CN1765510A - Alumina supporter containing composite zeolite and its preparation method - Google Patents
Alumina supporter containing composite zeolite and its preparation method Download PDFInfo
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Abstract
The invention discloses a carrier containing composite zeolite alumina and relative preparing method. The carrier utilizes the Y zeolite, ZSM-23 zeolite and alumina as carriers, while the property of zeolite can be changed via exchanging the metallic positive ions between the VIB group and/or VIII group to adjust the acid distribution of Y zeolite, especially the proportion of B acid and L acid. The invention can be used as the carrier of hydrogenation catalyst, to prepare fractionally the winter cleaning diesel fuel from poor diesel fuel.
Description
Technical field
The present invention relates to a kind of alumina support and preparation method thereof, be specifically related to a kind of alumina support that contains composite zeolite and preparation method thereof, in particular as carrier of hydrotreating catalyst and preparation method thereof.
Background technology
Zeolite is important catalysis material, as the main provider of acidity, plays important effect in catalytic cracking, hydrocracking reaction.The catalyst of many processes such as hydrotreatment in recent years,, hydrofinishing and hydro-upgrading is also brought into use modified zeolite.And in catalyst, use the kind of zeolite also to develop to two or more combination of zeolites by a kind of zeolite gradually.But because zeolite component is developed the qualification aspect the coordinated that purpose specificity and various ingredients exist, the less use composite zeolite of present carrier and catalyst thereof component at first in carrier.
US5536687 discloses a kind of middle oil type hydrocracking catalyst, contains the Y zeolite that β zeolite and lattice constant are not more than 2.445nm in this catalyst carrier.This carrier complexes carrying catalyst cracking activity height that hydrogenation metal obtained mainly uses on light oil type hydrogen cracking catalyst, is unsuitable for as hydrotreating catalyst.
CN 1317547A discloses a kind of FCC Catalysts and its preparation method that reduces content of olefin in gasoline, is made up of 0.5-5wt%ZSM-5 zeolite, 0.5-15wt% rare earth exchanged Y zeolite, 20-40wt% phosphorus and the composite modified overstable gamma zeolite of rare earth.Compare with conventional catalyst, guaranteeing obviously to reduce the olefin(e) centent of gasoline under the prerequisite that other products distribute and octane number is constant substantially.The cracking activity of this catalyst is too high, is unsuitable for as hydrotreating catalyst.
Summary of the invention
The object of the present invention is to provide a kind of alumina support that contains composite zeolite and preparation method thereof, it is suitable that the modified Y zeolite acid that this carrier adopts distributes, and particularly B acid is more reasonable with the ratio of L acid.This carrier is specially adapted to do the carrier of hydrotreating catalyst.
The alumina support that contains composite zeolite of the present invention comprises following component: modified Y zeolite, ZSM-23 zeolite and aluminium oxide.The character of used modified Y zeolite is as follows: contain group vib and/or group VIII metallic element 2wt%-10wt% in this modified Y zeolite, SiO
2/ Al
2O
3Mol ratio is 9.0-12.9, and lattice constant is 2.440-2.459nm, and specific area is 550-650m
2/ g, pore volume are 0.340-0.370ml/g, and infrared acidity is 1.37-1.60mmol/g, wherein the mol ratio 1 of B acid and L acid: 3-1: 5, and Na
2O weight content＜0.2%, better＜0.15%, best＜0.1%.Wherein said group vib and/or group VIII metallic element are one or more among W, Ni, Co, Fe, the Mo.
In the alumina support that contains composite zeolite of the present invention, be benchmark with the weight of carrier, the content of modified Y zeolite is 1%-20%, is preferably 5%-15%; The content of ZSM-23 zeolite is 1%-30%, is preferably 5%-20%; The content of aluminium oxide is 30%～98%, is preferably 40%-80%, adhesive 0～30%.
The specific area of carrier of the present invention is 280-330m
2/ g, pore volume are 0.50-0.60ml/g, and wherein the aperture accounts for the 80%-90% of total pore volume in the pore size distribution of 4-10nm, and infrared acidity is 0.36-0.50mmol/g.
The used modified Y zeolite of the present invention is prepared as follows by super-hydrophobic Y zeolite:
(1) super-hydrophobic Y zeolite is placed water, its mesolite is 1 with the ratio of the weight of water: 2-10 is preferably 1: 3-8, be warming up to 60 ℃-90 ℃, and stirred 0.5-2.0 hour.
(2) get and contain in group vib and/or the group VIII metal soluble salt one or more and be mixed with solution, add in above-mentioned steps (1) solution, with ammoniacal liquor regulator solution pH value, control pH value is 4-10, solution is under 50-90 ℃, stir fully exchange in aging 2-4 hour, after the filtration, made in dry 8-24 hour at 100 ℃-150 ℃.
Wherein said super-hydrophobic Y zeolite is obtained after under 500～600 ℃, 0.01～0.30MPa condition hydrothermal treatment consists 1-10 hour by the Y zeolite.Wherein the character of Y zeolite is as follows: NaO content is lower than 0.2wt%, silica alumina ratio 6-40 (chemical method), lattice constant 2.440-2.460nm.This Y zeolite can be by NH
4The NaY zeolite makes with fluosilicate liquid phase dealuminzation method, as the method for putting down in writing among the CN 1026313C.
The preparation process that contains the alumina support of composite zeolite of the present invention comprises:
(1) modified Y zeolite, ZSM-23 zeolite and aluminium oxide are mixed;
(2) in the mixture of step (1), add adhesive and peptizing agent solution or directly add peptizing agent solution and mix and pinch into paste, extruded moulding;
(3),,, obtain carrier of the present invention at 350～700 ℃ of roasting 1-12 hours 100～150 ℃ of dryings 0.5～24 hour with above-mentioned article shaped.
Preferably 100～140 ℃ of described baking temperatures are preferably 1～8 hour drying time.
Preferably 400～650 ℃ of described sintering temperatures, roasting time is preferably 1～8 hour.
Carrier of the present invention can be separately as catalyst component, also can be applicable to anyly carrier specific surface and pore structure be had relatively high expectations the field that needs to bring into play the different zeolites catalytic selectivity again simultaneously.
As required, catalyst carrier of the present invention can further support active metal component or other additive component, to adapt to the needs of differential responses.As for hydrotreating catalyst, generally need support the hydrogenation metal component, promptly adopt the saturated or excess solution dipping active metal component in hole, obtain hydrotreating catalyst after the carrier strip drying behind the carrying metal, the activation.
Supported carrier hydrogenation metal of the present invention can be used for the hydrotreatment process, is particularly suitable for the process that low condensation point clean diesel is produced in the poor ignition quality fuel hydrotreatment.In the alumina support that contains composite zeolite of the present invention owing to adopt Y zeolite after the metal cation modification, the acid of this modified Y zeolite distributes, especially the ratio of B acid and L acid is more reasonable, so that the catalyst of its preparation can reduce the cracking of diesel oil distillate effectively, guarantee diesel yield, promote the saturated open loop of aromatic hydrogenation, also improved the catalyst anti-carbon deposition ability simultaneously, prolonged the service life of catalyst.
In addition, owing to adopt the ZSM-23 zeolite, the oval non-intersection straight channel that its ten-ring constitutes has isomery selectivity and shape selective preferably in the carrier of the present invention, has only linear paraffin can enter the duct in ZSM-23 and reacts, and side chain is stayed the place, aperture.And, improved the isomerization reaction selectivity of catalyst prepared therefrom because the preferable ovality of ZSM-23 becomes branched-chain hydrocarbons that the space is provided for molecule isomery in the duct, when improving Cetane number to greatest extent, reduce the condensation point of diesel oil significantly.
The synergy of two kinds of zeolites makes catalyst have ability of aromatic hydrocarbons open loop preferably and preferable heterogeneous activity simultaneously.When guaranteeing diesel yield, improve the Cetane number of diesel oil, reduce the condensation point of diesel product.
The specific embodiment
The employed ZSM-23 zeolite of carrier of the present invention can adopt that all are suitable for ZSM-23 zeolite of the present invention in the prior art, and its character is as follows: SiO
2/ A1
2O
3Mol ratio (chemical method) is 40-100, better is 50-90, Na
2O weight content＜0.2%, better＜0.15%, best＜0.1%, infrared acidity is 0.1-0.4mmol/g, better is 0.15-0.4mmol/g.
ZSM-23 zeolite in the carrier of the present invention is preferably selected fine grain ZSM-5-23 zeolite for use, and its particle diameter is 1～100nm.Such as fine grain ZSM-5-23 zeolite that adopts the method preparation among the U.S. Pat P 5,160,500.When containing fine grain ZSM-5-23 zeolite in the carrier of the present invention, chain carrier increases when adopting non-fine grain ZSM-5-23 zeolite, and fine grain ZSM-5-23 zeolite cavity shortens, and is beneficial to the diffusion of reactant and product.
Aluminium oxide used in the present invention can adopt the conventional aluminium oxide that is used to prepare catalyst carrier, the preferred aluminium oxide that adopts through additive modification.Described in the aluminium oxide of additive modification, auxiliary agent (in element) content is 3wt%-7wt%, and wherein said auxiliary agent is one or more in boron, fluorine and the zirconium.The character of this modified aluminas: specific area is 320-370m
2/ g, pore volume are 0.7～1.1ml/g.This modified aluminas can adopt the preparation method among the Chinese patent CN1458232A: adopt preferably Carbonization Preparation aluminium oxide precursor of conventional method, get its filter cake, making beating is warming up to 50～90 ℃, is preferably 65～75 ℃, the auxiliary agent that adds certain content, and under 50～90 ℃ of temperature, stirred 5～120 minutes, be preferably 30～90 minutes, filter, drying makes modified aluminas.
The present invention is in preparation catalyst carrier process, usually adopt adhesive, used adhesive can be the aperture refractory inorganic oxides, as in clay, silica, aluminium oxide, sial, zirconia and the titanium oxide-magnesia one or more, is preferably little porous aluminum oxide.The character of common used aperture refractory inorganic oxides is as follows: specific area is 220-300m
2/ g, pore volume are 0.45-0.52ml/g.Also can not use adhesive during preparing carriers of the present invention, but after each component involved in the present invention mixed, directly add a certain amount of peptization acid and mix alunite, extruded moulding.
The present invention can adopt extrusion aid during extrusion in the process of preparing carriers, extrusion aid commonly used can be: one or more in sesbania powder, citric acid, oxalic acid, cellulose, starch, the high molecular surfactant etc.
Involved in the present invention to peptizing agent can be: one or more in aluminum sulfate, citric acid, nitric acid, acetic acid, the oxalic acid etc.
Support shapes after the described moulding can be sheet, spherical, cylinder bar and special-shaped bar (clover, bunge bedstraw herb), preferably cylinder bar and special-shaped bar (clover, bunge bedstraw herb).The diameter of carrier can be 0.8～2.0mm slice and＞the thick bar of 2.5mm.
The characteristics of carrier of the present invention are described below by specific embodiment.
The specific area of product of the present invention and pore volume are to adopt ASAP2400, and cryogenic nitrogen absorption (77K) calculates according to BET formula.Acid amount and acid matter adopt infrared spectrometer to record, and the adsorbent that uses is pyridine.
Embodiment 1
The preparation of modified Y zeolite Y-A:
(1) the Y zeolite is handled under 0.1MPa, 550 ℃ of steam obtained super-hydrophobic Y zeolite Y-W in 1 hour; Wherein the Y zeolite is Wenzhou catalyst plant production, and its character is as follows: silica alumina ratio (chemical method) 10.01, lattice constant 2.448nm, Na
2O content 0.05wt%, butt 75wt%.
(2) 300 gram super-hydrophobic Y zeolites are placed 1000ml water, stir and be warming up to 60 ℃.
(3) 181g nickel nitrate and 29g cobalt nitrate are made into 240ml solution, add in the above-mentioned zeolite solution with ammoniacal liquor, control pH value equals 6, adds back solution aging 2 hours, after the filtration, makes in 8 hours 110 ℃ of dryings, is designated as Y-A, and its physico-chemical property sees Table 1.
Embodiment 2
The preparation of modified Y zeolite Y-B:
Step (1) is with embodiment 1;
Step (2) places 1500ml water with 300 gram super-hydrophobic Y zeolites, stir and be warming up to 80 ℃, and adding 97.8g ferric nitrate stirs.
Step (3) is made into 200ml solution with 360g nickel nitrate and 62g cobalt nitrate, and adds in the above-mentioned zeolite solution with ammoniacal liquor, and control pH value equals 5, added back solution aging 2 hours, and after the filtration, made in 8 hours 110 ℃ of dryings, be designated as Y-B, its physico-chemical property sees Table 1.
Embodiment 3
The preparation of modified Y zeolite Y-C:
Step (1) is got 100KgNaY zeolite (Wenzhou catalyst plant product, butt 50%), is crushed to less than 20 orders, with 800 liters of NH that contain 120Kg
4NO
3Solution stirred 2 hours down at 70-75 ℃, repeat this exchange step 10 times, filter, and be washed to neutrality, obtain Na
2O content is the Y zeolite of 0.19wt%, oven dry.The zeolite of above-mentioned washing oven dry is put into the high-pressure rotary stove, be rapidly heated to 650 ℃, at 0.1Mpa, roasting is 2 hours under 100% water vapor pressure, obtains super-hydrophobic Y zeolite Y-C of the present invention.Its character is as follows: silica alumina ratio (chemical method) 11.2, lattice constant 2.448nm, Na
2O content 0.05wt%, butt 75wt%.
Step (2) places 1600ml water with the above-mentioned super-hydrophobic Y zeolite of 400 grams, stirs and is warming up to 75 ℃.
Step (3) is made into 430ml solution with 483.3g nickel nitrate and 69.6g cobalt nitrate, adds in the above-mentioned zeolite solution with ammoniacal liquor, and control pH value equals 5.5, added back solution aging 2 hours, and after the filtration, made in 8 hours 120 ℃ of dryings, be designated as Y-C, its physico-chemical property sees Table 1.
Embodiment 4
The preparation of modified Y zeolite Y-D:
Step (1) is with embodiment 3
Step (2) places 1200ml water with the above-mentioned super-hydrophobic Y zeolite of 333 grams, stirs and is warming up to 70 ℃.
Step (3) is made into 390ml solution with 120g nickel nitrate and 48.7g cobalt nitrate, adds in the above-mentioned zeolite solution with ammoniacal liquor, and control pH value equals 6.5, added back solution aging 2 hours, and after the filtration, made in 8 hours 120 ℃ of dryings, be designated as Y-D, its physico-chemical property sees Table 1.
Embodiment 5
The preparation of ZSM-23 zeolite Z-A (by embodiment 2 methods preparation among the U.S. Pat P 4076842) a collection of ZSM-23 molecular sieve of preparation is at first wanted obtain solution, contains 2.64 gram sodium aluminate (43.1wt%Al
2O
3, 33.1wt%Na
2O and 24.7wt%H
2O), 48 gram H
2O and 0.27 gram NaOH (concentration is 50% NaOH solution) add 28.8 gram pyrrolidines then, add 132 gram silica gel (30wt%SiO afterwards
2And 70wt%H
2O), solution is mixed until forming uniform colloid.This colloidal solution composition and mole proportioning are as follows:
R+/(R
++M.
+)＝0.93
Here, M is Na, R
+It is the cationic nitrogenous of deriving by pyrrolidines
OH
-/SiO
2＝0.048
The OH that pyrrolidines is derived
-Ion does not count
H
2O/OH
-＝246
The OH that pyrrolidines is derived
-Ion does not count
SiO
2/Al
2O
3＝59.1
Mixture kept 7 days under 350 conditions, finished crystallization process in this process.Crystalline product filters out from solution, and about 16 hours of continuous washing is dry under 230 conditions then.Show specific area 226m at 16 hours crystalline product of 1000 following roastings through physical analysis
2/ g.
Get the above-mentioned ZSM-23 zeolite of 500g and place the high-temperature roasting stove, be warming up to 700 ℃ with about 100 ℃/speed at one hour rating, constant temperature calcining is 12 hours then, be cooled to room temperature, make and take off amine ZSM-23 zeolite,, stirred 6 hours at 55 ℃ of following constant temperature with the NH4NO3 solution of 0.5N, liquid-solid ratio is 10, and filtered water is washed till neutrality then.Zeolite filter cake after the acid treatment is 110-220 ℃ of oven dry down.Above-mentioned zeolite is put in the airtight roaster of high temperature, be warming up to 550 ℃ with about 200 ℃/speed at one hour rating, feed 100% steam simultaneously, controlled pressure 0.1MPa, constant temperature and pressure roasting 2 hours, and then with the NH4NO3 solution of 3.0N, stirred 6 hours at 90 ℃ of following constant temperature, liquid-solid ratio is 10, and filtered water is washed till neutrality then.Zeolite filter cake after the acid treatment promptly gets zeolite Z-A 110-220 ℃ of oven dry down.Its physico-chemical property sees Table 1.This zeolite silica alumina ratio is 69.3 (chemical methods), and NaO% content is＜0.15wt%.
Embodiment 6
The preparation of modified aluminas L-1
Get the filter cake after the aluminium oxide precursor washing of Carbonization Preparation, surveying its butt is 20wt%, gets this filter cake 6000 grams, adds 24 liter deionized waters, making beating, and add 200 gram BF
3Diethyl ether solution (BF
3Content 46.8wt%), be warming up to 65 ℃, stirred 1 hour, filter, 110 ℃ of dryings 4 hours, sample is L-1, its physico-chemical property sees Table 1.
Embodiment 7
The preparation of modified aluminas L-2.
Get aluminium oxide precursor washing back filter cake 800 grams of aluminum sulfate method preparation, adds 4 liters of deionized waters, be warming up to 85 ℃ after stirring, add ammonium fluoroborate 11 grams, continue stirring 30 minutes, 110 ℃ of dryings 4 hours, sample L-2, its physico-chemical property sees Table 1.
Table 1 sample physico-chemical property
| The embodiment numbering | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Sample number into spectrum | Y-A | Y-B | Y-C | Y-D | Z-A | L-1 | L-2 |
| NiO，wt％ | 4.12 | 6.3 | 8.9 | 3.11 | - | - | - |
| CoO，wt％ | 0.57 | 0.89 | 0.73 | 0.89 | - | - | - |
| Fe，wt％ | - | 1.19 | - | - | - | - | - |
| Auxiliary agent (in element) content, wt% | - | - | - | - | - | 6.3 | 5.9 |
| Specific area, m 2/g | 612 | 574 | 552 | 624 | 220 | 360 | 320 |
| Pore volume, ml/g | 0.362 | 0.353 | 0.348 | 0.367 | - | 0.88 | 0.92 |
| Infrared acidity, mmol/g | 1.476 | 1.575 | 1.501 | 1.466 | 0.27 | - | - |
| The mol ratio of B acid and L acid | 1∶3.5 | 1∶4.6 | 1∶4.8 | 1∶3.2 | - | - | - |
| SiO 2/Al 2O 3Mol ratio (chemical method) | 9.87 | 9.59 | 11.2 | 11.1 | 69.3 | - | - |
| Lattice constant, nm | 2.441 | 2.444 | 2.451 | 2.456 | - | - | - |
| Na 2O content, wt% | 0.15 | 0.15 | 0.05 | 0.05 | ＜0.15 | - | - |
Embodiment 8
The preparation of support C of the present invention-1.
20.6 gram Y-A, 53 gram Z-A, 252.9 gram L-1,200 are restrained by SB powder (pore volume 0.46ml/g, specific area 260m
2/ g) adhesive (butt 30wt%) of preparation is put into roller, grind to can squeezing paste, and extrusion, 110 ℃ of dryings 4 hours, 550 ℃ of roastings 3 hours make support C-1, and its physico-chemical property sees Table 2.
Embodiment 9
The preparation of support C of the present invention-2.
41.2 gram Y-A, 16.5 gram Z-A, 235 gram L-1,300 grams are put into roller by the adhesive (butt 30wt%) of L-1 powder preparation, grind to squeezing paste, extrusion, 110 ℃ of dryings 4 hours, 550 ℃ of roastings 3 hours make support C-2, and its physico-chemical property sees Table 2.
Embodiment 10
The preparation of support C of the present invention-3.
61.8 gram Y-B, 13.4 gram Z-A, 261 gram L-2,196 are restrained by SB powder (pore volume 0.46ml/g, specific area 260m
2/ g) adhesive (butt 30wt%) of preparation is put into roller, grind to can squeezing paste, and extrusion, 110 ℃ of dryings 4 hours, 500 ℃ of roastings 3 hours make support C-3, and its physico-chemical property sees Table 2.
Embodiment 11
The preparation of support C of the present invention-4.
Method with form similar to Example 8ly substantially, keep Y-A, Z-A content constant, modified aluminas is changed to SB powder (pore volume 0.46ml/g, specific area 260m
2/ g), the gained carrier is C-4, its physico-chemical property sees Table 2.
Embodiment 12
The preparation of support C of the present invention-5.
36.26 gram Y-C, 87.36 gram Z-A, 603.46 gram L-1,431.2 are restrained by SB powder (pore volume 0.46ml/g, specific area 260m
2/ g) adhesive (butt 30wt%) of preparation is put into roller, grind to can squeezing paste, and extrusion, 120 ℃ of dryings 8 hours, 500 ℃ of roastings 8 hours make support C-5, and its physico-chemical property sees Table 2.
Embodiment 13
The preparation of support C of the present invention-6.
With 53.15 gram Y-D, 199.3 gram Z-A, 1161 gram L-2,851.4 grams are by SB powder (pore volume 0.46ml/g, specific area 260m
2/ g) preparation adhesive (butt 30wt%), put into roller, grind to can squeezing paste, extrusion, 120 ℃ of dryings 8 hours, 500 ℃ of roastings 8 hours make support C-6, its physico-chemical property sees Table 2.
Comparative example-1
This example is the preparation of reference carrier J-1.
Method is similar to Example 8 substantially with composition, only removes the Z-A component, and the gained carrier is J-1, and its physico-chemical property sees Table 2.
Comparative example-2
This example is the preparation of reference carrier J-2.
Method with form similar to Example 8ly substantially, keep Z-A content constant, the Y-A component is changed to the super-hydrophobic Y that does not carry out cation exchange-W zeolite (Wenzhou catalyst plant) among the embodiment 1, the gained carrier is J-2, its physico-chemical property sees Table 2.
Table 2 carrier physico-chemical property
| Embodiment of the invention carrier | The Comparative Examples carrier | |||||||
| Bearer number | C-1 | C-2 | C-3 | C-4 | C-5 | C-6 | J-1 | J-2 |
| Carrier is formed | ||||||||
| Modified Y zeolite, wt% | 5 | 10 | 15 | 5 | 4 | 3 | 18 | 5 |
| The ZSM-23 zeolite, wt% | 16 | 5 | 4 | 24 | 12 | 14 | 16 | |
| Aluminium oxide, wt% | 59 | 55 | 61 | 51 | 64 | 63 | 62 | 59 |
| Adhesive, wt% | 20 | 30 | 20 | 20 | 20 | 20 | 20 | 20 |
| Carrier character | ||||||||
| Specific area, m 2/g | 299 | 319 | 326 | 297 | 305 | 312 | 309 | 264 |
| Pore volume, ml/g | 0.532 | 0.511 | 0.547 | 0.589 | 0.554 | 0.534 | 0.516 | 0.589 |
| 4-10nm pore volume integration rate, % | 83 | 82 | 88 | 82 | 87 | 89 | 71 | 69 |
| Infrared acidity, mmol/g | 0.362 | 0.367 | 0.385 | 0.363 | 0.371 | 0.374 | 0.529 | 0.406 |
In order to further specify the effect of carrier of the present invention, with the supported carrier hydrogenation active metals, be prepared into catalyst A and catalyst B, be used for the hydrotreatment process of poor ignition quality fuel.
Embodiment 16
This example is the preparation of catalyst A.
With support C-1 usefulness ammonium metatungstate, nickel nitrate aqueous solution dipping, 110 ℃ of dryings 4 hours, 500 ℃ of roastings 3 hours make catalyst A.In the catalyst of gained, Z-A zeolite 11wt%, super-hydrophobic Y zeolite 3.5wt%, modified aluminas 40wt%, the content of NiO are 5.10wt%, the content of CoO is 0.14wt%, WO
3Content be 26.0wt%, surplus is the adhesive aluminium oxide, its character is as follows: specific surface is 171m
2/ g, pore volume are 0.305ml/g, and 4-10nm pore volume integration rate is 80%.
Embodiment 17
This example is the preparation of reference catalyst B.
Method with form similar to Example 16ly substantially, the Y-A component is changed to the super-hydrophobic Y that does not carry out cation exchange-W zeolite (Wenzhou catalyst plant) among the embodiment 1.Finally consisting of of this catalyst: Z-A11wt%, super-hydrophobic Y zeolite Y-W 3.5wt%, modified aluminas 40wt%, WO
324.69wt%, NiO 4.71wt%, surplus is the adhesive aluminium oxide, its character is as follows: specific surface is 185m
2/ g, pore volume are 0.323ml/g, and 4-10nm pore volume integration rate is 69%.
The character of table 3 diesel raw material and diesel product
| Feedstock oil | Diesel product | ||
| Catalyst A | Catalyst B | ||
| Boiling range, ℃ | 175～370 | 181～367 | 180～366 |
| Sulphur, μ g/g | 5500 | 28 | 39 |
| Nitrogen, μ g/g | 711 | 2.0 | 3.9 |
| Condensation point, ℃ | -3 | -26 | -20 |
| Cetane number | 25 | 35.1 | 33.3 |
| Diesel yield, wt% | - | 99.5 | 92.8 |
By table 1 data as can be seen, the y-type zeolite after the modification, little although its infrared total acidity changes, its B acid ratio reduces greatly, and the increasing degree of L acid ratio is enhanced.Reaction result by table 3 can be found out, compares with catalyst B, and catalyst A guarantees diesel yield to reducing the cracking of diesel oil distillate, and it is very favourable to improve the isomerization reaction selectivity.
Adopt modified Y zeolite and ZSM-23 zeolite in the carrier of the present invention simultaneously, synergism by two kinds of zeolites, make catalyst have ability of aromatic hydrocarbons open loop preferably and preferable heterogeneous activity simultaneously, and the catalyst aperture accounts for the 75%-90% of total pore volume in the pore size distribution of 4-10nm, the aperture is very concentrated, help the diffusion of feedstock oil like this, better bring into play catalytic activity.By the result of table 3 as can be seen, adopt the catalyst of preparing carriers of the present invention more to help improving the diesel oil distillate quality, make the higher and pour point depression better effects if of yield of diesel oil distillate.
Claims (12)
1, a kind of alumina support that contains composite zeolite comprises modified Y zeolite, ZSM-23 zeolite and aluminium oxide, and the character of described modified Y zeolite is as follows: contain group vib and/or group VIII metallic element 2wt%-10wt%, SiO
2/ Al
2O
3Mol ratio is 9.0-12.9, and lattice constant is 2.440-2.459nm, and specific area is 550-650m
2/ g, pore volume are 0.340-0.370ml/g, and infrared acidity is 1.37-1.60mmol/g, wherein the mol ratio 1 of B acid and L acid: 3-1: 5, and Na
2O weight content＜0.2%.
2, according to the described carrier of claim 1, it is characterized in that the weight with carrier is benchmark, the content of modified Y zeolite is 1%-20%, and the content of ZSM-23 zeolite is 1%-30%, and the content of aluminium oxide is 30%～98%, adhesive 0～30%.
3, according to the described carrier of claim 1, it is characterized in that: the weight with carrier is benchmark, and the content of modified Y zeolite is 5%-15%, and the content of ZSM-23 zeolite is 5%-20%, and the content of aluminium oxide is 40%-85%, adhesive 0～25%.
4,, it is characterized in that described group vib and/or group VIII metallic element are one or more among W, Ni, Co, Fe, the Mo according to the described carrier of claim 1.
5, according to the described carrier of claim 1, the specific area that it is characterized in that described carrier is 280-330m
2/ g, pore volume are 0.50-0.60ml/g, and wherein the aperture accounts for the 80%-90% of total pore volume in the pore size distribution of 4-10nm, and infrared acidity is 0.36-0.50mmol/g.
6,, it is characterized in that the character of described ZSM-23 zeolite is as follows: SiO according to the described carrier of claim 1
2/ Al
2O
3Mol ratio is 40-100, and infrared acidity is 0.1-0.4mmol/g, Na
2O weight content＜0.2%.
7, according to the described carrier of claim 6, it is characterized in that described ZSM-23 zeolite is little crystal grain zeolite, its particle diameter is 1～100nm.
8, according to the described carrier of claim 1, it is characterized in that described aluminium oxide is the aluminium oxide through additive modification, its character is as follows: specific area is 320-370m
2/ g, pore volume are 0.7～1.1ml/g, and auxiliary agent is 3wt%-7wt% in the content of element, and described auxiliary agent is one or more in boron, fluorine and the zirconium.
9, the arbitrary described preparation method who contains the alumina support of composite zeolite of claim 1～8 comprises the steps:
(1) modified Y zeolite, ZSM-23 zeolite and aluminium oxide are mixed;
(2) in the mixture of step (1), add adhesive or directly add peptizing agent solution and mix and pinch into paste, extruded moulding;
(3),,, obtain carrier of the present invention at 350～700 ℃ of roasting 1-12 hours 100～150 ℃ of dryings 0.5～24 hour with above-mentioned article shaped.
10, in accordance with the method for claim 9, it is characterized in that described modified Y zeolite is prepared as follows by super-hydrophobic Y zeolite:
(1) super-hydrophobic Y zeolite is placed water, its mesolite is 1 with the ratio of the weight of water: 2-10, be warming up to 60 ℃-90 ℃, and stirred 0.5-2.0 hour;
(2) get and contain in group vib and/or the group VIII metal soluble salt one or more and be mixed with solution, add in above-mentioned steps (1) solution, regulator solution pH value, be controlled at 4-10, solution is under 50-90 ℃, stir fully exchange in aging 2-4 hour, after the filtration, made in dry 8-24 hour at 100 ℃-150 ℃.
11, in accordance with the method for claim 10, it is characterized in that described super-hydrophobic Y zeolite is obtained after under 500～600 ℃, 0.01～0.30MPa condition hydrothermal treatment consists 1-10 hour by the Y zeolite; Wherein the character of Y zeolite is as follows: NaO content is lower than 0.2wt%, silica alumina ratio 6-40, lattice constant 2.440-2.460nm.
12, Preparation of catalysts method according to claim 10 is characterized in that the described super-hydrophobic Y zeolite of step (1) and the ratio of the weight of water are 1: 3-8.
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