CN105618116A - Preparation method of hydro-cracking catalyst - Google Patents
Preparation method of hydro-cracking catalyst Download PDFInfo
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Abstract
The method comprises the following steps: 1, modified Y molecular sieve, amorphous silica-alumina and/or aluminum oxide are well mixed according to a certain ratio; dilute nitric acid is added, such that a slurry is formed; extrusion molding is carried out; and drying and roasting are carried out, such that a silica-alumina carrier containing modified Y molecular sieve is obtained; 2, an impregnation solution containing active metal is used for impregnating the carrier obtained in the step 1; after impregnation, the carrier is dried and roasted, such that the hydro-cracking catalyst is obtained. The surface layer silica-alumina ratio of the modified Y molecular sieve is higher than the bulk phase silica-alumina ratio. The hydro-cracking catalyst prepared with the method provided by the invention has good reaction activity and nitrogen resistance, and can be applied in different hydro-cracking reaction processes for increasing diesel production, increasing chemical engineering raw material production, catalyzing diesel hydro-conversion, and the like.
Description
Technical field
The preparation method that the present invention relates to a kind of hydrocracking catalyst.
Background technology
The features such as hydrocracking technology has that adaptability to raw material is strong, production operation and big, the good product quality of products scheme motility, various heavy inferior chargings can be converted into the high-quality jet fuel of market in urgent need, diesel oil, lube basestocks and chemical industry Petroleum and tail oil preparing ethylene by steam cracking raw material, become one of modern oil refining and the most important heavy oil deep processing technique of petro chemical industry, at home and abroad obtain increasingly extensive application. The core of hydrocracking process is hydrocracking catalyst. Hydrocracking catalyst is typical bifunctional catalyst, has hydrogenation and cracking dual-use function. Wherein hydrogenating function generally has the sulphided state form of W, Mo, Ni isoreactivity metal to provide, cracking function is then provided by molecular sieve, at present, hydrocracking process is the most widely used is modified Y molecular sieve, but owing to the character of acidic zeolite carrier makes it that nitride is especially sensitive, nitride is readily adsorbed in molecular sieve surface and causes molecular sieve poisoning, and therefore activity is substantially reduced, and is difficult to long-term stability in the industrial production and runs. Further, along with the increase of acid density on molecular sieve, the anti-nitrogen ability of catalyst is remarkably decreased. For this problem, at present conventional method is by Y molecular sieve carrying out dealuminzation or dealumination complement silicon processes and reduces the method for acid site quantity on molecular sieve and solve, but the method processing procedure is to carry out dealuminzation inside and outside whole molecular sieve simultaneously, therefore, while improving the silica alumina ratio of molecular sieve, owing to acid centre reduces, its activity is greatly reduced. So, improving catalyst anti-nitrogen ability and keeping also existing between hydrogenation cracking activity insoluble contradiction, conventional molecular sieve modified process difficult takes into account the two problem simultaneously.
CN200710158784.0 discloses a kind of hydrocracking catalyst containing Y molecular sieve and preparation method thereof, in this invention, Y type molecular sieve is to obtain after processing hydrothermal treatment consists with the mixed aqueous solution of aluminium salt and acid, the catalyst activity prepared is higher, but resistance to nitrogen ability is poor.
CN200810012212.6 discloses a kind of carrier of hydrocracking catalyst and preparation method thereof, and hydrocracking catalyst prepared by this invention has higher resistance to nitrogen ability still, and cracking activity is relatively low.
CN98114489.6 discloses the hydrocracking catalyst of a kind of nitrogen-resistant type multiferous middle oil, produces a large amount of intermediate oils for heavy distillate one-stage serial hydrocracking, and cracking zone feed nitrogen content is up to 100 �� g/g, but this catalyst activity is poor.
Summary of the invention
For the deficiencies in the prior art, the preparation method that the present invention carries a kind of hydrocracking catalyst, hydrocracking catalyst prepared by the inventive method has good reactivity and anti-nitrogen ability, and preparation method is simple, it is adaptable to commercial Application.
The preparation method of the hydrocracking catalyst of the present invention, including following content:
One, by modified Y molecular sieve, amorphous silicon aluminium and/or aluminium oxide mix homogeneously according to a certain ratio, extruded moulding after addition dust technology pulping, dry, roasting obtains the silica-alumina supports containing modified Y molecular sieve; Wherein the concentration of dust technology is 3wt% ~ 30wt%; Described drying condition is: dry 1 ~ 5 hour at 80 ~ 120 DEG C; Roasting condition is: roasting 1 ~ 5 hour at 400 ~ 700 DEG C;
Two, adopt the impregnation liquid containing active metal that the carrier of step one is impregnated, the carrier drying after dipping, roasting, obtain hydrocracking catalyst; Wherein said active metal is selected from the group VIII in the periodic table of elements and/or vib metals element, and group VIII active metal can be Ni and/or Co, and vib active metal can be W and/or Mo; The liquid-solid ratio wherein impregnated is 1.5:1 ~ 3:1, the mode adopting saturated dipping well known in the art carries out, in impregnation liquid, the content of group vib metallic compound is calculated as 20 ~ 60g/100ml by corresponding oxide, the content of group VIII metallic compound is calculated as 3 ~ 20g/100ml by corresponding oxide, and in impregnation liquid, the concentration of metallic compound can adjust accordingly according to product needed; Wherein said drying condition is: dry 2 ~ 8 hours at 90 ~ 150 DEG C; Roasting condition is: roasting 1 ~ 5 hour at 400 ~ 700 DEG C;
Wherein said modified Y molecular sieve mass percent in silica-alumina supports is 15% ~ 90%, it is preferable that 30% ~ 70%, and surplus is amorphous silica-alumina and/or aluminium oxide; Modified Y molecular sieve lattice constant is 2.425 ~ 2.455nm; (silica alumina ratio specifically described herein is SiO to molecular sieve phase silica alumina ratio2/Al2O3Mol ratio) it is 8 ~ 30, wherein surface layer silica alumina ratio 20 ~ 100, preferably 40 ~ 80, surface layer silica alumina ratio is higher than body phase silica alumina ratio 20 ~ 70, and wherein said surface layer refers to the molecular sieve outer surface thickness range to internal 5 ~ 400nm, it is preferable that 10 ~ 200nm, more preferably 50 ~ 190nm, surface layer is primary in Y molecular sieve crystal grain, intact with molecular sieve internal cohesion, does not block molecular sieve internal gutter; Sodium oxide weight/mass percentage composition is less than 1.0%, it is preferable that less than 0.5%; Modified Y molecular sieve specific surface area 650 ~ 900m2/ g; Pore volume 0.30 ~ 0.50ml/g; Meleic acid content 0.3 ~ 1.2mmol/g, it is preferable that 0.4 ~ 1.0mmol/g; Relative crystallinity 80 ~ 120%.
In the inventive method, the preparation method of the modified Y molecular sieve described in step one, including following content:
(1) in ammonium salt aqueous solution, Ammonium Salt Ionic exchange is carried out with NaY zeolite for former powder;
(2) Y molecular sieve after the ammonium exchange obtained in step (1) is carried out hydrothermal treatment consists;
(3) the Y molecular sieve aluminum salt solution after step (2) hydrothermal treatment consists is processed;
(4) the Y molecular sieve dried to step (3) gained;
(5) Y molecular sieve that step (4) obtains impregnates in organic solvent, then rapid draing;
(6) Y molecular sieve that step (5) obtains is carried out dealumination complement silicon process;
(7) step (6) Y molecular sieve after dealumination complement silicon processes is through filtration, dry, roasting, obtains modified Y molecular sieve.
Ammonium Salt Ionic exchange process described in step (1) is as follows: with NaY zeolite for raw material in ammonium salt aqueous solution, at 60 ~ 120 DEG C, it is preferable that at 60 ~ 90 DEG C, exchanges 1 ~ 3 hour, and exchange times is 1 ~ 4 time, the NaY zeolite after being exchanged, Na2O content is less than 3.0%; The wherein SiO of NaY zeolite raw material2/Al2O3Mol ratio is 3 ~ 6, sodium oxide weight/mass percentage composition 6% ~ 7%; Ammonium salt is one or more in ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, ammonium salt aqueous solution concentration 0.3 ~ 6.0mol/L, it is preferable that 1.0 ~ 3.0mol/L.
When step (2) described hydrothermal treatment process is at self steam or passes into steam, hydrothermal conditions is: temperature is 500 ~ 600 DEG C, and pressure is 0.01 ~ 0.5MPa, and the process time is 1.0 ~ 6.0 hours.
The aluminium salt used by aluminium salt processing procedure described in step (3) can be aluminum chloride, aluminum sulfate, aluminum nitrate etc. Aluminium salt concentration is 0.05 ~ 2mol/L, and treatment temperature is 50 ~ 120 DEG C, and the process time is 0.5 ~ 3 hour.
Baking temperature described in step (4) is 90 ~ 300 DEG C, and drying time is 2 ~ 10 hours.
One or more in alkane, petroleum ether, carbon tetrachloride, benzene, toluene, ethylbenzene, dimethylbenzene, ethylbenzene of organic solvent described in step (5), impregnation method adopts supersaturation dipping, and dip time is 1 ~ 5h; Baking temperature is 50 ~ 300 DEG C, it is preferable that baking temperature is higher than the boiling point of organic solvent, and drying time is 1 ~ 60 minute, it is preferable that 3 ~ 20 minutes.
Dealumination complement silicon described in step (6) processes as method well known to those skilled in the art, conventional ammonium fluosilicate dealumination complement silicon method can be adopted, namely first the Y molecular sieve that step (5) obtains is added water and be made into the water sample mixing of liquid-solid ratio 3 ~ 6, then, adding concentration is that 0.8 ~ 2mol/L ammonium fluosilicate aqueous solution processes 1 ~ 4 hour in 70 ~ 100 DEG C. Other are such as SiCl4Gas phase dealumination complement silicon is also suitable.
Calcination process condition described in step (7) is: roasting 2 ~ 4 hours at 400 ~ 600 DEG C.
Hydrocracking catalyst prepared by the inventive method, with overall catalyst weight gauge, including following component: the silica-alumina supports 55% ~ 85% containing modified Y molecular sieve, active metal 15% ~ 45%, wherein active metal is in metal-oxide; Described modified Y molecular sieve mass percent in silica-alumina supports is 15% ~ 90%, it is preferable that 30% ~ 70%, and surplus is amorphous silica-alumina and/or aluminium oxide; The specific surface area of described catalyst is 200 ~ 400m2/ g, pore volume is 0.2 ~ 0.5ml/g.
Described active metal is selected from the group VIII in the periodic table of elements and/or vib metals element, group VIII active metal can be Ni and/or Co, vib active metal can be W and/or Mo, group VIII active metallic content is 3% ~ 15%, vib active metallic content is 10% ~ 40%, in metal-oxide.
The present invention adopts transmission electron microscope X ray electronic spectroscopy to carry out microsection component analyzing to come measure and calculation molecular sieve surface layer and body phase silica alumina ratio.
Hydrocracking catalyst of the present invention can be applicable to the different hydrocracking reaction processes such as high-yield diesel oil, more producing chemical industry raw material and catalytic diesel oil hydro-conversion, general operational requirement(GOR) is: reaction pressure 6.0 ~ 20.0MPa, reaction temperature 350 ~ 420 DEG C, feed volume air speed 0.1 ~ 2.0h-1, hydrogen to oil volume ratio is 500:1 ~ 2000:1.
In the inventive method; by Y molecular sieve being modified process; namely dipping in the organic solvent being not readily dissolved in water is first used; then it is rapidly heated dry; rapidly remove molecular sieve outer layer organic solvent; thus remaining the organic solvent within molecular sieve; framework silicon-aluminum within such molecular sieve is protected; therefore; follow-up ammonium fluosilicate dealumination complement silicon processing procedure mainly carries out on the outer surface; ammonium fluosilicate process after, more modified Y is carried out conventional drying, roasting can remove the organic solvent in molecular sieve. The inventive method is by optionally carrying out dealumination complement silicon to Y molecular sieve outer surface, improve the silica alumina ratio of Y molecular sieve outer surface, the hydrocracking catalyst prepared compared to conventional method modified molecular screen can improve catalyst reaction activity or improve the anti-nitrogen ability of hydrocracking catalyst under the premise of identical activity when keeping close anti-nitrogen ability.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) photo of the modified Y molecular sieve of embodiment 1 preparation.
Detailed description of the invention
The present invention is further described by the examples below, but is not so limited the present invention.
Embodiment 1
Molecular sieve modified processing procedure:
(1) taking the former powder 200g of NaY molecular sieve prepared by test chamber, mix according to liquid-solid ratio 3:1 with the ammonium nitrate that concentration is 0.5mol/L, 70 DEG C exchange 3 hours, repeat this process 3 times, and in the Y molecular sieve after exchange, Na content is with Na2O is calculated as 2.5%;
(2) Y molecular sieve 530 DEG C that step (1) is obtained, hydrothermal treatment consists 2 hours under 0.1MPa;
(3) step (2) gained molecular sieve mixes with distilled water stirring according to liquid-solid ratio 5:1, then heats to 80 DEG C, adds the aluminum sulfate solution 400ml of 0.5mol/L, isothermal reaction 2 hours in the process of stirring.
(4) 150 DEG C of dry 8h of step (3) gained molecular sieve
(5) molecular sieve 2 hours of normal heptane solvent soaking step (4) gained is taken;
(6) molecular sieve after step (5) process dries 8 minutes in 130 DEG C;
(7) molecular sieve of step (6) gained mixes with distilled water according to liquid-solid ratio 5:1, then, adds the ammonium fluosilicate solution 100ml that concentration is 0.8mol/L, and 80 DEG C process 2 hours;
(8) Y molecular sieve after step (7) ammonium fluosilicate processes, 120 DEG C dry 2 hours, after 550 DEG C of roastings 2 hours, obtains modified Y molecular sieve, is numbered Y-1
It is 45 that Y-1 molecular sieve transmission electron microscope EDAX results measures its outer surface to the silica alumina ratio of 80nm thickness, and the silica alumina ratio of molecular sieve is 11. XRD analysis result shows that its lattice constant is 2.440nm, relative crystallinity 98%. Pore volume 0.36ml/g, specific surface area 750m2/ g, it is 0.95mmol/g that infrared analysis result measures Y-1 meleic acid amount.
Hydrocracking catalyst preparation process:
(1) configuration W-Ni dipping solution: taking configuration 1000ml dipping solution after ammonium metatungstate 430g and nickel nitrate 440g is dissolved in water, in gained dipping solution, active metal is with WO3With NiO cubage respectively 36g/100ml and 11g/100ml, solution numbers RY-1;
(2) taking the mixing of Y-160g and 40g macroporous aluminium oxide, add 4g/100ml dust technology and mix in a mixer and roll to extruding shape, on banded extruder, extruded moulding obtains carrier T-1;
(3) take T-160g to add 120mlRY-1 impregnation liquid and impregnate 2 hours, then 120 DEG C dry 4 hours, 500 DEG C of roastings 3 hours, obtain hydrocracking catalyst, be numbered Cat-1.
Embodiment 2
Molecular sieve modified processing procedure:
(1) taking the former powder of NaY molecular sieve prepared by test chamber, mix according to liquid-solid ratio 3:1 with the ammonium nitrate that concentration is 0.8mol/L, 70 DEG C exchange 3 hours, repeat this process 3 times, and in the Y molecular sieve after exchange, Na content is with Na2O is calculated as 2.0%.
(2) Y molecular sieve 560 DEG C that step (1) is obtained, hydrothermal treatment consists 2 hours under 0.1MPa;
(3) step (2) gained molecular sieve mixes with distilled water stirring according to liquid-solid ratio 6:1, then heats to 90 DEG C, adds the aluminum sulfate solution 600ml of 0.8mol/L, isothermal reaction 2 hours in the process of stirring.
(4) 200 DEG C of dry 4h of step (3) gained molecular sieve;
(5) molecular sieve 3 hours of toluene solvant soaking step (4) gained is taken;
(6) dry 30 minutes of 130 DEG C of molecular sieve after step (5) process;
(7) molecular sieve of step (6) gained mixes with distilled water according to liquid-solid ratio 5:1, then, adds the ammonium fluosilicate solution 150ml that concentration is 0.9mol/L, and 90 DEG C process 2 hours;
(8) Y molecular sieve after step (7) ammonium fluosilicate processes, 120 DEG C dry 2 hours, after 550 DEG C of roastings 2 hours, obtains modified Y molecular sieve, is numbered Y-2.
Hydrocracking catalyst preparation process:
(1) configuration W-Ni dipping solution: taking configuration 1000ml dipping solution after ammonium metatungstate 480g and nickel nitrate 480g is dissolved in water, in gained dipping solution, active metal is with WO3With NiO cubage respectively 40g/100ml and 12g/100ml, solution numbers RY-2;
(2) taking the mixing of Y-230g and 70g macroporous aluminium oxide, add 4g/100ml dust technology and mix in a mixer and roll to extruding shape, on banded extruder, extruded moulding obtains carrier T-2;
(3) take T-260g to add 120mlRY-2 impregnation liquid and impregnate 2 hours, then 120 DEG C dry 4 hours, 500 DEG C of roastings 3 hours, obtain hydrocracking catalyst, be numbered Cat-2.
Y-2 molecular sieve transmission electron microscope EDAX results measures its outer surface to 180nm thickness, surface layer silica alumina ratio be 58, the silica alumina ratio of molecular sieve phase is 13. XRD analysis result shows that its lattice constant is 2.437nm, relative crystallinity 95%. Pore volume 0.38ml/g, specific surface area 700m2/ g, it is 0.72mmol/g that infrared analysis result measures Y-2 meleic acid amount.
Embodiment 3
Molecular sieve modified processing procedure:
(1) taking the former powder of NaY molecular sieve prepared by test chamber, mix according to liquid-solid ratio 3:1 with the ammonium nitrate that concentration is 2.0mol/L, 80 DEG C exchange 1.0 hours, repeat this process 2 times, and in the Y molecular sieve after exchange, Na content is with Na2O is calculated as 1.8%.
(2) Y molecular sieve 560 DEG C that step (1) is obtained, hydrothermal treatment consists 2 hours under 0.1MPa;
(3) step (2) gained molecular sieve mixes with distilled water stirring according to liquid-solid ratio 6:1, then heats to 90 DEG C, adds the aluminum sulfate solution 600ml of 0.8mol/L, isothermal reaction 2 hours in the process of stirring.
(4) 250 DEG C of dry 2h of step (3) gained molecular sieve;
(5) molecular sieve 4 hours of xylene solvent soaking step (4) gained is taken;
(6) dry 15 minutes of 200 DEG C of molecular sieve after step (5) process;
(7) molecular sieve of step (6) gained mixes with distilled water according to liquid-solid ratio 5:1, then, adds the ammonium fluosilicate solution 150ml that concentration is 1mol/L, and 95 DEG C process 2 hours;
(8) Y molecular sieve after step (7) ammonium fluosilicate processes, 120 DEG C dry 2 hours, after 550 DEG C of roastings 2 hours, obtains modified Y molecular sieve, is numbered Y-3.
Hydrocracking catalyst preparation process:
(1) configuration W-Ni dipping solution: taking configuration 1000ml dipping solution after ammonium metatungstate 480g and nickel nitrate 480g is dissolved in water, in gained dipping solution, active metal is with WO3With NiO cubage respectively 40g/100ml and 12g/100ml, solution numbers RY-3;
(2) taking the mixing of Y-330g and 70g macroporous aluminium oxide, add 4g/100ml dust technology and mix in a mixer and roll to extruding shape, on banded extruder, extruded moulding obtains carrier T-3;
(3) take T-360g to add 120mlRY-3 impregnation liquid and impregnate 2 hours, then 120 DEG C dry 4 hours, 500 DEG C of roastings 3 hours, obtain hydrocracking catalyst, be numbered Cat-3.
Y-3 molecular sieve transmission electron microscope EDAX results measures its outer surface to 150nm thickness, surface layer silica alumina ratio be 60, the silica alumina ratio of molecular sieve phase is 13. XRD analysis result shows that its lattice constant is 2.438nm, relative crystallinity 95%. Pore volume 0.38ml/g, specific surface area 695m2/ g, it is 0.73mmol/g that infrared analysis result measures Y-3 meleic acid amount.
Embodiment 4
Molecular sieve modified processing procedure:
(1) taking the former powder 200g of NaY molecular sieve prepared by test chamber, mix according to liquid-solid ratio 3:1 with the ammonium nitrate that concentration is 0.5mol/L, 70 DEG C exchange 3 hours, repeat this process 2 times, and in the Y molecular sieve after exchange, Na content is with Na2O is calculated as 2.7%;
(2) Y molecular sieve 530 DEG C that step (1) is obtained, hydrothermal treatment consists 2 hours under 0.1MPa;
(3) step (2) gained molecular sieve mixes with distilled water stirring according to liquid-solid ratio 5:1, then heats to 90 DEG C, adds the aluminum sulfate solution 400ml of 0.5mol/L, isothermal reaction 1.5 hours in the process of stirring.
(4) 100 DEG C of dry 9h of step (3) gained molecular sieve;
(5) molecular sieve 2 hours of normal octane solvent soaking step (4) gained is taken;
(6) molecular sieve after step (5) process dries 12 minutes in 140 DEG C;
(7) molecular sieve of step (6) gained mixes with distilled water according to liquid-solid ratio 5:1, then, adds the ammonium fluosilicate solution 100ml that concentration is 0.8mol/L, and 80 DEG C process 2 hours;
(8) Y molecular sieve after step (7) ammonium fluosilicate processes, 120 DEG C dry 2 hours, after 550 DEG C of roastings 2 hours, obtains modified Y molecular sieve, is numbered Y-4.
It is 45 that Y-4 molecular sieve transmission electron microscope EDAX results measures its outer surface to the silica alumina ratio of 100nm thickness, and the silica alumina ratio of molecular sieve phase is 12. XRD analysis result shows that its lattice constant is 2.439nm, relative crystallinity 98%. Pore volume 0.35ml/g, specific surface area 730m2/ g, it is 0.92mmol/g that infrared analysis result measures Y-4 meleic acid amount.
Hydrocracking catalyst preparation process:
(1) configuration W-Ni dipping solution: taking configuration 1000ml dipping solution after ammonium metatungstate 430g and nickel nitrate 440g is dissolved in water, in gained dipping solution, active metal is with WO3With NiO cubage respectively 36g/100ml and 11g/100ml, solution numbers RY-4;
(2) taking the mixing of Y-460g and 40g macroporous aluminium oxide, add 4g/100ml dust technology and mix in a mixer and roll to extruding shape, on banded extruder, extruded moulding obtains carrier T-4;
(3) take T-460g to add 120mlRY-4 impregnation liquid and impregnate 2 hours, then 120 DEG C dry 4 hours, 500 DEG C of roastings 3 hours, obtain hydrocracking catalyst, be numbered Cat-4.
Comparative example 1
Use the wide variety of a kind of hydrocracking catalyst of industry, it is counted as BCat-1, in its catalyst formulation except modified Y molecular sieve, all the other compositions and method for preparing catalyst are all identical with embodiment 1, and the Y molecular sieve character that catalyst BCat-1 uses is as follows: molecular sieve SiO2/Al2O3Mol ratio is 10. XRD analysis result shows that its lattice constant is 2.446nm, relative crystallinity 95%, pore volume 0.33ml/g, specific surface area 720m2/ g, meleic acid amount is 1.0mmol/g.
Comparative example 2
Use the wide variety of a kind of hydrocracking catalyst of industry, it is counted as BCat-2, in its catalyst formulation except modified Y molecular sieve, all the other compositions and method for preparing catalyst are all identical with embodiment 2, and the Y molecular sieve character that catalyst BCat-2 uses is as follows: molecular sieve SiO2/Al2O3Mol ratio is 16. XRD analysis result shows that its lattice constant is 2.438nm, relative crystallinity 90%, pore volume 0.38ml/g, specific surface area 690m2/ g, meleic acid amount is 0.70mmol/g.
Embodiment 5
In order to investigate embodiment and comparative example prepares the reactivity worth of catalyst, catalyst has been carried out evaluation test on midget plant, evaluating apparatus adopts single hop series connection once to pass through flow process, one anti-filling industrial wide variety of pretreating catalyst by hydrocracking FF-36(Sinopec Fushun Petrochemical Research Institute), two instead load the hydrocracking catalyst prepared according to embodiment 1 ~ 4 and comparative example 1 ~ 2 respectively, and feedstock property, appreciation condition and evaluation result are listed in table 1 ~ table 5.
Table 1 raw oil character.
Table 2 appreciation condition.
Table 3 evaluation result.
Table 4 embodiment 1 and comparative example 1 catalyst stability contrast test.
Table 5 embodiment 2 and comparative example 2 catalyst stability contrast test.
Embodiment 1 ~ 2 and comparative example 1 ~ 2 catalyst contrast test on evaluating apparatus show, adopt catalyst prepared by the inventive method suitable with the distribution of comparative example catalyst prod and character, anti-nitrogen ability is higher, when the operating when refining stage generates oil nitrogen content 80ppm, the reactivity of embodiment 1 and embodiment 2 catalyst is higher, and along with this advantage of the prolongation of the duration of runs becomes apparent from.
Claims (17)
1. the preparation method of a hydrocracking catalyst, it is characterized in that including following content: one, by modified Y molecular sieve, amorphous silicon aluminium and/or aluminium oxide mix homogeneously according to a certain ratio, extruded moulding after addition dust technology pulping, dry, roasting obtains the silica-alumina supports containing modified Y molecular sieve; Two, adopt the impregnation liquid containing active metal that the carrier of step one is impregnated, the carrier drying after dipping, roasting, obtain hydrocracking catalyst;
Wherein said modified Y molecular sieve has the feature that modified Y molecular sieve lattice constant is 2.425 ~ 2.455nm; Molecular sieve phase silica alumina ratio is 8 ~ 30, wherein surface layer silica alumina ratio 20 ~ 100, and surface layer silica alumina ratio is higher than body phase silica alumina ratio 20 ~ 70, and wherein said surface layer refers to the molecular sieve outer surface thickness range to internal 5 ~ 400nm; Modified Y molecular sieve specific surface area 650 ~ 900m2/ g; Pore volume 0.30 ~ 0.50ml/g; Meleic acid content 0.3 ~ 1.2mmol/g; Relative crystallinity 80 ~ 120%.
2. in accordance with the method for claim 1, it is characterised in that: the mass percent in silica-alumina supports of the modified Y molecular sieve described in step one is 15% ~ 90%, and surplus is amorphous silica-alumina and/or aluminium oxide.
3. in accordance with the method for claim 1, it is characterised in that: the preparation method of the modified Y molecular sieve described in step one, including following content: (1) carries out Ammonium Salt Ionic exchange with NaY zeolite for former powder in ammonium salt aqueous solution; (2) Y molecular sieve after the ammonium exchange obtained in step (1) is carried out hydrothermal treatment consists; (3) the Y molecular sieve aluminum salt solution after step (2) hydrothermal treatment consists is processed; (4) the Y molecular sieve dried to step (3) gained; (5) the Y molecular sieve impregnation process in organic solvent that step (4) obtains, then rapid draing; (6) Y molecular sieve that step (5) obtains is carried out dealumination complement silicon process; (7) step (6) Y molecular sieve after dealumination complement silicon processes is through filtration, dry, roasting, obtains modified Y molecular sieve.
4. in accordance with the method for claim 3, it is characterised in that: Ammonium Salt Ionic exchange process described in step (1) is as follows: with NaY zeolite for raw material in ammonium salt aqueous solution, at 60 ~ 120 DEG C, exchange 1 ~ 3 hour, exchange times is 1 ~ 4 time, the NaY zeolite after being exchanged, Na2O content is less than 3.0%; The wherein SiO of NaY zeolite raw material2/Al2O3Mol ratio is 3 ~ 6, sodium oxide weight/mass percentage composition 6% ~ 7%; Ammonium salt is one or more in ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, ammonium salt aqueous solution concentration 0.3 ~ 6.0mol/L.
5. in accordance with the method for claim 3, it is characterised in that: step (2) described hydrothermal conditions is: temperature is 500 ~ 600 DEG C, and pressure is 0.01 ~ 0.5MPa, and the process time is 1.0 ~ 6.0 hours.
6. in accordance with the method for claim 3, it is characterised in that: the aluminium salt described in step (3) is aluminum chloride, aluminum sulfate or aluminum nitrate, and aluminium salt concentration is 0.05 ~ 2mol/L; Treatment temperature is 50 ~ 120 DEG C, and the process time is 0.5 ~ 3 hour.
7. in accordance with the method for claim 3, it is characterised in that: the baking temperature described in step (4) is 90 ~ 300 DEG C, and drying time is 2 ~ 10 hours.
8. in accordance with the method for claim 3, it is characterised in that: one or more in alkane, petroleum ether, carbon tetrachloride, benzene, toluene, ethylbenzene, dimethylbenzene, anthracene, naphthalene or phenanthrene of the organic solvent described in step (5).
9. in accordance with the method for claim 3, it is characterised in that: the impregnation method described in step (5) adopts supersaturation dipping, and dip time is 1 ~ 5 hour.
10. in accordance with the method for claim 3, it is characterised in that: the baking temperature described in step (5) is 50 ~ 300 DEG C, and drying time is 1 ~ 60 minute.
11. the method described in claim 3 or 10, it is characterised in that: the baking temperature described in step (5) is higher than the boiling point of organic solvent.
12. in accordance with the method for claim 3, it is characterized in that: the dealumination complement silicon processing procedure described in step (6) is: being added water by the Y molecular sieve that step (5) obtains is made into the water sample mixing of liquid-solid ratio 3 ~ 6, then, adding concentration is that 0.8 ~ 2mol/L ammonium fluosilicate aqueous solution processes 1 ~ 4 hour in 70 ~ 100 DEG C.
13. in accordance with the method for claim 1, it is characterised in that: the drying condition described in step one is: dry 1 ~ 5 hour at 80 ~ 120 DEG C; Roasting condition is: roasting 1 ~ 5 hour at 400 ~ 700 DEG C.
14. in accordance with the method for claim 1, it is characterised in that: the active metal described in step 2 is selected from the group VIII in the periodic table of elements and/or vib metals element; Wherein group VIII active metal is Ni and/or Co, and vib active metal is W and/or Mo.
15. in accordance with the method for claim 1, it is characterised in that: the drying condition described in step 2 is: dry 2 ~ 8 hours at 90 ~ 150 DEG C; Roasting condition is: roasting 1 ~ 5 hour at 400 ~ 700 DEG C.
16. hydrocracking catalyst prepared by the method described in claim 1 ~ 10 any claim, it is characterized in that: with overall catalyst weight gauge, including following component: the silica-alumina supports 55% ~ 85% containing modified Y molecular sieve, active metal 15% ~ 45%, wherein active metal is in metal-oxide; Described modified Y molecular sieve mass percent in silica-alumina supports is 15% ~ 90%, and surplus is amorphous silica-alumina and/or aluminium oxide; Described active metal is selected from the group VIII in the periodic table of elements and/or vib metals element; The specific surface area of described catalyst is 200 ~ 400m2/ g, pore volume is 0.2 ~ 0.5ml/g.
17. hydrocracking catalyst prepared by the method described in claim 1 ~ 10 any claim is applied to the hydrocracking reaction process of high-yield diesel oil, more producing chemical industry raw material and catalytic diesel oil hydro-conversion, it is characterized in that operating condition is: reaction pressure 6.0 ~ 20.0MPa, reaction temperature 350 ~ 420 DEG C, feed volume air speed 0.1 ~ 2.0h-1, hydrogen to oil volume ratio is 500:1 ~ 2000:1.
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| CN112717984A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
| CN112717982A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
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| CN116020525B (en) * | 2021-10-25 | 2024-07-05 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method and application thereof |
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