CN103100430A - Hydrocracking catalyst carrier and preparation method thereof - Google Patents
Hydrocracking catalyst carrier and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydrocracking catalyst carrier and a preparation method thereof. The hydrocracking catalyst carrier comprises: a modified beta molecular sieve, a modified Y type molecular sieve and alumina. Specifically, the modified beta molecular sieve is prepared by: subjecting a crystallized beta molecular sieve slurry directly to ammonium exchange and a template agent removal treatment, then first conducting a hydrothermal treatment, and performing an aluminum salt solution treatment, under the condition of maintaining a high beta molecular sieve crystallinity, removing part of non-framework aluminum uniformly, thus obtaining the beta molecular sieve with the characteristics of high Si/Al ratio, large specific surface area, appropriate acidity and acid distribution, and reasonable pore structure, etc. The modified beta molecular sieve especially has a suitable cracking effect and a very good isomerization effect on long-chain alkane and the long side chain alkyl of aromatic hydrocarbon and cyclane, and has a synergistic effect with the Y type molecular sieve, so that the prepared hydrocracking catalyst can have very high catalytic activity and middle distillate selectivity. And the condensation point of diesel fraction is substantially reduced, and the product properties of middle distillate are improved.
Description
Technical field
The present invention relates to a kind of carrier of hydrocracking catalyst and preparation method thereof, particularly having adopted beta-molecular sieve and Y zeolite is main cracking component, is applicable to prepare the hydrocracking catalyst of production high-quality intermediate oil.
Background technology
In recent years, oil product market, countries in the world constantly increases the demand of high-quality middle cut oil product always, and along with developing rapidly of economy, it is more outstanding that this imbalance between supply and demand seems.Hydrocracking technology has become the best means of heavy oil deep processing production high-quality cleaning intermediate oil with its exclusive advantage.
At present, in countries in the world, the activity of oil type hydrocracking catalyst is not very high, and the condensation point of gained diesel oil is also higher, is difficult to satisfy the refinery and existing apparatus is transformed or increased treating capacity to reach the purpose of further volume increase intermediate oil.
The raise productivity and improve the quality key of intermediate oil of hydrocracking is to develop and use suitable catalyst.Although contain the hydrocracking catalyst of single molecular sieve component, very high activity is arranged, its middle distillates oil selectivity is relatively poor, and the catalyst that contains composite molecular screen but shows and can improve activity and can improve again optionally synergy.
The hydrocracking technology core is catalyst, and the key component that plays cracking in this type of catalyst mostly is Y zeolite and beta-molecular sieve.With respect to Y zeolite, beta-molecular sieve has three-dimensional twelve-ring pore structure, but the supercage structure as Y zeolite not, its main feature is two 6 ring unit's bug hole structures of two 4 rings and four 5 rings, main aperture road diameter is at 0.56-0.75nm, the duct characteristics of beta-molecular sieve make it, and fracture has good effect to the chain hydrocarbon-selective in cracking reaction, and has a very strong isomery performance, can be used for Low Freezing Point middle oil cut as the cracking component, be widely used industrial.
Introduced a kind of optionally method of hydrocracking of the β of utilization zeolite in CN101578353A.The β zeolite do not carry out hydrothermal treatment consists or at relatively low temperature hydrothermal treatment consists, the mol ratio of silica and aluminium oxide is less than 30:1 and the SF of 28wt% at least
6Adsorbance, the catalyst that this β zeolite that obtains by modification prepares as the cracking component, intermediate oil selectively not high.
CN1351121A has announced a kind of hydrocracking catalyst that contains modified beta zeolite and preparation method thereof.Mention the β Zeolite modifying method in the method and directly carry out the ammonium salt exchange for the β zeolite slurry after synthetic, and take off ammonium, acid treatment and hydrothermal treatment consists and obtain β zeolite after modification through roasting.in the method, first the β zeolite is carried out acid treatment, and then carry out hydrothermal treatment consists, to adopt mineral acid treatment in the acid treatment process, will destroy the skeleton structure of part molecular sieve in this course, molecular sieve crystallinity descends, the non-skeleton structure that forms bulk is stayed in molecular sieve pore passage, be difficult to be removed, affect acid distribution and the acid strength of modified molecular screen, in addition, also carried out high-temperature water heat treatment after acid treatment, also can form a certain amount of non-framework aluminum in molecular sieve, this will directly affect pore structure and the Acidity of molecular sieve, the acid distribution of molecular sieve and the variation of Acidity will directly affect thus molecular sieve as the performance of the catalyst of cracking component, especially affect the character of hydrocracking diesel oil and hydrogenation tail oil.
US 5,350, and 501, US 5,447,623, US 5,279,726, US 5,536,687 introduced the catalyst of a kind of β of containing zeolite and Y zeolite.During for the production of intermediate oil, it consists of: Y molecular sieve (1 ~ 15w%), and beta-molecular sieve (1 ~ 15w%), decentralized sial, aluminium oxide, metal W and Ni.Wherein beta-molecular sieve used is to obtain the Hydrogen beta-molecular sieve through the mode that template is removed in ion-exchange and roasting.This catalyst reaction is active and middle distillates oil selectivity is all not bery high, is difficult to satisfy manufacturer's aggrandizement apparatus disposal ability, further increases production the needs of intermediate oil.
CN1393521A discloses a kind of middle oil type hydrocracking catalyst and preparation method thereof, and the catalyst used carrier is the complex type molecular sieve of amorphous aluminum silicide, aluminium oxide and Y and β.Wherein composite molecular screen be with after the former powder burning-off of beta-molecular sieve template with after modified Y molecular sieve mixes, then through H
+And NH
4 +Mixed solution is processed and is got.The method is with the first burning-off template of the former powder of beta-molecular sieve, like this to the degree of crystallinity of decrease molecular sieve, also affects the acidity of molecular sieve, match with other component, the catalytic activity of this catalyst is not high, and the product quality of the intermediate oil of boat coal and diesel oil is general, needs further to improve.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides a kind of carrier of hydrocracking catalyst and preparation method thereof.This carrier of hydrocracking catalyst adopts the Y zeolite of a kind of high silica alumina ratio, bigger serface, acid suitable, the rational beta-molecular sieve of pore structure and a kind of modification jointly to do as the cracking component.The beta molecular sieve that uses can keep on skeleton complete basis, and the remove portion non-framework aluminum can act synergistically with Y zeolite again, and prepared catalyst has active height and high-output qulified midbarrel wet goods characteristics.
Carrier of hydrocracking catalyst of the present invention comprises modified beta molecular sieve, Modified Zeolite Y and aluminium oxide, wherein said modified beta molecular sieve, and its character is as follows: specific surface 450m
2/ g～750m
2/ g is preferably 500～700m
2/ g, total pore volume 0.30ml/g～0.45mL/g, SiO
2/ Al
2O
3Mol ratio 40～100, preferred 50～80, relative crystallinity is 120%～140%, meleic acid amount 0.1～0.5mmol/g, the mol ratio of Gu Jia Lv ∕ non-framework aluminum is that 5～20, B acid/L acid is 0.30～0.50, Na
2O≤0.15wt% is preferably≤0.10wt%.
Described carrier of hydrocracking catalyst, with the weighing scale of carrier, the content of modified beta molecular sieve is 5%～20%, and the content of Modified Zeolite Y is 10%～40%, and the content of aluminium oxide is 40%～85%.
Described modified Y molecular sieve, its character is as follows: specific surface 850m
2/ g～950m
2/ g, total pore volume 0.43mL/g～0.55mL/g, degree of crystallinity 90%～130%, silica alumina ratio 20～150, cell parameter 2.425～2.433nm, meleic acid amount 0.1～0.4mmol/g.This Y zeolite can adopt the prior art preparation.
Carrier of hydrocracking catalyst character of the present invention is as follows: specific area is 300～500m
2/ g, pore volume are 0.5～1.0mL/g.
The preparation method of carrier of hydrocracking catalyst of the present invention comprises the steps:
With modified beta molecular sieve, modified Y molecular sieve, aluminium oxide, adhesive mechanical mixture, moulding, then drying and roasting, make catalyst carrier;
Wherein said modified beta molecular sieve comprises being prepared as follows step:
(1) the beta-molecular sieve slurries after crystallization directly carry out ammonium exchange, filtration, washing, drying;
(2) dried beta-molecular sieve carries out the Template removal processing;
(3) beta-molecular sieve that has taken off template carries out hydrothermal treatment consists again.
(4) with the beta molecular sieve of aluminum saline solution treatment step (3) gained, then filter, wash and drying.
In step (2), it is to adopt conventional method to carry out that described Template removal is processed, and generally adopts the aerobic high-temperature process, processes dried beta-molecular sieve in open kiln, and treatment temperature is 400～800 ℃, and the processing time is 5～20 hours.
In step (3), described hydrothermal treatment consists is to operate in dedicated molecular sieve used hydrothermal treatment consists stove, and treatment conditions are: gauge pressure 0.05～0.4MPa, be preferably 0.1～0.2MPa, 450～750 ℃ of temperature are preferably 500～700 ℃, 0.5～5 hour processing time, preferred 1～3 hour.
In step (4), in the solution of described aluminium salt, the concentration of aluminium salt is (with Al
3+Meter) 0.1～2.0mol/L, preferred 0.5～1.5mol/L.It is formulated that the solution of described aluminium salt can adopt aluminium salt to be added to the water, and aluminium salt can be one or more in aluminum nitrate, aluminium chloride, aluminum sulfate.The solution of aluminium salt and the weight ratio of molecular sieve are 3:1～50:1.Described treatment conditions: 40～120 ℃ of temperature, be preferably 70～100 ℃, the time is 0.5～8.0 hour, preferred 1.0～3.0 hours.Described washing condition: until cleaning solution pH value is near neutrality, then under the condition of 100～120 ℃ dry 3～6 hours.
The beta-molecular sieve of modification that the present invention adopts first carries out hydrothermal treatment consists after taking off ammonium, the method that rear employing aluminium salt is processed is come modified beta molecular sieve, can evenly deviate from the part non-framework aluminum under the condition that keeps the beta-molecular sieve high-crystallinity, make molecular sieve have suitable acid distribution and pore structure.Using aluminium salt to process is under a kind of condition of relative mitigation, can guarantee under the prerequisite of saboteur's sieve skeleton frame not, uniformly the part non-framework aluminum that forms after hydrothermal treatment consists is removed, improved the ratio of framework aluminum and non-framework aluminum in the molecular sieve, improved the pore passage structure of molecular sieve, made its absorption that more is conducive to reactant and product, reaction and diffusion.In addition, adopt aluminium salt to process beta-molecular sieve, because the silica alumina ratio of beta-molecular sieve itself is higher, also will there be a small amount of aluminium to move back in the skeleton structure of molecular sieve in processing procedure, stablize the skeleton structure of molecular sieve, improved the degree of crystallinity of molecular sieve, improved the Acidity of modified molecular screen.This modified beta molecular sieve has high silica alumina ratio, bigger serface, acidity and acid suitable, the characteristics such as pore structure is reasonable that distribute.The modified beta molecular sieve that the present invention selects has suitable splitting action and good isomerization to the long side chain n-alkyl of long chain alkane and aromatic hydrocarbons, cycloalkane, make the prepared hydrocracking catalyst can be when keeping high diesel yield, reduce by a relatively large margin the condensation point of diesel oil distillate, reach the effect of volume increase low-coagulation diesel oil.
Modified beta molecular sieve of the present invention and Modified Zeolite Y are jointly as cracking center, both given full play to its performance characteristics separately, the concerted catalysis effect that two kinds of molecular sieves are produced, be that the modification beta molecular sieve has good isomerization to the long side chain on alkane or aromatic hydrocarbons, can effectively reduce the condensation point of product, Y zeolite has very high selectivity of ring-opening to aromatic hydrocarbons simultaneously, improves the product property of purpose product.The prepared hydrocracking catalyst of carrier of the present invention has active high, can high-output qulified midbarrel oil product (boat coal+diesel oil), and can hold concurrently simultaneously and produce the hydrogenation tail oil of high-quality.
When being used for heavy oil hydrocracking by the hydrocracking catalyst of carrier of the present invention preparation, particularly condition of high voltage (12～20MPa) and process wax slop (VGO, CGO and DAO) and or poor ignition quality fuel (coker gas oil and catalytic diesel oil etc.) miscella, have very high catalytic activity and intermediate oil selective, and the freezing point reduction amplitude of diesel oil distillate is large, the product property of intermediate oil improves, and can satisfy the needs that the refinery increases operating flexibility, increase device disposal ability, further increases production intermediate oil.
The specific embodiment
In carrier of hydrocracking catalyst of the present invention, aluminium oxide can adopt aluminium oxide used in conventional hydrocracking catalyst, as macroporous aluminium oxide and ∕ or little porous aluminum oxide.
Aluminium oxide pore volume 0.7～1.0mL/g that carrier of hydrocracking catalyst of the present invention is used, specific area 200～500m
2/ g.
Adhesive therefor of the present invention is to be made by little porous aluminum oxide and inorganic acid and/or organic acid.Aperture aluminium oxide pore volume used is 0.3～0.5mL/g, and specific area is 200～400m
2/ g.
Modified beta molecular sieve in carrier of hydrocracking catalyst of the present invention, concrete preparation method is as follows:
(1) the beta-molecular sieve slurries after crystallization directly carry out ammonium exchange, filtration, washing, drying
Beta-molecular sieve after above-mentioned crystallization is generally take organic ammonium (as tetraethyl ammonium hydroxide) as template, synthesizes with hydrothermal crystallization method.Its chemical SiO
2/ Al
2O
3(mol ratio) is generally 20～30, Na
2The content of O is 3.0～4.0wt%.Beta-molecular sieve slurries after crystallization directly carry out the ammonium salt exchange, and the concentration of ammonium salt in slurries is 0.5～5.0mol/L, and several is carried out in the ammonium exchange, make Na in the rear molecular sieve of exchange
2The O weight content is less than 0.3%, and general ammonium exchange 1～5 time can reach requirement.Beta-molecular sieve after ammonium salt exchange filters, washes, drying;
(2) dried beta-molecular sieve carries out the Template removal processing
Added template in the process of the synthetic beta-molecular sieve of crystallization, if this template is present in molecular sieve, will be to having a direct impact take the catalyst of beta-molecular sieve as the cracking component, stop up the duct of beta-molecular sieve, and then form the acid centre that carbon distribution occupies molecular sieve, affect the cracking performance performance of catalyst.Therefore need template is removed, the mode of removing template generally adopts the aerobic roasting, the beta-molecular sieve that namely treatment step (1) obtains in open kiln, and treatment temperature is 400～800 ℃, the processing time is 5～20 hours, controls carbon residue≤0.2 wt%;
(3) beta-molecular sieve that has taken off template carries out hydrothermal treatment consists again
The molecular sieve that obtains in hydrothermal treatment step (2) is to carry out in the hydrothermal treatment consists stove of special use, the hydrothermal treatment consists condition is: adopt the 100wt% water vapour, at gauge pressure 0.05～0.4MPa, be preferably 0.1～0.2MPa, 450～750 ℃ of temperature, be preferably 500～700 ℃, 0.5～5.0 hour processing time, preferred 1.0～3.0 hours;
(4) use the beta-molecular sieve of solution treatment steps (3) gained of aluminium salt, then filter, wash and drying
Add aluminum saline solution in return-flow system and airtight container, wherein the aluminium salinity is (with Al
3+Meter) 0.1～2.0mol/L, preferred 0.5～1.5mol/L stirs and is warmed up to 40～120 ℃, is preferably 70～100 ℃, then the weight ratio by aluminum salt solution and molecular sieve is 3:1～50:1, the molecular sieve that adds step (3) to obtain, constant temperature stirred 0.5～8.0 hour, preferred 1.0～3.0 hours, filter, wash, the washing until cleaning solution pH value near neutrality, and under the condition of 100～120 ℃ the drying 3～6 hours, obtain beta-molecular sieve of the present invention.Wherein the solution of aluminium salt can be one or more the aqueous solution in aluminium chloride, aluminum nitrate, aluminum sulfate.
The detailed process of carrier of hydrocracking catalyst preparation of the present invention is:
Modified beta molecular sieve, Modified Zeolite Y, aluminium oxide and adhesive are mixed, then extruded moulding carries out drying and roasting, is prepared into carrier, described drying can be carried out at the temperature of 80 ℃ to 150 ℃ 3～6 hours, and roasting is 500 ℃～600 ℃ roastings 2.5～6 hours.
Carrier of hydrocracking catalyst of the present invention is the supported active metal component by conventional methods, is prepared into hydrocracking catalyst.Adopt carrying method conventional in prior art, preferred infusion process, can be saturatedly soak, excessive soak or complexing is soaked, namely with the solution impregnated catalyst carrier that contains required active component, carrier after dipping was 100 ℃～150 ℃ dryings 1～12 hour, then 450 ℃～550 ℃ roastings 2.5～6.0 hours, make final catalyst.
The following examples are used for illustrating in greater detail the present invention, but scope of the present invention is not only limited to the scope of these embodiment.
Analytical method of the present invention: specific area and pore volume adopt the low temperature liquid nitrogen physisorphtion, silica alumina ratio adopts chemical method, framework silicon-aluminum is adopted by the NMR method and is measured, meleic acid amount, B acid amount and L acid amount adopt the pyridine adsorption infra-red sepectrometry, wherein the summation of B acid amount and L acid amount is the meleic acid amount, sodium content adopts plasma emission spectrometry, and Electronic Speculum adopts the projection Electronic Speculum, and relative crystallinity adopts XRD method to measure.In the present invention, wt% is mass fraction.
Embodiment 1
Modified beta molecular sieve of the present invention is take tetraethyl ammonium hydroxide as template, adopts hydrothermal crystallization method to synthesize.Get the synthetic former powder slurry of the beta-molecular sieve 10000mL of industry, wherein contain approximately 2000g of solid phase beta-molecular sieve, its chemical sial SiO
2/ Al
2O
3(mol ratio) than being 27.49, specific area is 101m
2/ g, pore volume are 0.19cm
3/ g, sodium oxide content are 3.67wt%.Add appropriate water purification in slurry, and add a certain amount of ammonium nitrate, make liquid-solid ratio (weight) be 10:1, the concentration of ammonium nitrate is 2mol/L, stir, be warmed up to 95～100 ℃, constant temperature stirred 2 hours, then filter, filter cake secondary again carries out ammonium exchange, and the condition of exchange is with identical for the first time, washs at last beta-molecular sieve till the pH value neutrality, put into dry zone dry, drying is 8 hours under 100～120 ℃.Get dried beta-molecular sieve and deviate from the template processing, adopt open kiln to process, 570 ℃ of constant temperature were processed 15 hours.Gained molecular sieve label is B-1, and character sees Table 1.
Embodiment 2
Getting 200g B-1 is raw material, and B-1 is carried out hydrothermal treatment consists, and at water vapor pressure 0.15MPa, treatment temperature is 550 ℃, and the processing time is 2 hours.The gained molecular sieve is B-2, and character sees Table 1.
Getting 200g B-1 is raw material, and B-1 is carried out hydrothermal treatment consists, and at water vapor pressure 0.15MPa, treatment temperature is 650 ℃, and the processing time is 2 hours.The gained molecular sieve is B-3, and character sees Table 1.
Embodiment 3
Taking 60g B-2 molecular sieve puts into reflux and flask that can be airtight, add to contain concentration 0.8mol/L aluminum sulfate aqueous solution 1000ml, stirred 1.0 hours at 95 ℃ of lower constant temperature, filter, and use the hot deionized water washing leaching cake, stop washing with the pH value of cleaning solution after 7.Filter cake 120 ℃ of dryings 5 hours in baking oven obtain beta molecular sieve of the present invention, and it numbers B-4, and molecular sieve character sees Table 1.
Embodiment 4
Taking 60g B-2 molecular sieve puts into reflux and flask that can be airtight, add to contain concentration 0.4mol/L aluminum sulfate aqueous solution 1500ml, stirred 2 hours at 90 ℃ of lower constant temperature, filter, and use the hot deionized water washing leaching cake, stop washing with the pH value of cleaning solution after 7.Filter cake 120 ℃ of dryings 5 hours in baking oven.Obtain beta molecular sieve of the present invention, it numbers B-5, and molecular sieve character sees Table 1.
Embodiment 5
Taking 60g B-3 molecular sieve puts into reflux and flask that can be airtight, add to contain concentration 0.6mol/L aluminum nitrate aqueous solution 2500ml, stirred 1.5 hours at 80 ℃ of lower constant temperature, filter, and use the hot deionized water washing leaching cake, stop washing with the pH value of cleaning solution after 7.Filter cake 120 ℃ of dryings 5 hours in baking oven obtain beta molecular sieve of the present invention, and it numbers B-6, and molecular sieve character sees Table 1.
Embodiment 6
Taking 60g B-3 molecular sieve puts into reflux and flask that can be airtight, add to contain concentration 1.0mol/L alchlor aqueous solution 300ml, stirred 2.0 hours at 90 ℃ of lower constant temperature, filter, and use the hot deionized water washing leaching cake, stop washing with the pH value of cleaning solution after 7.Filter cake 120 ℃ of dryings 5 hours in baking oven obtain beta molecular sieve of the present invention, and it numbers B-7, and molecular sieve character sees Table 1.
Comparative Examples 1
Get B-1 molecular sieve 300g, adopt the hydrochloric acid of 0.5mol/L to process, treatment conditions are: liquid-solid ratio 10:1, stirred 2.5 hours at temperature 70 C constant temperature, filter, and use the hot deionized water washing leaching cake, stop washing with the pH value of cleaning solution after 7, filter cake 120 ℃ of dryings 5 hours in baking oven.At water vapor pressure 0.15MPa, treatment temperature is 550 ℃ with dried molecular sieve, and the processing time is 2 hours.The gained molecular sieve is B-8, and character sees Table 1.
Comparative Examples 2
Get B-1 molecular sieve 300g, adopt the nitric acid of 0.7mol/L to process, treatment conditions are: liquid-solid ratio 10:1, stirred 2.5 hours at 80 ℃ of constant temperature of temperature, filter, and use the hot deionized water washing leaching cake, stop washing with the pH value of cleaning solution after 7, filter cake 120 ℃ of dryings 5 hours in baking oven.At water vapor pressure 0.1MPa, treatment temperature is 600 ℃ with dried molecular sieve, and the processing time is 2 hours.The gained molecular sieve is B-9, and character sees Table 1.
Comparative Examples 3
Get B-1 molecular sieve 300g, adopt the sulfuric acid of 0.3mol/L to process, treatment conditions are: liquid-solid ratio 15:1, stirred 2.5 hours at 95 ℃ of constant temperature of temperature, filter, and use the hot deionized water washing leaching cake, stop washing with the pH value of cleaning solution after 7, filter cake 120 ℃ of dryings 5 hours in baking oven.At water vapor pressure 0.2MPa, treatment temperature is 650 ℃ with dried molecular sieve, and the processing time is 2 hours.The gained molecular sieve is B-10, and character sees Table 1.
The character of table 1 embodiment and Comparative Examples gained molecular sieve
| ? | Embodiment 1 | Embodiment 2 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Numbering | B-1 | B-2 | B-3 | B-4 | B-5 |
| Silica alumina ratio | 27.80 | 27.80 | 27.80 | 59.9 | 63.4 |
| Specific area, m 2/g | 685 | 653 | 639 | 691 | 689 |
| Pore volume, ml/g | 0.389 | 0.403 | 0.416 | 0.421 | 0.426 |
| Relative crystallinity, % | 96 | 93 | 91 | 132 | 135 |
| Infrared acidity, mmol/g | 1.1 | 0.42 | 0.31 | 0.37 | 0.34 |
| Framework aluminum/non-framework aluminum | ? | ? | ? | 18.5 | 11.6 |
| B acid/L acid | ? | ? | ? | 0.45 | 0.38 |
| Na 2O，wt% | 0.23 | 0.23 | 0.23 | 0.03 | 0.02 |
Table 1 is continuous
| ? | Embodiment 5 | Embodiment 6 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| Numbering | B-6 | B-7 | B-8 | B-9 | B-10 |
| Silica alumina ratio | 71.6 | 61.3 | 51.6 | 56.9 | 49.8 |
| Specific area, m 2/g | 677 | 647 | 621 | 632 | 643 |
| Pore volume, ml/g | 0.409 | 0.413 | 0.401 | 0.415 | 0.409 |
| Relative crystallinity, % | 131 | 138 | 123 | 120 | 125 |
| Infrared acidity, mmol/g | 0.26 | 0.27 | 0.35 | 0.30 | 0.25 |
| Framework aluminum/non-framework aluminum | 8.3 | 9.7 | 3.5 | 4.2 | 4.0 |
| B acid/L acid | 0.32 | 0.33 | 0.18 | 0.16 | 0.18 |
| Na 2O，wt% | 0.02 | 0.03 | 0.06 | 0.05 | 0.06 |
Embodiment 7
With 22.22 gram B-5 molecular sieves (butt 90wt%), 44.44 gram Y zeolite (SiO
2/ Al
2O
3=50, lattice constant 2.431nm, pore volume 0.45ml/g, specific area 900m
2/ g, butt 90wt%), 157.1 gram macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 100 gram adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) are put into the roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, get carrier HCS-1.
Carrier is with the maceration extract room temperature dipping of tungstenic and nickel 2 hours, 120 ℃ of dryings 4 hours, and 500 ℃ of roastings of temperature programming 4 hours get catalyst HC-1, and carrier and corresponding catalyst character see Table 2.
Embodiment 8
With 33.33 gram B-5 molecular sieves (butt 90wt%), 44.44 gram Y zeolite (SiO
2/ Al
2O
3=50, lattice constant 2.431nm, pore volume 0.45ml/g, specific area 900m
2/ g, butt 90wt%), 142.86 gram macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 100 gram adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) are put into the roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, get carrier HCS-2.
Carrier is with the maceration extract room temperature dipping of tungstenic and nickel 2 hours, 120 ℃ of dryings 4 hours, and 500 ℃ of roastings of temperature programming 4 hours get catalyst HC-2, and carrier and corresponding catalyst character see Table 2.
Embodiment 9
With 11.11 gram B-6 molecular sieves (butt 90wt%), 66.67 gram Y zeolite (SiO
2/ Al
2O
3=50, lattice constant 2.431nm, pore volume 0.45ml/g, specific area 900m
2/ g, butt 90wt%), 142.86 gram macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 100 gram adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) are put into the roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, get carrier HCS-3.
Carrier is with the maceration extract room temperature dipping of tungstenic and nickel 2 hours, 120 ℃ of dryings 4 hours, and 500 ℃ of roastings of temperature programming 4 hours get catalyst HC-3, and carrier and corresponding catalyst character see Table 2.
Embodiment 10
With 44.44 gram B-6 molecular sieves (butt 90wt%), 55.56 gram Y zeolite (SiO
2/ Al
2O
3=50, lattice constant 2.431nm, pore volume 0.45ml/g, specific area 900m
2/ g, butt 90wt%), 88.89 gram macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 100 gram adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) are put into the roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, get carrier HCS-4.
Carrier is with the maceration extract room temperature dipping of tungstenic and nickel 2 hours, 120 ℃ of dryings 4 hours, and 500 ℃ of roastings of temperature programming 4 hours get catalyst HC-4, and carrier and corresponding catalyst character see Table 2.
Comparative Examples 4
With 33.33 gram B-10 molecular sieves (butt 90wt%), 44.44 gram Y zeolite (SiO
2/ Al
2O
3=50, lattice constant 2.431nm, pore volume 0.45ml/g, specific area 900m
2/ g, butt 90wt%), 142.86 gram macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 100 gram adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) are put into the roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, get carrier HCDS-1.
Carrier is with the maceration extract room temperature dipping of tungstenic and nickel 2 hours, 120 ℃ of dryings 4 hours, and 500 ℃ of roastings of temperature programming 4 hours get catalyst HCD-1, and carrier and corresponding catalyst character see Table 2.
Comparative Examples 5
With 11.11 gram B-10 molecular sieves (butt 90wt%), 66.67 gram Y zeolite (SiO
2/ Al
2O
3=50, lattice constant 2.431nm, pore volume 0.45ml/g, specific area 900m
2/ g, butt 90wt%), 142.86 gram macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 100 gram adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) are put into the roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, get carrier HCDS-2.
Carrier is with the maceration extract room temperature dipping of tungstenic and nickel 2 hours, 120 ℃ of dryings 4 hours, and 500 ℃ of roastings of temperature programming 4 hours get catalyst HDC-2, and carrier and corresponding catalyst character see Table 2.
Comparative Examples 6
This Comparative Examples is to change the B-5 molecular sieve in embodiment 8 into the B1 molecular sieve, and other is with embodiment 8 preparation carrier HCDS-3, and character sees Table 2.
Carrier is with the maceration extract room temperature dipping of tungstenic and nickel 2 hours, 120 ℃ of dryings 4 hours, and 500 ℃ of roastings of temperature programming 4 hours get catalyst HCD-3, and carrier and corresponding catalyst character see Table 2.
Embodiment 11
The present embodiment has been introduced by catalyst activity evaluation result of the present invention.Estimate on the fixed bed hydrogenation experimental rig, appreciation condition is: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity 1.5h
-1, use vacuum distillate (VGO) as feedstock oil, feedstock oil character is listed in table 3.Catalyst HC-2, HCD-1 and HCD-3 are estimated under identical process conditions, and the evaluation result that obtains is listed in table 4.
Can be found out by evaluation result, prepared catalyst of the present invention is under identical process conditions, and intermediate oil is selective, yield and product quality all are better than reference catalyst.
The physico-chemical property of table 2 catalyst carrier and catalyst
| ? | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative Examples 4 | Comparative Examples 5 | Comparative Examples 6 |
| Carrier forms and character | ? | ? | ? | ? | ? | ? | ? |
| Numbering | HCS-1 | HCS-2 | HCS-3 | HCS-4 | HCDS-1 | HCDS-2 | HCDS-3 |
| Modified beta molecular sieve, wt% | 10 | 15 | 5 | 20 | 15 | 5 | 15 |
| Modified Y molecular sieve, wt% | 20 | 20 | 30 | 25 | 20 | 30 | 20 |
| Macroporous aluminium oxide, wt% | 55 | 50 | 50 | 40 | 50 | 50 | 50 |
| Adhesive, wt% | 15 | 15 | 15 | 15 | 15 | 15 | 15 |
| Pore volume, mL/g | 436 | 450 | 466 | 481 | 411 | 428 | 302 |
| Specific area, m 2/g | 0.67 | 0.64 | 0.64 | 0.66 | 0.61 | 0.59 | 0.60 |
| Catalyst forms and character | ? | ? | ? | ? | ? | ? | ? |
| Numbering | ? | HC-2 | ? | ? | HCD-1 | ? | HCD-3 |
| WO 3，wt% | ? | 21.59 | ? | ? | 22.06 | ? | 21.50 |
| NiO，wt% | ? | 5.3 | ? | ? | 5.2 | ? | 5.3 |
| Pore volume, mL/g | ? | 329 | ? | ? | 299 | ? | 232 |
| Specific area, m 2/g | ? | 0.47 | ? | ? | 0.44 | ? | 0.37 |
Table 3 feedstock oil character
| Feedstock oil | Vacuum distillate (VGO) |
| Density (20 ℃), g/cm 3 | 0.9072 |
| Boiling range, ℃ | ? |
| IBP/10% | 305/361 |
| 30%/50% | 394/417 |
| 70%/90% | 443/481 |
| 95%/EBP | 509/533 |
| Condensation point, ℃ | 34 |
| Sulphur, wt% | 1.98 |
| Nitrogen, μ g/g | 1228 |
| Carbon, wt% | 85.28 |
| Hydrogen, wt% | 12.46 |
| The BMCI value | 45.0 |
Table 4 HC-2, HCD-1 and HCD-3 Evaluation results
| Catalyst | HC-2 | HCD-1 | HCD-3 |
| Feedstock oil | Vacuum distillate (VGO) | Vacuum distillate (VGO) | Vacuum distillate (VGO) |
| Volume space velocity, h -1 | 1.5 | 1.5 | 1.5 |
| The reaction stagnation pressure, MPa | 14.7 | 14.7 | 14.7 |
| Hydrogen to oil volume ratio | 1200 | 1200 | 1200 |
| Reaction temperature, ℃ | 372 | 374 | 380 |
| Product yield and character | ? | ? | ? |
| Heavy naphtha | ? | ? | ? |
| Yield, wt% | 9.1 | 11.2 | 12.6 |
| Virtue is dived, wt% | 65.8 | 62.3 | 59.8 |
| Jet fuel | ? | ? | ? |
| Yield, wt% | 47.6 | 44.9 | 42.0 |
| Smoke point, mm | 28 | 26 | 24 |
| Aromatic hydrocarbons, v% | 4.5 | 4.8 | 5.6 |
| Diesel oil | ? | ? | ? |
| Yield, wt% | 22.8 | 22.5 | 21.6 |
| Condensation point, ℃ | -18 | -6 | -5 |
| Cetane number | 68.6 | 67.3 | 61.7 |
| Tail oil | ? | ? | ? |
| Yield, wt% | 15.9 | 15.1 | 16.1 |
| Condensation point, ℃ | 12 | 19 | 20 |
| The BMCI value | 12.4 | 14.6 | 15.3 |
| Intermediate oil is selective, wt% | 83.7 | 80.6 | 77.0 |
| Chemical hydrogen consumption, wt% | 2.63 | 2.72 | 2.75 |
| Liquid is received, wt% | 97.9 | 96.7 | 96.1 |
Claims (15)
1. a carrier of hydrocracking catalyst, comprise modified beta molecular sieve, Modified Zeolite Y and aluminium oxide, wherein said modified beta molecular sieve, and its character is as follows: specific area 450m
2/ g～750m
2/ g, total pore volume 0.30ml/g～0.45ml/g, SiO
2/ Al
2O
3Mol ratio 40～100, relative crystallinity are 120%～140%, meleic acid amount 0.1～0.5mmol/g, and the mol ratio of Gu Jia Lv ∕ non-framework aluminum is that 5～20, B acid/L acid is 0.30～0.50, Na
2O≤0.15wt%.
2. according to catalyst carrier claimed in claim 1, it is characterized in that described modified beta molecular sieve character is as follows: specific surface is 500～700m
2/ g.
3. according to the described catalyst carrier of claim 1 or 2, it is characterized in that the SiO of described modified beta molecular sieve
2/ Al
2O
3Mol ratio 50～80.
4. according to catalyst carrier claimed in claim 1, it is characterized in that described modified Y molecular sieve, its character is as follows: specific surface 850m
2/ g～950m
2/ g, total pore volume 0.43mL/g～0.55mL/g, degree of crystallinity 90%～130%, silica alumina ratio 20～150, cell parameter 2.425～2.433nm, meleic acid amount 0.1～0.4mmol/g.
5. according to claim 1,2 or 4 described catalyst carriers, it is characterized in that described carrier of hydrocracking catalyst, take the weight of carrier as benchmark, the content of modified beta molecular sieve is 5%～20%, the content of Modified Zeolite Y is 10%～40%, and the content of aluminium oxide is 40%～85%.
6. according to catalyst carrier claimed in claim 1, it is characterized in that described carrier of hydrocracking catalyst character is as follows: specific area is 300～500m
2/ g, pore volume are 0.5～1.0mL/g.
7. the preparation method of the arbitrary described carrier of hydrocracking catalyst of claim 1 ~ 6, comprise the steps:
With modified beta molecular sieve, modified Y molecular sieve, aluminium oxide, adhesive mechanical mixture, moulding, then drying and roasting, make catalyst carrier;
Wherein said modified beta molecular sieve comprises being prepared as follows step:
(1) the beta-molecular sieve slurries after crystallization directly carry out ammonium exchange, filtration, washing, drying;
(2) dried beta-molecular sieve carries out the Template removal processing;
(3) beta-molecular sieve that has taken off template carries out hydrothermal treatment consists again;
(4) with the beta molecular sieve of aluminum saline solution treatment step (3) gained, then filter, wash and drying;
In step (3), described hydrothermal treatment consists condition is: gauge pressure 0.05～0.4MPa, 450～750 ℃ of temperature, 0.5～5 hour processing time; In step (4), in the solution of described aluminium salt, the concentration of aluminium salt is with Al
3+Count 0.1～2.0mol/L, the solution of aluminium salt and the weight ratio of molecular sieve are 3:1～50:1, described treatment conditions: 40～120 ℃ of temperature, the time is 0.5～8.0 hour.
8. according to preparation method claimed in claim 7, it is characterized in that in step (3), described hydrothermal treatment consists condition is: gauge pressure 0.1～0.2MPa, temperature is 500～700 ℃, the processing time is 1～3 hour.
9. according to preparation method claimed in claim 8, it is characterized in that in step (4), in the solution of described aluminium salt, the concentration of aluminium salt is with Al
3+Count 0.5～1.5mol/L.
10. according to preparation method claimed in claim 7, it is characterized in that the described treatment conditions of step (4): temperature is 70～100 ℃, and the time is 1.0～3.0 hours.
11. according to preparation method claimed in claim 7, it is characterized in that described aluminium salt is one or more in aluminum nitrate, aluminium chloride, aluminum sulfate.
12. according to preparation method claimed in claim 7, it is characterized in that the described drying condition of step (4) is as follows: drying is 3～6 hours under the condition of 100～120 ℃.
13. according to preparation method claimed in claim 7, it is characterized in that in step (2), described Template removal is processed and adopted the aerobic high-temperature process, treatment temperature is 400～800 ℃, and the processing time is 5～20 hours.
14. according to preparation method claimed in claim 7, it is characterized in that Na in beta-molecular sieve after the exchange of step (1) ammonium
2The O weight content is less than 0.3%.
15. according to preparation method claimed in claim 7, it is characterized in that, after moulding, the condition that carrier carries out dry and roasting is as follows: 80 ℃ ~ 150 ℃ dryings 3～6 hours, 500 ℃～600 ℃ roastings 2.5～6.0 hours.
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| CN104667971A (en) * | 2013-11-26 | 2015-06-03 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier and preparation method thereof |
| CN104667967A (en) * | 2013-11-26 | 2015-06-03 | 中国石油化工股份有限公司 | Diesel hydroupgrading catalyst and preparation method thereof |
| CN106669799A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst for maximum-yield production of low freezing point diesel fuel |
| CN107344116A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | Hydrocracking catalyst and its preparation method and application |
| CN107344120A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | Carrier of hydrocracking catalyst and its preparation method |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104667971A (en) * | 2013-11-26 | 2015-06-03 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier and preparation method thereof |
| CN104667967A (en) * | 2013-11-26 | 2015-06-03 | 中国石油化工股份有限公司 | Diesel hydroupgrading catalyst and preparation method thereof |
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| CN104667971B (en) * | 2013-11-26 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of carrier of hydrocracking catalyst and preparation method thereof |
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| CN106669799B (en) * | 2015-11-09 | 2019-03-19 | 中国石油化工股份有限公司 | The hydrocracking catalyst preparation method of maximum production low-coagulation diesel oil |
| CN107344116A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | Hydrocracking catalyst and its preparation method and application |
| CN107344120A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | Carrier of hydrocracking catalyst and its preparation method |
| CN107344120B (en) * | 2016-05-05 | 2019-11-15 | 中国石油化工股份有限公司 | Carrier of hydrocracking catalyst and its preparation method |
| CN107344116B (en) * | 2016-05-05 | 2019-11-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst and its preparation method and application |
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