosure is carried out at special hydro-thermal process and pickling using phosphorus containing molecular sieve raw material
The phosphorus containing molecular sieve haveing excellent performance has been made in reason, and B acid acid amount is further increased with L acid acid molar ratio value, using the phosphorous molecule
The hydrocracking catalyst of sieve preparation has higher hydrogenation cracking activity and selectivity of ring-opening.
Other feature and advantage of the disclosure will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Attached drawing is and to constitute part of specification for providing further understanding of the disclosure, with following tool
Body embodiment is used to explain the disclosure together, but does not constitute the limitation to the disclosure.In the accompanying drawings:
Fig. 1 is the Al for preparing embodiment 1-3 and preparing molecular sieve prepared by comparative example 1-427- NMR structure spectrogram.
Specific embodiment
It is described in detail below in conjunction with specific embodiment of the attached drawing to the disclosure.It should be understood that this place is retouched
The specific embodiment stated is only used for describing and explaining the disclosure, is not limited to the disclosure.
Disclosure first aspect: providing a kind of hydrocracking catalyst, on the basis of the dry weight of catalyst, the catalysis
Agent includes the first metal of 1~40 weight % with the carrier of 45~90 weight % of dry basis, in terms of metal oxide
Component, and the second metal component of 1~15 weight % in terms of metal oxide；Preferably, it is with the dry weight of catalyst
Benchmark, the catalyst include 12~35 weights with the carrier of 55~85 weight % of dry basis, in terms of metal oxide
Measure the first metal component of %, and the second metal component of 2~10 weight % in terms of metal oxide.The carrier includes containing
Phosphorus Y type molecular sieve, aluminium oxide and silica, the weight ratio of the phosphorus-contained gamma-type molecular sieve, aluminium oxide and silica are 1:(0.03
~20): (0.03~20), preferably 1:(0.1~15): (0.1~15).First metal is the metal selected from group VIB；
Second metal component is the metal selected from group VIII.
In the hydrocracking catalyst of the disclosure, the phosphorus-contained gamma-type molecular sieve as carrier component has special performance, makes
Obtaining hydrocracking catalyst has higher hydrogenation cracking activity and selectivity of ring-opening.In terms of oxide, the phosphorus-contained gamma-type molecule
The phosphorus content of sieve is 0.3~5 weight 0.2~0.95mL/g of %, Kong Rongwei, and the ratio of the infrared B acid of pyridine and L acid is 2~10.
The ratio of phosphorus-contained gamma-type molecular sieve the B acid acid amount and L acid acid amount with higher.Especially specifically, described to contain
Phosphorus Y type molecular sieve not only remains the ratio of higher framework aluminum and non-framework aluminum, also retains centainly in non-framework aluminum position
The position -4~-6ppm or the position 3~7ppm non-framework aluminum.Specifically, the Al of the molecular sieve27In-NMR structure spectrogram,
In 60 ± 1ppm and the framework aluminum of -1 ± 1ppm and peak height ratios, that is, I of non-framework aluminum60ppm/I-1ppmIt is 5~40；And non-skeleton
There are two types of obvious characteristic peaks at the 0ppm chemical shift of aluminium: -1 ± 1ppm, and -5.5 ± 2ppm or 3~7ppm, the peak of the two
Ratios, that is, I-1ppm/I±6ppmIt is 0.4~2, preferably 0.8~2, wherein I±6ppmTake -5.5 ± 2ppm and 3~7ppm peak height
The larger value.
The phosphorus-contained gamma-type molecular sieve is to carry out special hydro-thermal process and pickling processes using phosphorus containing molecular sieve raw material to prepare
It obtains.Specifically, the phosphorus-contained gamma-type molecular sieve is prepared by a method comprising the following steps to obtain:
A, make phosphorus containing molecular sieve raw material at 350-700 DEG C of temperature, pressure be 0.1-2MPa and in the presence of water vapor into
Row hydro-thermal process 0.5-10h, the molecular sieve material after obtaining hydro-thermal process；In terms of oxide and with the dry of phosphorus containing molecular sieve raw material
On the basis of base weight amount, the phosphorus content of the phosphorus containing molecular sieve raw material is 0.1~15 weight %, and sodium content is 0.5~4.5 weight
Measure %；
B, add water to be beaten the molecular sieve material after the hydro-thermal process that step a is obtained, molecular sieve pulp is obtained, by this
Molecular sieve pulp is heated to 40~95 DEG C, then keeps temperature and acid solution, the acid are continuously added into the molecular sieve pulp
The ratio of sour weight and the dry weight of the phosphorus containing molecular sieve raw material is (0.01-0.6) in solution: 1, with molecule described in 1L
On the basis of screening the pulp liquid, with H+Meter, the addition speed of the acid solution are 0.05-10 mols/hr, isothermal reaction after acid adding
0.5-20h collects solid product.
According to the disclosure, in step a, the phosphorus containing molecular sieve raw material refers to phosphorous molecular sieve.By using phosphorous molecule
Raw material is sieved, the phosphorus aluminium species outside framework of molecular sieve can be improved the skeleton stability of molecular sieve, to further increase molecular sieve
Performance.The structure of the phosphorus containing molecular sieve raw material can be faujasite molecular sieve structure, preferably phosphorous Y type molecule
Sieve, lattice constant can be 2.425~2.47nm, and specific surface area can be 250~750m2/ g, Kong Rongke with for 0.2~
0.95ml/g.Further, the specific choice of the Y type molecular sieve can change in very large range, as long as making described contain
Phosphorus molecular sieve raw material meets above-mentioned condition, for example, the Y type molecular sieve can be for selected from NaY, HNaY (hydrogen Y type molecule
Sieve), REY (rare earth Y type molecular sieve), USY (super-stable Y molecular sieves) etc..The cation-bit of the phosphorous Y type molecular sieve can be with
It is occupied by one or more of sodium ion, ammonium ion, hydrogen ion；Or it is also possible to before molecular sieve introduces phosphorus
Or later, by conventional ion exchange, keep sodium ion therein, ammonium ion, hydrogen ion all or part of by other ion institutes
Replace.The phosphorus containing molecular sieve raw material can be commercially available commodity, arbitrary prior art preparation can also be used, for example, can
Using the disclosed preparation of method or patent Zl200410071122.6 for preparing USY disclosed in patent ZL00123139.1
The method etc. of PUSY, the disclosure repeats no more.
According to the disclosure, in step a, the water content of the phosphorus containing molecular sieve raw material is preferably 10~40 weight %.Have
The phosphorus containing molecular sieve raw material of above-mentioned water content can be by filtering after adding water to be beaten in molecular sieve, being dried to obtain.Also, it is described to contain
Phosphorus molecular sieve raw material is preferably graininess, and particle size range be 1mm~500mm phosphorus containing molecular sieve raw material content can for containing
10~100 weight % of phosphorus molecular sieve raw material gross weight, preferably 30~100 weight %.Further, particle size range 5mm
The content of the phosphorus containing molecular sieve raw material of~100mm is 30~100 weight % of phosphorus containing molecular sieve raw material gross weight.Wherein, described
Granularity is in terms of the circumscribed circular diameter of particle.Carrying out hydro-thermal process using the phosphorus containing molecular sieve raw material of above-mentioned particle size range can obviously change
The mass transfer effect of kind hydro-thermal process reduces material and runs damage, improves the stability of operation.The granularity controlling party of the Molecular sieve raw material
Method can be this field routine, such as sieve method, extrusion method, rolling ball method etc..
According to the disclosure, the meaning of the described plus water mashing in step b is well known to those skilled in the art, after mashing
To the molecular sieve pulp in the weight of water and the ratio of dry weight of phosphorus containing molecular sieve raw material can be (14-5): 1.
According to the disclosure, in step b, the molecular sieve pulp is preferably heated to 50~85 DEG C, then keeps temperature simultaneously
Acid solution continuously is added into the molecular sieve pulp, the stopping when weight of the acid in the acid solution of addition reaches set amount.
It is the most key in the preparation step of the phosphorus-contained gamma-type molecular sieve, by the way of continuous acid adding, pickling is carried out in acid adding
Reaction, and acid adding speed is slower, so that dealumination process more mitigates, is conducive to the performance for improving molecular sieve.
According to the disclosure, the acid solution can be continuously added at one time in the molecular sieve pulp, i.e., according to spy
Fixed acid adding speed continues to add whole acid solutions, and then constant temperature is reacted again.Particularly, in order to improve the utilization of material
Rate simultaneously reduces waste output, and the acid solution can also be added several times.For example, the acid solution can be according to specific acid adding
Speed, which is divided 2-10 times, to be added in the molecular sieve pulp, after each acid adding can isothermal reaction be further continued for carrying out down for a period of time
Primary acid adding, until adding the acid solution of set amount.When the acid solution is added several times, in the acid solution
The ratio of the dry weight of the weight and phosphorus containing molecular sieve raw material of acid is preferably (0.01-0.3): 1.The acid of the acid solution
Concentration can be 0.01~15.0mol/L, and pH value can be 0.01~3.The acid can for conventional inorganic acid and/it is organic or
Acid, such as can be at least one in phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid and acetic acid
Kind.
According to the disclosure, the preparation step of the phosphorus-contained gamma-type molecular sieve can also include: that acid solution is being added in step b
During be added ammonium salt into the molecular sieve pulp, the ammonium salt can be in ammonium nitrate, ammonium chloride and ammonium sulfate
At least one, the ratio of the dry weight of the weight and phosphorus containing molecular sieve raw material of the ammonium salt can be (0.1-2.0): 1.Institute
Stating ammonium salt can be added independently of the acid solution into the molecular sieve pulp, can also amount as required be formulated as containing ammonium
The aqueous solution of salt and acid, and the aqueous solution is added into the molecular sieve pulp.
According to the disclosure, the preparation step of the phosphorus-contained gamma-type molecular sieve can also include: collection solid product, then water
It washes, dry, obtain phosphorus-contained gamma-type molecular sieve.The washing and the dry conventional steps to prepare molecular sieve, the disclosure be not special
Limitation.For example, the drying can be to be carried out using the methods of baking oven, mesh belt, converter heating, dry condition can be with are as follows:
Temperature is 50~350 DEG C, preferably 70~200 DEG C；Time be 1~for 24 hours, preferably 2~6h.
According to the disclosure, the aluminium oxide may include gibbsite such as water mine aluminium (gibbsite), bayerite promise three
Diaspore (bayerite nordstrandite) and a diaspore such as boehmite (boehmite, diaspor,
pseudoboehmite)。
According to the disclosure, under preferable case, first metal is molybdenum and/or tungsten；Second metal is selected from iron, nickel
At least one of with cobalt.
Disclosure second aspect: providing a kind of method for preparing hydrocracking catalyst described in disclosure first aspect,
It is impregnated this method comprises: contacting the maceration extract containing metal precursor with carrier, the material that then will be obtained after dipping
It is dry.Wherein any one method well known to art technology can be used with the contact impregnation method of carrier in maceration extract, such as
It include loading group vib metal component, group VIII metal component and organic additive disclosed in patent CN200810241082.3
Method on to catalyst carrier, wherein group vib metal component, group VIII metal component and organic additive are loaded to and urged
Process on agent carrier is any one in following manner:
Mode 1: catalyst carrier is contacted with the first solution, is then contacted again with the second solution, or catalyst is carried
Body is contacted with the second solution, is then contacted again with the first solution, wherein the first solution contains the compound of group vib metal component
With the compound of group VIII metal component, the second solution contains the compound of group vib metal component but without group VIII metal group
The compound divided, the first solution and/or the second solution contain the organic additive；
Mode 2: catalyst carrier is contacted with third solution, is then contacted again with the 4th solution, or catalyst is carried
Body is contacted with the 4th solution, is then contacted again with third solution, wherein and third solution contains the compound of group vib metal component,
4th solution contain group VIII metal component compound and organic additive but be free of group vib metal component compound, third
Compound and organic additive of the solution with or without group VIII metal component,
Wherein, after each contact, the catalyst carrier docked after touch is heated.
The preparation method of the carrier is well known to those skilled in the art, and the disclosure does not have special limitation.For example, should
Method can also include: to mix phosphorus-contained gamma-type molecular sieve, aluminium oxide, the precursor of silica, solvent and optional auxiliary agent, so
It forms afterwards and dry, obtains the carrier.It is 0 weight %~60 that the precursor of the silica, which is selected from silica solution, loss on ignition,
At least one of Silica hydrogel, White Carbon black and superfine silicon dioxide of weight %.The molding method can be using routine
Various methods, such as compression molding, roller forming or extruded moulding.The solvent is common molten during shaping of catalyst
Agent.When using the method for extrusion molding, appropriate amount of addition agent is preferably added in order to form.
Optionally, the preparation method of the carrier include: by phosphorus-contained gamma-type molecular sieve, aluminium oxide, silica precursor,
Then peptizing agent and optional mix lubricant form, are dry, roasting obtains the carrier.The peptizing agent can for containing
Acid solution contains aqueous slkali, at least one in acid organic acid or inorganic acid known to those skilled in the art
Kind, such as in phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, tungstenic and/or molybdenum heteropolyacid, citric acid, tartaric acid, formic acid and acetic acid
At least one can also add in acid-containing solution so that it keeps the cations such as acid ammonium, iron, cobalt, nickel, aluminium；Packet containing aqueous slkali
Include at least one of ammonia, organic amine, urea.
The disclosure does not require the shape of the carrier particularly, can be spherical shape, bar shaped, hollow bar shaped, spherical shape,
Bulk etc., bar shaped carrier can be more clover shapes such as cloverleaf pattern, bunge bedstraw herb shape and their deformable body.
In a kind of optional embodiment of the disclosure, carrier side as disclosed in patent CN107029779A
Method preparation, specifically: (1) phosphorus-contained gamma-type molecular sieve, aluminium oxide, the precursor of silica, peptizing agent, lubricant and water are mixed,
Obtain mixture, the dosage of each component make the amount of the substance of peptizing agent and the weight ratio of powder 0.28 in the mixture ×
10-4~4.8 × 10-4Mol/g, the ratio between weight and the amount of substance of peptizing agent of water are 2.0 × 103~30 × 103G/mol, institute
The weight for stating powder is the sum of the phosphorus-contained gamma-type molecular sieve, aluminium oxide, the weight of precursor of silica, the peptizing agent object
The amount of matter refers to the molal quantity that H proton is measured in the peptizing agent；The lubricant be one of sesbania powder, graphite or
Two kinds, on the basis of powder weight, lubricant content in powder is 1~9 weight %；(2) step (1) is obtained mixed
It closes object kneading, molding, drying and roasts, obtain carrier.
According to the disclosure, the metal precursor includes the first metal precursor and the second metal precursor.Wherein, described
First metal precursor is the soluble compound containing first metal, inorganic acid, the first metal including the first metal
Inorganic salts and at least one of the first metallo-organic compound；The inorganic salts can be for selected from nitrate, carbonate, alkali
At least one of formula carbonate, hypophosphites, phosphate, sulfate and chloride；In first metallo-organic compound
Organic substituent be selected from least one of hydroxyl, carboxyl, amido, ketone group, ether, alkyl.For example, working as first gold medal
Belong to be molybdenum when, first metal precursor can for selected from molybdic acid, para-molybdic acid, molybdate, paramolybdate and at least one
Kind；When first metal is tungsten, first metal precursor can be for selected from wolframic acid, metatungstic acid, ethyl metatungstic acid, tungsten
At least one of hydrochlorate, metatungstate, ethyl metatungstate.Second metal precursor is bimetallic containing described the
Soluble compound, including in bimetallic inorganic acid, bimetallic inorganic salts and the second metallo-organic compound extremely
Few one kind；The inorganic salts can for selected from nitrate, carbonate, subcarbonate, hypophosphites, phosphate, sulfate and
At least one of chloride；Organic substituent in second metallo-organic compound be selected from hydroxyl, carboxyl, amido,
At least one of ketone group, ether, alkyl.
According to the disclosure, organic additive can also be contained in the maceration extract；The concentration of the organic additive can be with
For 2-300g/L.The organic additive is oxygen-containing organic compound and/or organic compounds containing nitrogen.Specifically, described oxygen-containing
Organic compound can be for selected from ethylene glycol, glycerine, polyethylene glycol (molecular weight can be 200~1500), diethylene glycol, fourth
In glycol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2- cyclohexanediamine tetraacetic acid, citric acid, tartaric acid and malic acid
At least one；The organic compounds containing nitrogen can be for selected from ethylenediamine, diethylenetriamines, 1,2-diaminocyclohexane tetraacetic acid, ammonia
At least one of guanidine-acetic acid, nitrilotriacetic acid, ethylenediamine tetra-acetic acid and ethylenediamine tetra-acetic acid ammonium.
In the method for preparing hydrocracking catalyst of the disclosure, the temperature of the contact is not particularly limited, and can be
The attainable various temperature of maceration extract institute.The time of dipping is also not particularly limited, as long as catalyst carrier can be made to load institute
The metal active constituent predecessor of requirement.Under normal circumstances, dipping temperature is higher, and impregnation concentration is bigger, reaches same
Impregnation increment (i.e. catalyst carrier dipping after with the weight difference before dipping) needed for time it is shorter；Vice versa.When required leaching
After stain amount and condition determine, those skilled in the art are easy to select suitable dip time according to the introduction of the disclosure.This public affairs
It opens and dipping method is not required particularly, the dipping can be saturation dipping, be also possible to supersaturated dipping.The dipping
Environment there is no particular limitation, can be under air-proof condition according to the conventional method in this field, can also be in open environment
Middle progress can supplement the aqueous solvent of loss in dipping process, can not also supplement.It can be passed through in dipping process various
Gas, such as air, nitrogen, vapor etc. can not also be passed through any new component.
In the method for preparing hydrocracking catalyst of the disclosure, the condition of the drying does not have special limitation, can be with
It is various drying conditions commonly used in the art, such as can be with are as follows: temperature is 80-350 DEG C, and preferably 100-300 DEG C, the time is
0.5-24 hours, preferably 1-12 hours.
It can also include that will be carried out after the dry materials after contact in the method for preparing hydrocracking catalyst of the disclosure
The step of roasting, described to be roasted to the conventional steps for preparing catalyst, the disclosure does not have special limitation.The condition of the roasting
It such as can be with are as follows: temperature is 350-600 DEG C, preferably 400-550 DEG C；Time is 0.2-12 hours, preferably 1-10 hours.
The hydrocracking catalyst that the disclosure provides can be used as various acid catalysis catalyst for catalytic cracking, hydro-isomerization
Change, be alkylated, being hydrocracked etc. in reaction, especially suitable for being hydrocracked to hydrocarbon raw material, having with production compared with low boiling
The hydrocarbon fraction of point and lower molecular weight.Therefore, the disclosure third aspect: being provided described in a kind of disclosure first aspect plus hydrogen
Application of the Cracking catalyst in the hydrocracking reaction of hydrocarbon raw material.
Wherein, the hydrocarbon raw material can be various heavy mineral oils or synthetic oil or their mixed fraction oil, such as straight
Evaporate gas oil (straight run gas oil), vacuum gas oil (VGO) (vacuum gas oil), metal removal oil
(demetallized oils), reduced crude (atmospheric residue), de-asphalted vacuum residue (deasphalted
Vacuum residue), coker distillate (coker distillates), catalytic cracking distillate oil (cat craker
Distillates), shale oil (shale oil), asphalt sand oil (tar sand oil), liquefied coal coil (coal liquid)
Deng.Particularly, catalyst being hydrocracked to produce boiling range and be especially suitable for heavy and inferior distillate oil that the disclosure provides
149-371 DEG C, especially boiling range are the hydrocracking process of 180-370 DEG C of intermediate oil.
The hydrocracking catalyst that the disclosure provides preferably also wraps in the application in the hydrocracking reaction of hydrocarbon raw material
Include using before the hydrocracking catalyst, in presence of hydrogen, at a temperature of 140-370 DEG C with sulphur, hydrogen sulfide or
Presulfurization is carried out to the hydrocracking catalyst containing sulfur feedstock, this presulfurization can carry out outside device, can also be in situ in device
Vulcanization, is translated into sulfide type.
When the catalyst that the disclosure provides is used for distillate hydrocracking, it can make under the conditions of conventional hydrocracking process
With for example, the condition of the hydrocracking reaction are as follows: 200-650 DEG C of reaction temperature, preferably 300-510 DEG C, reaction pressure 3-24
Megapascal, preferably 4-15 megapascal, liquid hourly space velocity (LHSV) 0.1-10 hour -1 0.2-5 hours preferred -1, hydrogen to oil volume ratio 100-5000, preferably
200-1000。
The device of the hydrocracking reaction can it is any be enough to make the hydrocarbon raw material under hydrogenation conditions with
It is carried out in the catalytic reaction unit of catalyst, such as can be fixed bed reactors, moving-burden bed reactor, ebullated bed
Reactor or paste state bed reactor.
The disclosure is described further below by embodiment, but does not therefore limit content of this disclosure.
The Kong Rong of molecular sieve, specific surface area use 2400 type automatic absorbing of U.S. Micromertics instrument company ASAP
Instrument, by static state low temperature adsorption capacity method measurement (use national standard GB/T5816-1995 method), method particularly includes: 250 DEG C,
Degassing 4h is vacuumized under 1.33Pa to contact at -196 DEG C with adsorbate, static state reaches adsorption equilibrium using nitrogen as adsorbate；
The amount for calculating adsorbent absorption nitrogen by remaining in the difference in gas phase after nitrogen air inflow and absorption, then uses BJH formula
Calculated hole diameters distribution calculates specific surface area and pore volume with BET formula.
Lattice constant is measured using the D5005 type X-ray diffractometer of Siemens, professional standard SH/T0339-
92 methods.Experiment condition: Cu target, Ka radiation, solid probe, tube voltage 40kV, tube current 40mA, step-scan, stride
0.02 °, reset time 2s, 5 °~70 ° of scanning range.
Phosphorus content, the sodium content of molecular sieve use Rigaku electric machine industry Co., Ltd. 3271E type X-ray fluorescence spectra
Instrument measurement, measuring method are as follows: pressed powder pellet molding, rhodium target, laser voltage 50kV, laser current 50mA, with scinticounting
Device and proportional counter detect each element the intensity of spectral line, carry out quantitative and semi-quantitative analysis to constituent content with external standard method.
The B acid acid amount of molecular sieve and the ratio of L acid acid amount use Bio-Rad IFS-3000 type determination of infrared spectroscopy.Tool
Body method are as follows: by sieve sample itself it is finely ground after be pressed into about 10mg/cm2From blade, be placed in the pond in situ of infrared spectrometer
In, in 350 DEG C, 10-3Pa vacuum degree lower surface purified treatment 2 hours is cooled to room temperature and introduces pyridine saturated vapor, adsorption equilibrium
After 15 minutes, desorption is vacuumized at 350 DEG C 30 minutes, be cooled to room temperature survey absorption and determine pyridine vibrational spectrum.Scanning range
For 1400cm-1-1700cm-1, with 1540 ± 5cm-1The infrared Absorption value and sample sheet weight of bands of a spectrum and the ratio of area define
[the infrared Absorption value of unit area, unit mass sample indicates are as follows: AB (cm its B acid amount2·g)-1].With 1450 ±
5cm-1The infrared Absorption value and sample sheet weight of bands of a spectrum and the ratio of area define its L acid amount [unit area, unit mass sample
The infrared Absorption value of product indicates are as follows: AL (cm2·g)-1], the value of AB/AL is defined as to the B acid acid of the zeolite molecular sieve
The ratio of amount and L acid acid amount.
Molecular sieve carries out sample analysis using Varian UNITYINOVA300M type Nuclear Magnetic Resonance, wherein Al MAS
NMR resonant frequency be 78.162MHzs, spinner velocity 3000Hz, the duplicate delays time be 0.5s, sampling time 0.020s,
1.6 μ s of pulsewidth, spectrum width 54.7kHz, 2000 points of data acquisition, cumulative number 800 times, test temperature is room temperature.
Dry weight/hydro-thermal process Molecular sieve raw material dry weight of molecular sieve obtained by molecular sieve yield (%)=preparation
× 100%.
Preparation embodiment 1-3 is used to illustrate the method for preparing phosphorus containing molecular sieve that the disclosure provides.
Prepare embodiment 1
Take NaY molecular sieve (middle Effect of Catalysis In Petrochemistry agent Chang Ling branch company production, trade name NaY, lattice constant 2.468nm, than
Surface area is 680m2/ g, Kong Rongwei 0.30ml/g, Na2O content is 13.0 weight %, Al2O3Content is 22 weight %) 300g,
(the NH of 2.0mol/L is added4)2HPO4Aqueous solution, mashing, total dosage of water are 1000ml, and filtering repeats gained filter cake above-mentioned
Process three times, then in 100 DEG C of dry 1h, phosphorus containing molecular sieve raw material is obtained, the lattice constant of the phosphorus containing molecular sieve raw material is measured
For 2.468nm, specific surface area 590m2/ g, Kong Rongwei 0.37ml/g, P2O5Content is 4.8 weight %, Na2O content is 3.5 weights
Measure %.
It takes in above-mentioned phosphorus containing molecular sieve raw material 100g merging hydrothermal treatment device, is passed through 100% water vapour, is warming up to 450
DEG C, pressure is 0.8MPa in control device, takes out the molecular sieve material after hydro-thermal process after constant progress hydro-thermal process 8h.
Weight ratio according to hydrochloric acid, ammonium chloride and phosphorus containing molecular sieve raw material (butt) is that 0.2:0.4:1 prepares hydrochloric acid-chlorination
Aqueous ammonium 100ml, in the aqueous solution, the concentration of hydrochloric acid is 0.05mol/L, and the concentration of ammonium chloride is 0.07mol/L.
Molecular sieve material 50g (butt) after taking above-mentioned gained hydro-thermal process, addition 500ml deionized water, stirring to pulp,
Molecular sieve pulp is obtained, is warming up to 80 DEG C.On the basis of 1L molecular sieve pulp, with H+Meter, will according to the speed of 2mol/h
Hydrochloric acid-aqueous ammonium chloride solution of above-mentioned preparation is at the uniform velocity added in molecular sieve pulp in three times, isothermal reaction 4h after each acid adding,
Then it filters, filter cake is taken to continue acid adding next time in the same way.After last time acid adding finishes and reacts 4h,
It collects solid product and obtains phosphorus containing molecular sieve Y-1, Al in 180 DEG C of dry 3h27- NMR structure spectrogram is as shown in Figure 1, property
As shown in table 1.
Prepare embodiment 2
Taking PSRY molecular sieve, (middle Effect of Catalysis In Petrochemistry agent Chang Ling point, company's production, trade name PSRY, lattice constant are
2.456nm, specific surface area 620m2/ g, Kong Rongwei 0.39ml/g, Na2O content is 2.2 weight %, P2O5Content is 1.5 weights
Measure %, Al2O3Content is 18 weight %) 300g, deionized water mashing is added, total dosage of water is 1000ml, filtering, at 70 DEG C
Dry 2h obtains the phosphorus containing molecular sieve raw material that water content is 35 weight %.
Above-mentioned phosphorus containing molecular sieve raw material is crushed, sieves that (wherein 1mm~500mm particle accounts for phosphorus containing molecular sieve for 5-20 mesh
70 weight % of raw material gross weight), it is placed in hydrothermal treatment device, is passed through 100% vapor, is warming up to 580 DEG C, control device
Interior pressure is 0.4MPa, takes out the molecular sieve material after hydro-thermal process after constant progress hydro-thermal process 2h.
It is that 0.02:1 prepares aqueous sulfuric acid 250ml according to the weight ratio of sulfuric acid and phosphorus containing molecular sieve raw material (butt), it should
In aqueous solution, the concentration of sulfuric acid is 0.2mol/L.
Molecular sieve material 50g (butt) after taking above-mentioned gained hydro-thermal process, addition 500ml deionized water, stirring to pulp,
Molecular sieve pulp is obtained, is warming up to 80 DEG C.On the basis of 1L molecular sieve pulp, with H+Meter, will be upper according to the speed of 0.5mol/h
The aqueous sulfuric acid for stating preparation is at the uniform velocity added in molecular sieve pulp in three times, and isothermal reaction 2h, is then filtered after each acid adding,
Filter cake is taken to continue acid adding next time in the same way.After last time acid adding finishes and reacts 2h, solid is collected
Product obtains phosphorus containing molecular sieve Y-2, Al in 100 DEG C of dry 8h27- NMR structure spectrogram is as shown in Figure 1, property such as 1 institute of table
Show.
Prepare embodiment 3
Phosphorus containing molecular sieve is prepared according to the method for preparation embodiment 2, difference is, phosphorus containing molecular sieve raw material is crushed, and sieves
It is divided into 5-20 mesh (the wherein 70 weight % that 5mm~100mm particle accounts for phosphorus containing molecular sieve raw material gross weight), it is then real according to preparation
The method for applying example 2 carries out hydro-thermal process and subsequent operation, obtains phosphorus containing molecular sieve Y-3, property is as shown in table 1.
Preparation comparative example 1-4 is for illustrating the method for preparing phosphorus containing molecular sieve different from the disclosure.
Prepare comparative example 1
The phosphorus containing molecular sieve of this preparation comparative example is PSRY molecular sieve identical with preparation embodiment 2, and preparation method can
The preparation method of the P-contained zeolite with reference to disclosed in CN1088407C, this method include by phosphorus-containing compound and raw material zeolite 0.1-
40 weight ratio directly mixes, and heats at least 0.1 hour in 50-550 DEG C in confined conditions, is washed with deionized to obtain
Product to no acid ion, recycle P-contained zeolite.It is named as RY-1, Al27- NMR structure spectrogram is as shown in Figure 1, property
Matter is as shown in table 1.
Prepare comparative example 2
Take not phosphorous HY molecular sieve (production of middle Effect of Catalysis In Petrochemistry agent Chang Ling branch company, trade name HY, lattice constant
2.465nm, specific surface area 580m2/ g, Kong Rongwei 0.33ml/g, Na2O content is 0.3 weight %, Al2O3Content is 22 weights
Measure %) 100g merging hydrothermal treatment device in, be passed through 100% water vapour, be warming up to 450 DEG C, pressure is in control device
The molecular sieve material after hydro-thermal process is taken out after 0.8MPa, constant progress hydro-thermal process 8h.
Weight ratio according to hydrochloric acid, ammonium chloride and phosphorus containing molecular sieve raw material is that 0.08:1.5:1 prepares hydrochloric acid-ammonium chloride water
Solution 50ml, in the aqueous solution, the concentration of hydrochloric acid is 0.1mol/L, and the concentration of ammonium chloride is 0.16mol/L.
Molecular sieve material 50g (butt) after taking above-mentioned gained hydro-thermal process, addition 500ml deionized water, stirring to pulp,
Molecular sieve pulp is obtained, is warming up to 80 DEG C.On the basis of 1L molecular sieve pulp, with H+Meter, will according to the speed of 2mol/h
Hydrochloric acid-aqueous ammonium chloride solution of above-mentioned preparation is at the uniform velocity added in molecular sieve pulp in three times, isothermal reaction 4h after each acid adding,
Then it filters, filter cake is taken to continue acid adding next time in the same way.After last time acid adding finishes and reacts 4h,
It collects solid product and obtains phosphorus containing molecular sieve RY-2, Al in 180 DEG C of dry 3h27- NMR structure spectrogram is as shown in Figure 1, property
As shown in table 1.
Prepare comparative example 3
PSRY molecular sieve (with preparation embodiment 2) 300g is taken, the NH that concentration is 0.5mol/L is added4Cl aqueous solution 600ml,
It is beaten with deionized water, total dosage of water is 1000ml, is heated to 90 DEG C, carries out ammonium and exchanges 3h.Then it filters, uses deionized water
Twice of washing, heats 4h under 600 DEG C, normal pressure for filter cake.
Weight ratio according to hydrochloric acid, ammonium chloride and phosphorus containing molecular sieve raw material is that 0.5:0.36:1 prepares hydrochloric acid-ammonium chloride water
Solution 300ml, in the aqueous solution, the concentration of hydrochloric acid is 0.6mol/L, and the concentration of ammonium chloride is 0.3mol/L.
Molecular sieve material 50g (butt) after taking above-mentioned gained hydro-thermal process, addition 500ml deionized water, stirring to pulp,
Molecular sieve pulp is obtained, is warming up to 80 DEG C.On the basis of 1L molecular sieve pulp, with H+Meter, will according to the speed of 2mol/h
Hydrochloric acid-aqueous ammonium chloride solution of above-mentioned preparation is at the uniform velocity added in molecular sieve pulp in three times, isothermal reaction 4h after each acid adding,
Then it filters, filter cake is taken to continue acid adding next time in the same way.After last time acid adding finishes and reacts 4h,
It collects solid product and obtains phosphorus containing molecular sieve RY-3, Al in 180 DEG C of dry 3h27- NMR structure spectrogram is as shown in Figure 1, property
As shown in table 1.
Prepare comparative example 4
PSRY molecular sieve (with preparation embodiment 2) 300g is taken, deionized water mashing is added, total dosage of water is 1000ml,
Filtering obtains the phosphorus containing molecular sieve raw material that water content is 65% in 70 DEG C of dry 2h.
Gained phosphorus containing molecular sieve raw material is placed in hydrothermal treatment device, is warming up to 580 DEG C, pressure is in control device
The molecular sieve material after hydro-thermal process is taken out after 0.4MPa, constant progress hydro-thermal process 2h.
It is that 0.8:1 prepares aqueous sulfuric acid 500ml, the aqueous solution according to the weight ratio of sulfuric acid and phosphorus containing molecular sieve raw material
In, the concentration of sulfuric acid is 0.2mol/L.
Molecular sieve material 50g (butt) after taking above-mentioned gained hydro-thermal process, addition 500ml deionized water, stirring to pulp,
Molecular sieve pulp is obtained, is warming up to 80 DEG C.The aqueous sulfuric acid of above-mentioned preparation is added into molecular sieve pulp in three times, every time
The mode of acid adding is directly to pour into, then isothermal reaction 2h, and filtering takes filter cake to continue in the same way next time
Acid adding.After last time acid adding finishes and reacts 2h, solid product is collected in 100 DEG C of dry 8h and obtains phosphorus containing molecular sieve RY-
4, Al27- NMR structure spectrogram is as shown in Figure 1, property is as shown in table 1.
Table 1
Seen from table 1, the ratio of the phosphorus containing molecular sieve that the disclosure provides B acid acid amount with higher and L acid acid amount, and
It can be improved molecular sieve yield in the case where the particle size range for controlling phosphorus containing molecular sieve raw material.
The preparation method for the hydrocracking catalyst that embodiment 1-3 is used to illustrate that the disclosure provides.Comparative example 1-4 is for saying
The bright catalyst standby using the system with molecular sieve for preparing different from the disclosure.
Embodiment 1
By 222.5g grams of boehmite powder PB90 (production of middle Effect of Catalysis In Petrochemistry agent Chang Ling branch company, Kong Rong 0.9ml/g, water
Content is 28 weight %) with 39.5g Y-1 molecular sieve (water content is 19 weight %), (Beijing flying dragon horse economy and trade has 40g silica solution
Effect company, trade name JN-25, dioxide-containing silica 25%, silica particle diameter 9-11nm), 9 grams of sesbania powder mixing it is equal
It is even, the 170ml aqueous solution of nitric acid containing 7.8ml (Beijing chemical reagent factory, 65~68 weight % of nitric acid content) is added, is extruded into outer
Connecing circular diameter is 1.6 millimeters of trilobal item, 120 DEG C of drying, 600 DEG C roasting temperature 3 hours, obtain support C S-1.
After being cooled to room temperature, taking 100g CS-1 carrier to use, (Zigong, Sichuan cemented carbide works, tungsten oxide contain containing ammonium metatungstate
Amount is 52 grams of 82 weight %), (Xu Chi Chemical Co., Ltd., Jiangsu, nickel oxide content are 51 weight %) to basic nickel carbonate
8.7 grams, 10.5g citric acid 80ml aqueous solution dipping, 120 DEG C are dried 10 hours, and hydrocracking catalyst manufactured in the present embodiment is obtained
Agent, composition are shown in Table 2.
Embodiment 2-3
Catalyst is prepared according to the method for embodiment 1, and difference is, molecular sieve used is respectively Y-2 and Y-3, catalysis
Agent composition is shown in Table 2.
Embodiment 4
The JN-25 silica solution of 300g embodiment 1,120 DEG C of dry 10hr are taken, gained particulate abrasive is surveyed at > 100 mesh particles
Obtaining its water content is 5%, obtains Si-95.
97.2g boehmite powder SB powder (production of Sasol company, trade name SB powder, contents on dry basis 0.72) is same
39.5gHY molecular sieve (production of middle Effect of Catalysis In Petrochemistry agent Chang Ling branch company, trade name HY, contents on dry basis 0.76) uniformly mixing, then plus
Enter 10.3g Y-2 molecular sieve (water content be 19 weight %), the 90gSi-95 that takes above-mentioned preparation, 2.4 grams of sesbania powder be uniformly mixed,
The 200ml aqueous solution of nitric acid containing 2ml (Beijing chemical reagent factory, 65~68 weight % of nitric acid content) is added, is extruded into circumscribed circle
Diameter is 1.6 millimeters of trilobal item, 120 DEG C of drying, 550 DEG C roasting temperature 3 hours, obtain support C S-4.
After being cooled to room temperature, 100g CS-4 carrier (Tianjin four directions Chemical Co., Ltd., molybdenum oxide containing ammonium heptamolybdate is taken
Content is 82 weight %) 24.1 grams of 90ml aqueous solution dipping, 120 DEG C drying 10 hours, then (Jiangsu is slowly with nickel nitrate is contained
Slow Chemical Co., Ltd., nickel oxide content are 25.6 weight %) 46.2 grams of 50ml aqueous solution dipping, 90 DEG C are dried 5 hours, and 420
DEG C roasting 3 hours, obtain hydrocracking catalyst manufactured in the present embodiment.
Embodiment 5
By 42.3g grams of boehmite powder PB100 (production of middle Effect of Catalysis In Petrochemistry agent Chang Ling branch company, Kong Rong 1.05ml/g, water
Content is 29 weight %) with 172.8g Y-3 molecular sieve (water content is 19 weight %), (Beijing flying dragon horse economy and trade of 40g silica solution
Effective company, trade name JN-25, dioxide-containing silica 25%, silica particle diameter 9-11nm), 10 grams of sesbania powder mixing
Uniformly, the 120ml aqueous solution of urea containing 20g (Beijing chemical reagent factory) is added, is extruded into three that circumscribed circle diameter is 1.6 millimeters
Leaf item, 120 DEG C drying, 600 DEG C roasting temperature 3 hours, obtain support C S-5.
After being cooled to room temperature, 100g carrier (Zigong, Sichuan cemented carbide works, tungsten oxide content 91 containing ammonium metatungstate is taken
Weight %) 39.2 grams, 20.56 grams of nickel nitrate (Xu Chi Chemical Co., Ltd., Jiangsu, nickel oxide content are 25.6 weight %),
0.26g ethylene glycol 85ml aqueous solution dipping, 180 DEG C are dried 3 hours, and hydrocracking catalyst manufactured in the present embodiment is obtained, and are formed
It is shown in Table 2.
Comparative example 1-4
Catalyst is prepared according to the method for embodiment 1, and difference is, molecular sieve used is respectively RY-1, RY-2, RY-3
And RY-4.
Table 2
Testing example
Catalyst urging for hydrocracking reaction of this testing example for testing example 1-3 and comparative example 1-4
Change activity.Wherein, raw materials used oil is the husky vacuum gas oil (VGO) that gently subtracts two, and physico-chemical property is shown in Table 3.Reaction result is shown in Table 4.
Table 3
| Project | Feedstock oil |
| Density (20 DEG C) (g/cm3) | 0.8885 |
| S (weight %) | 16000 |
| N(mg/L) | 352 |
| Simulation distillation (ASTM D-2887) (DEG C) | |
| Initial boiling point | 291 |
| 50 weight % | 391 |
| 90 weight % | 421 |
In this testing example, the evaluation method of catalyst is: by catalyst breakage at 2-3 millimeters of diameter of particle,
It is packed into 20 milliliters of catalyst in 30 milliliters of fixed bed reactors, is first used under a hydrogen atmosphere containing 2 weight % carbon disulfide before reacting
Kerosene is vulcanized according to the procedure below, is then switched reaction raw materials and is reacted.
Vulcanization program: being warming up to 150 DEG C, introduces sulfurized oil, constant temperature 1h Wen Bo to be adsorbed is by two reactors, with 60
DEG C/h is warming up to 230 DEG C, stablize 2h, is warming up to 360 DEG C with 60 DEG C/h, stablizes 6h.Reaction raw materials oil is replaced, reaction temperature is adjusted
Following reaction condition, and at least stable 20h.
Reaction condition: being 365 DEG C, hydrogen partial pressure 6.4MPa in reaction temperature, liquid hourly space velocity (LHSV) (LHSV) 1h-1, hydrogen-oil ratio (body
Product) be 800 under conditions of carry out hydrocracking reaction.The results are shown in Table 3.
It is big in conversion ratio (%)=(be greater than in 350 DEG C of fraction amounts-generation oil in raw material and be greater than 350 DEG C of fraction amounts)/raw material
In 350 DEG C of fraction amount × 100%.
Table 4
| Catalyst | Conversion ratio (%) |
| Embodiment 1 | 58.6 |
| Embodiment 2 | 63.3 |
| Embodiment 3 | 61.9 |
| Embodiment 4 | 69.2 |
| Embodiment 5 | 91.6 |
| Comparative example 1 | 34.8 |
| Comparative example 2 | 39.5 |
| Comparative example 3 | 28.3 |
| Comparative example 4 | 51.4 |
From table 4, it can be seen that under identical reaction conditions, relative to the molecular sieve of conventional method preparation, containing this public affairs
The catalyst of the phosphorus containing molecular sieve of offer its catalytic activity is provided and improves 7.2~63.3%.
The preferred embodiment of the disclosure is described in detail in conjunction with attached drawing above, still, the disclosure is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the disclosure, a variety of letters can be carried out to the technical solution of the disclosure
Monotropic type, these simple variants belong to the protection scope of the disclosure.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the disclosure to it is various can
No further explanation will be given for the combination of energy.
In addition, any combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally
Disclosed thought equally should be considered as disclosure disclosure of that.
Claims (20)
1. a kind of hydrocracking catalyst, which is characterized in that on the basis of the dry weight of catalyst, which includes with dry
The carrier of 45~90 weight % of base weight meter, the first metal component of 1~40 weight % in terms of metal oxide, He Yijin
Belong to the second metal component of 1~15 weight % of oxide meter；
The carrier includes phosphorus-contained gamma-type molecular sieve, aluminium oxide and silica, the phosphorus-contained gamma-type molecular sieve, aluminium oxide and silica
Weight ratio be 1:(0.03~20): (0.03~20)；First metal is the metal selected from group VIB；Second gold medal
Category group is divided into the metal selected from group VIII；
In terms of oxide, the phosphorus content of the phosphorus-contained gamma-type molecular sieve is 0.3~5 weight 0.2~0.95mL/g of %, Kong Rongwei, pyrrole
The ratio of the infrared B acid of pyridine and L acid is 2~10.
2. catalyst according to claim 1, wherein on the basis of the dry weight of catalyst, the catalyst include with
The carrier of 55~85 weight % of dry basis, the first metal component of 12~35 weight % in terms of metal oxide, and
The second metal component of 2~10 weight % in terms of metal oxide；
The weight ratio of the phosphorus-contained gamma-type molecular sieve, aluminium oxide and silica is 1:(0.1~15): (0.1~15).
3. catalyst according to claim 1 or 2, wherein the Al of the phosphorus-contained gamma-type molecular sieve27In-NMR structure spectrogram,
I60ppm/I-1ppmFor 5~40, I-1ppm/I±6ppmIt is 0.4~2.
4. catalyst according to claim 1 or 2, wherein the phosphorus-contained gamma-type molecular sieve passes through the side included the following steps
Method is prepared:
A, make phosphorus containing molecular sieve raw material at 350-700 DEG C of temperature, pressure is 0.1-2MPa and carries out water in the presence of water vapor
It is heat-treated 0.5-10h, the molecular sieve material after obtaining hydro-thermal process；In terms of oxide and with the dry basis of phosphorus containing molecular sieve raw material
On the basis of amount, the phosphorus content of the phosphorus containing molecular sieve raw material is 0.1~15 weight %, and sodium content is 0.5~4.5 weight %；
B, add water to be beaten the molecular sieve material after the hydro-thermal process that step a is obtained, molecular sieve pulp is obtained, by the molecule
Screening the pulp liquid is heated to 40~95 DEG C, then keeps temperature and acid solution, the acid solution are continuously added into the molecular sieve pulp
The ratio of the weight of middle acid and the dry weight of the phosphorus containing molecular sieve raw material is (0.01-0.6): 1, with molecule screening the pulp described in 1L
On the basis of liquid, with H+Meter, the addition speed of the acid solution are 0.05-10 mols/hr, isothermal reaction 0.5- after acid adding
20h collects solid product.
5. catalyst according to claim 4, wherein in step a, the phosphorus containing molecular sieve raw material is phosphorous Y type point
Son sieve, the lattice constant of the phosphorous Y type molecular sieve are 2.425~2.47nm, and specific surface area is 250~750m2/ g, Kong Rong
For 0.2~0.95ml/g.
6. catalyst according to claim 5, wherein in step a, the water content of the phosphorus containing molecular sieve raw material is 10~
40 weight %；
The phosphorus containing molecular sieve raw material is graininess, and the content of phosphorus containing molecular sieve raw material that particle size range is 1mm~500mm is
10~100 weight % of phosphorus containing molecular sieve raw material gross weight, the granularity is in terms of the circumscribed circular diameter of particle.
7. catalyst according to claim 6, wherein particle size range is containing for the phosphorus containing molecular sieve raw material of 1mm~500mm
Amount is 30~100 weight % of phosphorus containing molecular sieve raw material gross weight；
Preferably, the content for the phosphorus containing molecular sieve raw material that particle size range is 5mm~100mm is phosphorus containing molecular sieve raw material gross weight
30~100 weight %.
8. catalyst according to claim 4, wherein in step b, water in the molecular sieve pulp that is obtained after mashing
The ratio of weight and the dry weight of phosphorus containing molecular sieve raw material is (14-5): 1.
9. catalyst according to claim 4, wherein the preparation step of the phosphorus-contained gamma-type molecular sieve further include: step b
In, ammonium salt is added into the molecular sieve pulp during acid solution is added, the ammonium salt is selected from ammonium nitrate, ammonium chloride
At least one of with ammonium sulfate, the ratio of the dry weight of the weight and phosphorus containing molecular sieve raw material of the ammonium salt is (0.1-
2.0): 1.
10. catalyst according to claim 4, wherein in step b, the acid concentration of the acid solution is 0.01~
15.0mol/L, it is described acid in phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid and acetic acid extremely
Few one kind.
11. catalyst according to claim 4, wherein the preparation step of the phosphorus-contained gamma-type molecular sieve further include: collect
Then solid product is washed, is dry, obtaining phosphorus containing molecular sieve；The condition of the drying are as follows: temperature is 50~350 DEG C, preferably
70~200 DEG C；Time be 1~for 24 hours, preferably 2~6h.
12. catalyst according to claim 1, wherein first metal is molybdenum and/or tungsten；Second metal is
Selected from least one of iron, nickel and cobalt.
13. a kind of method for preparing hydrocracking catalyst described in any one of claim 1-12, which is characterized in that should
Method includes: to contact the maceration extract containing metal precursor with carrier to be impregnated, and then does the material obtained after dipping
It is dry.
14. according to the method for claim 13, wherein this method further include: by phosphorus-contained gamma-type molecular sieve, aluminium oxide, oxidation
Then precursor, peptizing agent and the optional mix lubricant of silicon form, are dry, roasting obtains the carrier；
The precursor of the silica be selected from Silica hydrogel that silica solution, loss on ignition are 0 weight of weight %~60 %, White Carbon black and
At least one of superfine silicon dioxide.
15. according to the method for claim 13, wherein the metal precursor includes the first metal precursor and the second gold medal
Belong to predecessor, wherein first metal precursor is the inorganic salts and first of inorganic acid selected from the first metal, the first metal
At least one of metallo-organic compound；The inorganic salts be selected from nitrate, carbonate, subcarbonate, hypophosphites,
At least one of phosphate, sulfate and chloride；Organic substituent in first metallo-organic compound be selected from
At least one of hydroxyl, carboxyl, amido, ketone group, ether, alkyl；
Second metal precursor is selected from bimetallic inorganic acid, bimetallic inorganic salts and the second Organometallic
Close at least one of object；The inorganic salts are selected from nitrate, carbonate, subcarbonate, hypophosphites, phosphate, sulphur
At least one of hydrochlorate and chloride；Organic substituent in second metallo-organic compound be selected from hydroxyl, carboxyl,
At least one of amido, ketone group, ether, alkyl.
16. according to the method for claim 13, wherein also contain organic additive in the maceration extract；It is described organic to add
The concentration for adding agent is 2-300g/L；The organic additive is selected from ethylene glycol, glycerine, polyethylene glycol, diethylene glycol, fourth two
Alcohol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2- cyclohexanediamine tetraacetic acid, citric acid, tartaric acid, malic acid, second two
Amine, diethylenetriamines, 1,2-diaminocyclohexane tetraacetic acid, amion acetic acid, nitrilotriacetic acid, ethylenediamine tetra-acetic acid and ethylenediamine tetrem
At least one of sour ammonium.
17. according to the method for claim 13, wherein the condition of the drying are as follows: temperature is 80-350 DEG C, and the time is
0.5-24 hours.
18. according to the method for claim 13, wherein this method further includes that will roast after the dry materials after contact
The step of, the condition of the roasting are as follows: temperature is 350-600 DEG C, and the time is 0.2-12 hours.
19. hydrocracking catalyst described in a kind of any one of claim 1-12 is in the hydrocracking reaction of hydrocarbon raw material
In application.
20. application according to claim 19, wherein the hydrocarbon raw material be selected from straight run gas oil, vacuum gas oil (VGO),
Metal removal oil, reduced crude, de-asphalted vacuum residue, coker distillate, catalytic cracking distillate oil, shale oil, asphalt sand oil and
At least one of liquefied coal coil；
The condition of the hydrocracking reaction are as follows: reaction temperature is 200-650 DEG C, preferably 300-510 DEG C；Reaction pressure is 3-
24 megapascal, preferably 4-15 megapascal；Liquid hourly space velocity (LHSV) is 0.1-10 hours-1, preferably 0.2-5 hours-1；Hydrogen to oil volume ratio is
100-5000, preferably 200-1000.
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