CN102773117A - Medium-oil-type hydrocracking catalyst and preparation method thereof - Google Patents
Medium-oil-type hydrocracking catalyst and preparation method thereof Download PDFInfo
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- CN102773117A CN102773117A CN2012102991476A CN201210299147A CN102773117A CN 102773117 A CN102773117 A CN 102773117A CN 2012102991476 A CN2012102991476 A CN 2012102991476A CN 201210299147 A CN201210299147 A CN 201210299147A CN 102773117 A CN102773117 A CN 102773117A
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Abstract
The invention discloses a hydrocracking catalyst and a preparation method thereof. The catalyst is prepared from the following components by mass percent: 5%-30% of dealuminizing Y zeolite, 15%-35% of hydrogenation reactive metal, 5%-25% of amorphous silicon aluminum and 20%-50% of alumina, wherein the mass percent of the hydrogenation reactive metal is calculated in the mass of oxide of the hydrogenation reactive metal. The catalyst is applied to a hydrocracking process, and an objective product of the catalyst is intermediate distillate oil. The catalyst is high in cracking activity, hydrogenation activity and product selectivity.
Description
Technical field
The present invention relates to a kind of middle oil type hydrocracking catalyst and preparation method thereof, this catalyst is fit to handle poor heavy raw material oil, voluminous intermediate oil.
Background technology
Hydrocracking is heavy raw oil faces reactions such as carrying out hydrogenation, desulfurization, denitrogenation, the rearrangement of hydrocarbon molecule recurring structure and cracking in the presence of hydrogen and the catalyst at HTHP a kind of conversion process.Hydrocracking technology be make full use of petroleum resources, improve the oil product quality, guarantee source green and environment-friendly, satisfy the effective means of energy market demand.Under the condition that relatively relaxes, from the poorer heavy raw oil of quality, produce more light-end products, reduce gas yield, improve liquid and receive, reduce the hydrogen consumption, be the developing direction of hydrocracking technology.
US6,174,429 relate to a kind of hydrocracking catalyst, contain the aluminium [amorphous in this catalyst and account for 1 ~ 99wt%; Lattice constant is 2.438nm, chemical SiO
2/ Al
2O
3(mol ratio) is 8, skeleton SiO
2/ Al
2O
3(mol ratio) is that 20 Modified Zeolite Y accounts for 0.1 ~ 80wt%; Group VIII metal accounts for 0.1 ~ 30wt%; The group VIB metal accounts for 1 ~ 40wt%; Auxiliary agent accounts for 0.1 ~ 20wt%; VII A family metal (at least a) accounts for 0 ~ 20wt%.This catalyst has active and stable preferably, but jet fuel and diesel yield are not high, and promptly the intermediate oil yield is not high.
CN02144945.7 discloses a kind of hydrocracking catalyst of producing intermediate oil to greatest extent, contains 5 ~ 25wt%SiO in this catalyst
2-Al
2O
3Mol ratio is 40 ~ 60 the unformed SiO of Y zeolite, 20 ~ 50wt%
2-Al
2O
3, 15 ~ 30wt% adhesive, and the group VIB metal of 10 ~ 30wt%, the group VIII metal of 4 ~ 10wt%, wherein VI B/ (VI B+ VIII) atomic ratio is 0.3 ~ 0.8.The lattice constant of Y zeolite wherein is 2.425 ~ 2.420nm, and relative crystallinity is 80 ~ 100%.This Y zeolite prepares through following method: the NaY zeolite is through a NH
4NO
3After the exchange, between pH value 1 ~ 3, use oxalic acid and NH
4NO
3Mixed liquor carries out secondary NH
4 +Exchange; Under 0.080 ~ 0.098MPa and 500 ~ 550 ℃ of conditions, use NH then
4NO
3Solution carries out the hydrothermal treatment consists first time, under 0.1 ~ 0.2MPa and 500 ~ 700 ℃, carries out the secondary hydrothermal treatment consists again; Use HNO at last
3Carry out acid treatment.Obviously, NH
4The NaY zeolite is at pH<peptization can occur at 3 o'clock, and cause zeolite structured avalanche, can not produce the Y zeolite of high-crystallinity.
CN200710158783.6 discloses a kind of hydrocracking catalyst; This catalyst belongs to the hydrocracking catalyst of voluminous intermediate oil, and its acidic cleavage component is a kind ofly to handle through ammonium hexafluorosilicate dealumination complement silicon and the NH after hydrothermal treatment consists with aluminium salt and inorganic acid or organic acid mixed aqueous solution
4The NaY molecular sieve makes, and the silica alumina ratio of this modified molecular screen is up to 30 ~ 150, and B acid/L acid is greater than 8.0.This catalyst applications is in the hydrocracking process process, and intermediate oil selectivity and reactivity are all good, produces fluorine-containing sewage when weak point is to produce modified zeolite, and environment is polluted, and is unfavorable for environmental protection.
Summary of the invention
The purpose of this invention is to provide a kind of in oil type hydrocracking catalyst and preparation method thereof, this catalyst applications is in heavy-oil hydrogenation cracking technical process, shows characteristics such as lytic activity height, hydrogenation activity are good, purpose product selectivity height, good stability.
A kind of hydrocracking catalyst provided by the present invention is processed by sealumination modified Y zeolite, hydrogenation active metals, amorphous aluminum silicide and aluminium oxide;
In the said catalyst, the quality percentage composition of said sealumination modified Y zeolite, hydrogenation active metals, amorphous aluminum silicide and aluminium oxide is respectively 5% ~ 30%, 15% ~ 35%, 5% ~ 25% and 20% ~ 50%; Wherein, the quality percentage composition of said hydrogenation active metals is in the quality of its oxide.
The composition of above-mentioned hydrocracking catalyst specifically can be sealumination modified Y zeolite 28.4%; Hydrogenation active metals 24.3%; Amorphous aluminum silicide 7.9% and aluminium oxide 39.4%, sealumination modified Y zeolite 15.3%, hydrogenation active metals 23.7%, amorphous aluminum silicide 13.7% and aluminium oxide 47.3% or sealumination modified Y zeolite 23%; Hydrogenation active metals 23.6%, amorphous aluminum silicide 10.74% and aluminium oxide 42.7%.
In the above-mentioned hydrocracking catalyst, the specific area of said catalyst is 220 ~ 350m
2/ g specifically can be 315m
2/ g, 339m
2/ g or 351m
2/ g, pore volume are 0.25 ~ 0.45mL/g, specifically can be 0.305mL/g, 0.324mL/g or 0.347mL/g.
In the above-mentioned hydrocracking catalyst, said hydrogenation active metals is group VIB metal and a group VIII metal in the periodic table of chemical element, and said group VIB metal is preferably molybdenum and/or tungsten, and said group VIII metal is preferably cobalt and/or nickel;
In the said catalyst, the quality percentage composition of said group VIB metal is 15.0% ~ 30.0%, and as 21.0%, 20.5% or 20.4%, the quality percentage composition of said group VIII metal is 3.0% ~ 8.0%, as 3.2% or 3.3%, all in the quality of its oxide.
In the above-mentioned hydrocracking catalyst, said sealumination modified Y zeolite has following physicochemical property:
SiO
2/ Al
2O
3Mol ratio is 10 ~ 60; Lattice constant is 2.425 ~ 2.438nm; Relative crystallinity>=90%; Specific area is 750 ~ 850m
2/ g; Na
2O quality percentage composition≤0.15%; 1.7 the secondary pore of ~ 10nm accounts for more than 50% of total pore volume; Infrared acidity is 0.200 ~ 0.60mmol/g; Ion exchange capacity≤0.05%; At 25 ℃, P/P
0Be under 1.0 conditions, the adsorbance of water<5.0%, in mass.
In the said amorphous aluminum silicide, SiO
2The quality percentage composition be 35 ~ 65%, as 50%, specific area is 350 ~ 500m
2/ g is like 370m
2/ g, pore volume is 0.8 ~ 1.0mL/g, like 0.85mL/g.
In the above-mentioned hydrocracking catalyst, said sealumination modified Y zeolite can prepare according to following method:
(1) with NH
4The NaY zeolite carries out hydrothermal treatment consists;
(2) zeolite that step (1) is obtained hangs down the exchange of pH ammonium;
(3) filter cake that obtains in the step (2) is carried out hydrothermal treatment consists;
(4) non-framework aluminum that removes in the zeolite that step (3) obtains with acid promptly obtains said sealumination modified Y zeolite.
In the above-mentioned hydrocracking catalyst, in the step (1), said NH
4The physicochemical property of NaY zeolite is following: degree of crystallinity>=90%; Lattice constant is 2.468 ~ 2.472nm; SiO
2/ Al
2O
3Mol ratio is 4.5 ~ 5.5; Na
2O content≤3.5% is the quality percentage composition;
The temperature of said hydrothermal treatment consists is 500～700 ℃; Specifically can be 560～650 ℃, 560 ℃, 600 ℃ or 650 ℃; Water vapor pressure is 0.01 ~ 1.0MPa; Specifically can be 0.1 ~ 0.15MPa, 0.10MPa or 0.15MPa, the time is 1.0 ~ 10.0 hours, specifically can be 2 hours, 3 hours or 3.5 hours.
Low pH ammonium exchange described in the step (2) is containing NH
4 +And H
+Mixed aqueous solution in carry out; In the said mixed aqueous solution, NH
4 +Molar concentration be 0.5 ~ 3.0mol/L, like 2.0mol/L, H
+Molar concentration be 0.05 ~ 0.6mol/L, specifically can be 0.15mol/L, 0.2mol/L or 0.28mol/L;
The temperature of said low pH ammonium exchange is 70 ~ 120 ℃, specifically can be 90 ~ 120 ℃, 90 ℃ or 120 ℃, and the time is 0.5 ~ 3.0 hour, specifically can be 1 hour, 1.5 hours or 2 hours;
Comprise 1 ~ 3 said low pH ammonium exchange in the step (2).
In the step (3), the temperature of said hydrothermal treatment consists is 500 ~ 800 ℃, specifically can be 650 ℃ or 680 ℃, and water vapor pressure is 0.01 ~ 1.0MPa, specifically can be 0.1MPa or 0.2MPa, and the time is 1.0 ~ 10.0 hours, specifically can be 2 hours, 3 hours or 4 hours;
The temperature of hydrothermal treatment consists described in the step (3) is higher 10 ~ 200 ℃ than the temperature of hydrothermal treatment consists described in the step (1), as 50 ℃ or 120 ℃.
In the step (4), said acid is hydrochloric acid, nitric acid etc.; The concentration of said acid is 0.1 ~ 3mol/L, specifically can be 0.4mol/L or 0.5mol/L;
The said temperature that removes is 60 ~ 120 ℃, specifically can be 80 ℃, 90 ℃ or 95 ℃, and the time is 0.5 ~ 5 hour, specifically can be 1 hour or 2 hours.
The present invention also provides above-mentioned Preparation of catalysts method, comprises the steps:
Said sealumination modified Y zeolite, hydrogenation active metals, amorphous aluminum silicide and adhesive are carried out that mechanical mixture rolls, extruded moulding, leave standstill agingly, promptly obtain said catalyst through dry and roasting then.
Among the above-mentioned preparation method, said adhesive is for to be formed by nitric acid and aperture aluminium oxide peptization; Said aperture aluminium oxide pore volume can be 0.3 ~ 0.6mL/g, and specific area can be 200 ~ 350m
2/ g;
Saidly leave standstill aging air humidity and can be 50 ~ 100%, as 75% ~ 95%, 75%, 90% or 95%, temperature can be 50 ~ 120 ℃, and as 70 ~ 80 ℃, 70 ℃, 75 ℃ or 80 ℃, the time can be 4 ~ 24 hours, as 6 ~ 10 hours, 6 hours, 8 hours or 10 hours;
The temperature of said drying can be 100 ~ 130 ℃, and the time can be 8 ~ 16 hours, as following dry 6 hours at 110 ℃;
The temperature of said roasting can be 450 ~ 550 ℃, and the time can be 4 ~ 8 hours, as 500 ℃ of following roastings 4 hours.
The application of hydrocracking catalyst provided by the invention in hydrocracking process; The hydrocracking process that is used for voluminous intermediate oil; Reaction process condition is: under the hydrogen existence condition; Reaction pressure can be 10 ~ 15MPa, and hydrogen to oil volume ratio can be 800 ~ 1500, and volume space velocity can be 0.8 ~ 2.5h during liquid
-1, reaction temperature can be 360 ~ 420 ℃.
The present invention has the following advantages:
The sealumination modified Y zeolite dealumination depth that the present invention adopted can choose at random, SiO
2/ Al
2O
3Mol ratio reach 60 can not destroy zeolite yet crystal structure, the sealumination modified Y zeolite of the inventive method preparation has the degree of crystallinity height, surface area is big, silica alumina ratio is high, lattice constant is little, secondary pore is abundant, acid site density is low, characteristics such as the acid site ratio height of moderate strength.Sealumination modified Y zeolite is used for the hydrocracking catalyst of voluminous intermediate oil, and high-ratio surface has not only promoted the performance of hydrogenation activity with flourishing secondary pore, and helps the diffusion of product; Hold the charcoal ability and also greatly strengthen, secondary pore is many, the low occurrence probability that has then reduced excessive fragmentation and second pyrolysis of acid site density; Thereby can make catalyst have good intermediate oil selectivity, degree of crystallinity is high, and the acid site ratio height of moderate strength then makes catalyst have good activity; Silica alumina ratio is high, and lattice constant is little, Stability Analysis of Structures; Heat and good hydrothermal stability then make catalyst have good stability.Behind the shaping of catalyst through leaving standstill ageing process; The hydrogenation activity component is moved, makes it to be more evenly distributed, thereby with dealuminated zeolite and the sial component is more effective combines; Hydrogenation active metals is used more effectively like this, and the hydrogenation performance of catalyst is able to strengthen.Catalyst applications of the present invention is in hydrocracking process, and the purpose product is an intermediate oil, and lytic activity is high, and hydrogenation activity is good, and product selectivity is good.
The specific embodiment
Employed experimental technique is conventional method like no specified otherwise among the following embodiment.
Used material, reagent etc. like no specified otherwise, all can obtain from commercial sources among the following embodiment.
Embodiment 1, preparation sealumination modified Y zeolite A
1. get 250 gram NH
4The NaY zeolite (produce, SiO by Wenzhou catalyst plant
2/ Al
2O
3Mol ratio is 5.1, lattice constant a
0=2.470nm, degree of crystallinity is 95%, Na
2O is 2.3w%, and butt is 70w%.) place heat-treatment furnace, control 500 ℃/hour heating rate, temperature is risen to 600 ℃, the water vapor pressure of keeping system simultaneously is 0.15MPa, handles 2.0 hours, sample is taken out in cooling.
2. with containing NH
4 +And H
+Concentration solution (ammonium chloride and the hydrochloric acid mixed solution) 1500mL that is respectively 2.0mol/L and 0.2mol/L contact and stir with sample, keep slurry temperature at 90 ℃, constant temperature 1.5 hours, the same terms reprocessing 1 time, filter cake is used water washing;
3. wet cake is placed heat-treatment furnace, temperature is risen to 650 ℃, the control water vapor pressure is 0.20MPa, constant temperature 3 hours, and sample is taken out in cooling;
4. final sample uses 1000mL concentration to remove the non-framework aluminum in the sample as the hydrochloric acid of 0.5mol/L, and the dealuminzation condition is to handle 2 hours at 80 ℃, obtains sealumination modified Y zeolite A, and its physico-chemical property is seen table 1.
Embodiment 2, preparation sealumination modified Y zeolite B
1. 2kg NH
4NaY zeolite (with embodiment 1) places heat-treatment furnace, in 2 hours, temperature is risen to 630 ℃, injects water vapour (logical steam rate 3.0kg/h), and keeps system pressure at 0.1MPa, and 630 ℃ of following constant temperature 3.5 hours, sample was taken out in cooling;
2. in autoclave, add entry 15kg, industrial NH
4NO
32.4kg, HNO
30.2kg with zeolite sample after the heat treatment for the first time (in the mixed solution, NH
4 +And H
+Concentration be respectively 2.0mol/L and 0.28mol/L), stirring is started in sealing, and temperature is risen to 120 ℃, constant temperature was handled 1 hour, filter cake the same terms is handled 1 time again, the elimination mother liquor is dried to cake moisture ≯ 25%.
3. sample places heat-treatment furnace, and 1. condition carries out the secondary hydrothermal treatment consists with step, and wherein the hydrothermal treatment consists temperature is 650 ℃, and the hydrothermal treatment consists time is 2 hours.
4. zeolite sample carried out chemical dealuminization 1.0 hours with the HCl of 14 liters of 0.4mol/L under 90 ℃, the elimination mother liquor, and the cakes with deionized water washing is to detecting less than Cl
-, obtaining sealumination modified Y zeolite B, its physico-chemical property is seen table 1.
Embodiment 3, preparation sealumination modified Y zeolite C
1. 300g NH
4NaY zeolite (with embodiment 1) places heat-treatment furnace, at 1 hour temperature is risen to 560 ℃, keeps pressure at 0.1MPa through zeolite self water vapour, constant temperature 3 hours, and zeolite sample is taken out in cooling.
2. with containing NH
4 +And H
+Concentration solution (ammonium nitrate and the nitric acid mixed solution) 200mL that is respectively 2.0mol/L and 0.15mol/L contact and stir with sample, temperature is risen to 90 ℃, and kept 2 hours, repeat 2 times, filter cake washs with water purification, drying.
3. zeolite sample is placed in the heat-treatment furnace, at 1.5 hours temperature is raised to 680 ℃, feeds water vapour 300g/h simultaneously, and the control system pressure is at 0.1 ± 0.02MPa, and the control system temperature kept 4 hours at 680 ℃, and sample is taken out in cooling then.
4. zeolite sample removed non-framework aluminum 1 hour with the HCl200mL of 0.2mol/L at 95 ℃, and the dealuminzation step repeats 2 times, obtains sealumination modified Y zeolite C, and its physico-chemical property is seen table 1.
Comparative Examples 1, preparation modified Y zeolite D
Get the NH of 3000mL 2mol/L
4Cl solution adds HCl the pH of solution is transferred to 3.5, mixes with 300g NaY zeolite and stirs, and temperature is risen to 90 ℃; Constant temperature 2 hours, the elimination mother liquor, filter cake was handled 1 hour at 90 ℃ with the HCl solution of 3000mL 0.2mol/L; Suction filtration, washing, wet cake place heat-treatment furnace in 1.5 hours, temperature to be risen to 650 ℃, and the pressure of keeping system with the water vapour of self is at 0.15MPa; Constant temperature 2.5 hours, zeolite sample were handled suction filtration, washing with the HCl solution of 3000mL0.3mol/L 1 hour at 90 ℃ again; Wet cake places heat-treatment furnace in 1.5 hours, temperature to be risen to 680 ℃, and the pressure of keeping system with the water vapour of self is at 0.15MPa, constant temperature 2.5 hours; Obtain modified Y zeolite D, its physico-chemical property is seen table 1.
Comparative Examples 2, preparation modified molecular screen E
The method that provides according to CN200710158783.6 prepares modified Y zeolite: get 2000gNa
2O content is the raw material NH of 2.8wt% (butt 70.3wt%)
4NaY; Put into and have the flask that reflux also can be airtight; Pull an oar with the 7800mL deionized water; And under stirring condition, be warmed up to 95 ℃ rapidly, and in 2 hours, drip the aqueous solution with even velocity then by the configuration of 453g ammonium hexafluorosilicate and 3000mL deionized water, add rear slurry constant temperature 2 hours under 95 ℃ of stirring conditions.Stop to stir, left standstill 10 minutes, isolate the molecular sieve on flask top with decantation; Through filter, washing, wet cake is put into tubular type hydrothermal treatment consists stove, temperature programming to 600 ℃; Processing is 2.5 hours under gauge pressure 0.2MPa, puts into then to have the flask that reflux also can be airtight, adds the mixed aqueous solution 1800mL that contains concentration 0.8mol/L aluminum sulfate and 0.3mol/L sulfuric acid; Stirred 2 hours at 90 ℃ of following constant temperature, filtration, washing, drying obtain modified Y zeolite E, and its physico-chemical property is seen table 1.
The physico-chemical property of the modified Y zeolite of table 1 embodiment 1-3 and Comparative Examples 1-2 preparation
Embodiment 4, preparation catalyst CA
With sealumination modified Y zeolite B 90 grams (butt 80wt%), molybdenum oxide 53.3 grams, nickel nitrate 32.5 grams, amorphous aluminum silicide (SiO
2Content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 75wt%) 26.7 grams, macroporous aluminium oxide (pore volume 1.0mL/g, specific area 400m
2/ g, butt 75wt%) 80 grams, adhesive (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3, the pore volume of little porous aluminum oxide is 0.46ml/g, specific area is 280m
2/ g) 133 grams place roller to mix to pinch, roll, to be pressed into paste, extruded moulding; It is 95% that catalyst after the moulding places air humidity, and temperature left standstill aging 10 hours at 70 ℃; And 110 ℃ of dryings 6 hours; Temperature programming rose to 500 ℃ of roastings 4 hours in 4 hours, made catalyst CA, and its physico-chemical property is seen table 2.
Among the catalyst carrier CA of present embodiment preparation, sealumination modified Y zeolite, MoO
3, NiO, amorphous aluminum silicide and aluminium oxide the quality percentage composition be respectively 28.4%, 21.0%, 3.3%, 7.9% and 39.4%.
Embodiment 5, preparation catalyst CB
With sealumination modified Y zeolite B 200 grams (butt 80wt%), molybdenum oxide 215 grams, nickel nitrate 130 grams, amorphous aluminum silicide (SiO
2Content 50wt%, pore volume 0.85mL/g, specific area 370m
2/ g, butt 75wt%) 192 grams, macroporous aluminium oxide (pore volume 1.0mL/g, specific area 400m
2/ g, butt 75wt%) 448 grams, adhesive (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3, the pore volume of little porous aluminum oxide is 0.46ml/g, specific area is 280m
2/ g) 532 grams place roller to mix to pinch, roll, to be pressed into paste, extruded moulding; It is 75% that catalyst after the moulding places air humidity, and temperature left standstill aging 6 hours at 80 ℃; And 110 ℃ of dryings 6 hours; Temperature programming rose to 500 ℃ of roastings 4 hours in 4 hours, made catalyst CB, and its physico-chemical property is seen table 2.
Among the catalyst carrier CB of present embodiment preparation, sealumination modified Y zeolite, MoO
3, NiO, amorphous aluminum silicide and aluminium oxide the quality percentage composition be respectively 15.3%, 20.5%, 3.2%, 13.7% and 47.3%.
Embodiment 6, preparation catalyst CC
With sealumination modified Y zeolite C 75 grams (butt 80wt%), molybdenum oxide 53.3 grams, nickel nitrate 32.5 grams, amorphous aluminum silicide (SiO
2Content 50wt%, pore volume 0.85mL/g, specific area 370m
2/ g, butt 75wt%) 37.5 grams, macroporous aluminium oxide (pore volume 1.0mL/g, specific area 400m
2/ g, butt 75wt%) 96 grams, adhesive (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3, the pore volume of little porous aluminum oxide is 0.46ml/g, specific area is 280m
2/ g) 133 grams place roller to mix stone roller, are pressed into paste, extruded moulding; It is 90% that catalyst after the moulding places air humidity, and temperature left standstill aging 8 hours at 75 ℃; And 110 ℃ of dryings 6 hours; Temperature programming rose to 500 ℃ of roastings 4 hours in 4 hours, made catalyst CC, and its physico-chemical property is seen table 2.
Among the catalyst carrier CC of present embodiment preparation, sealumination modified Y zeolite, MoO
3, NiO, amorphous aluminum silicide and aluminium oxide the quality percentage composition be respectively 23%, 20.4%, 3.2%, 10.74% and 42.7%.
Comparative Examples 3,
Change the sealumination modified Y zeolite B among the embodiment 4 into modified zeolite D, make catalyst CD, its physico-chemical property is seen table 2.
Comparative Examples 4,
Change the sealumination modified Y zeolite C of embodiment 6 into modified molecular screen E, not health behind the extruded moulding is directly carried out drying and roasting and is made catalyst CE, and its physico-chemical property is seen table 2.
The physico-chemical property of table 2 catalyst
The performance evaluation of embodiment 7, catalyst
On small-sized hydrocracking experimental rig, carry out; Catalyst CA, CC, the evaluation of CE reactivity worth adopt one-stage serial, and (raw material removes impurity such as wherein sulphur, nitrogen earlier through the Hydrobon catalyst bed; Pass through hydrocracking catalyst then) the single pass flow process; VGO is a raw material with triumph, and character is listed in table 3.
The main character of the evaluation result of catalyst CA, CC and CE and product boat coal is listed in table 4.
Table 3 triumph VGO main character
Table 4 hydrocracking process condition and catalytic result
Can find out by data in the table; Under identical working condition; Activity of such catalysts provided by the invention is a little less than the catalyst of Comparative Examples preparation, but its selectivity is better than the catalyst of Comparative Examples, and middle distillates oil selectivity is higher 2.1 ~ 2.8 percentage points than the catalyst of Comparative Examples.The arene content of product jet fuel is far below the catalyst of Comparative Examples, and smoke point is higher than the catalyst of Comparative Examples.Therefore catalyst of the present invention is a kind of hydrocracking catalyst of good voluminous intermediate oil.
Claims (10)
1. a hydrocracking catalyst is processed by sealumination modified Y zeolite, hydrogenation active metals, amorphous aluminum silicide and aluminium oxide;
In the said catalyst, the quality percentage composition of said sealumination modified Y zeolite, hydrogenation active metals, amorphous aluminum silicide and aluminium oxide is respectively 5% ~ 30%, 15% ~ 35%, 5% ~ 25% and 20% ~ 50%; Wherein, the quality percentage composition of said hydrogenation active metals is in the quality of its oxide.
2. catalyst according to claim 1 is characterized in that: the specific area of said catalyst is 220 ~ 350m
2/ g, pore volume are 0.25 ~ 0.45mL/g.
3. catalyst according to claim 1 and 2 is characterized in that: said hydrogenation active metals is group VIB metal and a group VIII metal in the periodic table of chemical element;
In the said catalyst, the quality percentage composition of said group VIB metal is 15.0 ~ 30.0%, and the quality percentage composition of said group VIII metal is 3.0 ~ 8.0%, all in the quality of its oxide.
4. according to each described catalyst among the claim 1-3, it is characterized in that: said sealumination modified Y zeolite has following physicochemical property:
SiO
2/ Al
2O
3Mol ratio is 10 ~ 60; Lattice constant is 2.425 ~ 2.438nm; Relative crystallinity>=90%; Specific area is 750 ~ 850m
2/ g; Na
2O quality percentage composition≤0.15%; 1.7 the secondary pore of ~ 10nm accounts for more than 50% of total pore volume; Infrared acidity is 0.200 ~ 0.60mmol/g; Ion exchange capacity≤0.05%; At 25 ℃, P/P
0Be under 1.0 conditions, the adsorbance of water<5.0%, in mass;
In the said amorphous aluminum silicide, SiO
2The quality percentage composition be 35 ~ 65%, specific area is 350 ~ 500m
2/ g, pore volume are 0.8 ~ 1.0mL/g.
5. according to each described catalyst among the claim 1-4, it is characterized in that: said sealumination modified Y zeolite prepares according to following method:
(1) with NH
4The NaY zeolite carries out hydrothermal treatment consists;
(2) zeolite that step (1) is obtained hangs down the exchange of pH ammonium;
(3) filter cake that obtains in the step (2) is carried out hydrothermal treatment consists;
(4) non-framework aluminum that removes in the zeolite that step (3) obtains with acid promptly obtains said sealumination modified Y zeolite.
6. catalyst according to claim 5 is characterized in that: in the step (1), and said NH
4The physicochemical property of NaY zeolite is following: degree of crystallinity>=90%; Lattice constant is 2.468 ~ 2.472nm; SiO
2/ Al
2O
3Mol ratio is 4.5 ~ 5.5; Na
2O content≤3.5% is the quality percentage composition;
The temperature of said hydrothermal treatment consists is 500～700 ℃, and water vapor pressure is 0.01 ~ 1.0MPa, and the time is 1.0 ~ 10.0 hours;
Low pH ammonium exchange described in the step (2) is containing NH
4 +And H
+Mixed aqueous solution in carry out; In the said mixed aqueous solution, NH
4 +Molar concentration be 0.5 ~ 3.0mol/L, H
+Molar concentration be 0.05 ~ 0.6mol/L;
The temperature of said low pH ammonium exchange is 70 ~ 120 ℃, and the time is 0.5 ~ 3.0 hour;
Comprise 1 ~ 3 said low pH ammonium exchange in the step (2);
In the step (3), the temperature of said hydrothermal treatment consists is 500 ~ 800 ℃, and water vapor pressure is 0.01 ~ 1.0MPa, and the time is 1.0 ~ 10.0 hours;
The temperature of hydrothermal treatment consists described in the step (3) is higher 10 ~ 200 ℃ than the temperature of hydrothermal treatment consists described in the step (1).
In the step (4), said acid is hydrochloric acid or nitric acid; The concentration of said acid is 0.1 ~ 3mol/L;
The said temperature that removes is 60 ~ 120 ℃, and the time is 0.5 ~ 5 hour.
7. each said Preparation of catalysts method among the claim 1-6 comprises the steps:
Said sealumination modified Y zeolite, hydrogenation active metals, amorphous aluminum silicide and adhesive are carried out that mechanical mixture rolls, extruded moulding, leave standstill agingly, promptly obtain said catalyst through dry and roasting then.
8. preparation method according to claim 7 is characterized in that: said adhesive is for to be formed by nitric acid and aperture aluminium oxide peptization; Said aperture aluminium oxide pore volume is 0.3 ~ 0.6mL/g, and specific area is 200 ~ 350m
2/ g;
Said to leave standstill aging air humidity be 50 ~ 100%, and temperature is 50 ~ 120 ℃, and the time is 4 ~ 24 hours;
The temperature of said drying is 100 ~ 130 ℃, and the time is 8 ~ 16 hours;
The temperature of said roasting is 450 ~ 550 ℃, and the time is 4 ~ 8 hours.
9. each said catalyst application in hydrocracking among the claim 1-6.
10. application according to claim 9 is characterized in that: the pressure of said hydrocracking is 10 ~ 15MPa, and hydrogen to oil volume ratio is 800 ~ 1500, and volume space velocity is 0.8 ~ 2.5h during liquid
-1, reaction temperature is 360 ~ 420 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102991476A CN102773117A (en) | 2012-08-21 | 2012-08-21 | Medium-oil-type hydrocracking catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2012102991476A CN102773117A (en) | 2012-08-21 | 2012-08-21 | Medium-oil-type hydrocracking catalyst and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103041842A (en) * | 2012-12-17 | 2013-04-17 | 中国海洋石油总公司 | Medium oil type hydrocracking catalyst and preparation method thereof |
| CN104250010A (en) * | 2013-07-22 | 2014-12-31 | 中国海洋石油总公司 | Silicon-aluminum carrier containing two modified molecular sieves, preparation method and application thereof |
| CN105251524A (en) * | 2015-10-15 | 2016-01-20 | 广东石油化工学院 | Catalytic cracking deoxidation catalyst for biomass liquefaction oil |
| CN105536855A (en) * | 2014-11-03 | 2016-05-04 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst containing Y molecular sieve |
| CN105536854A (en) * | 2014-11-03 | 2016-05-04 | 中国石油化工股份有限公司 | Method for preparing hydrocracking catalyst containing Y molecular sieve |
| CN106669779A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Medium-oil-type hydrocracking catalyst and preparation method thereof |
| CN108455625A (en) * | 2017-02-21 | 2018-08-28 | 中国石油化工股份有限公司 | A kind of Modified Zeolite Y of high stability and preparation method thereof |
| CN111686787A (en) * | 2020-06-10 | 2020-09-22 | 中国石油天然气集团有限公司 | Hydrocracking catalyst carrier, and preparation method and application thereof |
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| CN103041842B (en) * | 2012-12-17 | 2015-08-05 | 中国海洋石油总公司 | Oil type hydrocracking catalyst and preparation method thereof in one |
| CN103041842A (en) * | 2012-12-17 | 2013-04-17 | 中国海洋石油总公司 | Medium oil type hydrocracking catalyst and preparation method thereof |
| CN104250010B (en) * | 2013-07-22 | 2016-08-24 | 中国海洋石油总公司 | A kind of silica-alumina supports containing two kinds of modified molecular screens and preparation method and application |
| CN104250010A (en) * | 2013-07-22 | 2014-12-31 | 中国海洋石油总公司 | Silicon-aluminum carrier containing two modified molecular sieves, preparation method and application thereof |
| CN105536854B (en) * | 2014-11-03 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of method for preparing the hydrocracking catalyst containing Y molecular sieve |
| CN105536854A (en) * | 2014-11-03 | 2016-05-04 | 中国石油化工股份有限公司 | Method for preparing hydrocracking catalyst containing Y molecular sieve |
| CN105536855A (en) * | 2014-11-03 | 2016-05-04 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst containing Y molecular sieve |
| CN105536855B (en) * | 2014-11-03 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of preparation method of the hydrocracking catalyst containing Y molecular sieve |
| CN105251524A (en) * | 2015-10-15 | 2016-01-20 | 广东石油化工学院 | Catalytic cracking deoxidation catalyst for biomass liquefaction oil |
| CN106669779A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Medium-oil-type hydrocracking catalyst and preparation method thereof |
| CN106669779B (en) * | 2015-11-09 | 2019-08-06 | 中国石油化工股份有限公司 | A kind of middle oil type hydrocracking catalyst and preparation method thereof |
| CN108455625A (en) * | 2017-02-21 | 2018-08-28 | 中国石油化工股份有限公司 | A kind of Modified Zeolite Y of high stability and preparation method thereof |
| CN111686787A (en) * | 2020-06-10 | 2020-09-22 | 中国石油天然气集团有限公司 | Hydrocracking catalyst carrier, and preparation method and application thereof |
| CN111686787B (en) * | 2020-06-10 | 2023-10-03 | 中国石油天然气集团有限公司 | Hydrocracking catalyst carrier, and preparation method and application thereof |
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