CN105618122A - Nitrogen-resisting hydrocracking catalyst and preparation method thereof - Google Patents
Nitrogen-resisting hydrocracking catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nitrogen-resisting hydrocracking catalyst and a preparation method thereof. The nitrogen-resisting hydrocracking catalyst comprises the following components according to the total weight of the catalyst: 55-85% of a silicon-aluminum carrier containing a modified Y type molecular sieve, and 15-45% of an active metal in the form of a metal oxide, wherein the mass percentage of the modified Y type molecular sieve in the silicon-aluminum carrier is 15-90%, and the balance is amorphous silicon-aluminum and/or aluminum oxide; the crystal cell constant of the modified Y type molecular sieve is 2.425-2.455nm; the bulk phase silicon-aluminum ratio is 8-30, wherein the surface layer silicon-aluminum ratio is 20-80, and the surface layer silicon-aluminum ratio is higher than the bulk phase silicon-aluminum ratio; the specific surface area of the modified Y type molecular sieve is 600-800m<2>/g; the pore volume is 0.40-0.70ml/g; the infrared acid content is 0.3-1.5mmol/g; and the relative crystallinity is 70-110%. The hydrocracking catalyst disclosed by the invention has good reactivity and nitrogen resistance.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, more particularly to hydrocracking catalyst that a kind of anti-nitrogen ability is strong and preparation method thereof.
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 present invention carries a kind of anti-nitrogen hydrocracking catalyst and preparation method thereof, and hydrocracking catalyst of the present invention has good reactivity and anti-nitrogen ability.
The anti-nitrogen hydrocracking catalyst of the present invention, with overall catalyst weight gauge, including following component: the silica-alumina supports 55% ~ 85% containing modified Y molecular sieve, active metal is calculated as 15% ~ 45% with metal-oxide; 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;
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; Modified Y molecular sieve lattice constant is 2.425 ~ 2.455nm; (silica alumina ratio described in literary composition is SiO to body phase silica alumina ratio2/Al2O3Mol ratio) it is 8 ~ 30, wherein surface layer silica alumina ratio 20 ~ 80, preferably 30 ~ 60, surface layer silica alumina ratio is higher than body phase silica alumina ratio 20 ~ 70, wherein said surface layer refers to the molecular sieve outer surface thickness range to internal 5 ~ 400nm, preferably 10 ~ 200nm, more preferably 50 ~ 190nm, surface layer is primary in Y molecular sieve crystal grain before modified; 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 600 ~ 800m2/ g, pore volume 0.40 ~ 0.70ml/g; Meleic acid content 0.3 ~ 1.5mmol/g, it is preferable that 0.4 ~ 1.2mmol/g; Relative crystallinity 70 ~ 110%.
The specific surface area of described catalyst is 200 ~ 400m2/ g, pore volume is 0.2 ~ 0.5ml/g.
In hydrocracking catalyst of the present invention, the preparation method of described modified Y molecular sieve, 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) Y molecular sieve that step (2) is obtained carries out low concentration acid treatment;
(4) the Y molecular sieve dried to step (3) gained;
(5) Y molecular sieve after step (4) dried is fully contacted with gaseous state or liquid unsaturated olefin, then carries out carbon deposit reaction in oxygen-containing atmosphere;
(6) the carbon deposit Y molecular sieve quick high-temp calcination process prepared by step (5);
(7) Y molecular sieve after roasting step (6) obtained carries out acid dealumination treatment;
(8) step (7) through the Y molecular sieve of acid dealumination treatment through filtering, dried, carry out process of making charcoal, obtain 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%; Wherein the silica alumina ratio of NaY zeolite raw material 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 acid used in the described low concentration acid treatment process of step (3) is mineral acid and/or organic acid, one or more in sulphuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid or acetic acid; Mineral acid and/or organic acid concentration are with H+It is calculated as 0.1 ~ 0.7mol/L, it is preferable that 0.2 ~ 0.5mol/L. Gu low concentration acid treatment process liquid/mass ratio be generally 3:1 ~ 30:1; Treatment temperature 30 ~ 80 DEG C; 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.
Unsaturated olefin described in step (5) is charcoal atomic number be 2 ~ 10 positive structure or the alkene of isomery, alkadienes; Wherein said unsaturated olefin and molecular sieve are fully contacted and refer to that gaseous state or liquid unsaturated olefin diffuse into inside molecular sieve; When using gaseous state unsaturated olefin, gaseous state unsaturated olefin and molecular sieve contact conditions be: pressure 0.1 ~ 1.0MPa; 0.1 ~ 2 hour time of contact; When using liquid unsaturated hydrocarbons, liquid unsaturated olefin and molecular sieve contact conditions be: pressure 0.1 ~ 1.0MPa, 0.5 ~ 4 hour time of contact, molecular sieve answers thorough impregnation in liquefied olefines. Described alkene and molecular sieve are fully contacted and generally carry out at normal temperatures, and described unsaturated hydrocarbons state phase is under room temperature phase.
The mixture that oxygen-containing atmosphere is air, oxygen and nitrogen described in step (5) or the one in the mixture of oxygen and noble gas, oxygen volume fraction in the gas phase is 10% ~ 100%, it is preferred to air; Carbon deposit reaction condition is: reaction temperature 50 ~ 500 DEG C, it is preferable that 100 ~ 400 DEG C, and the response time is 1 ~ 50 hour, it is preferable that 2 ~ 40 hours.
Quick high-temp roasting condition described in step (6) is: sintering temperature is 400 ~ 600 DEG C, and roasting time is 2 ~ 50 minutes, it is preferable that 5 ~ 20 minutes. General processing procedure is be directly added into the Y molecular sieve of carbon deposit in the Muffle furnace being warming up to sintering temperature in advance or other firing equipments to carry out roasting.
Sour dealumination treatment process described in step (7) is conventional method, namely processes, with mineral acid and/or organic acid mixed solution, the Y molecular sieve that step (6) obtains. The mineral acid of step (6) acid treatment process use or organic acid are one or more in sulphuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid or acetic acid, and mineral acid and/or organic acid concentration are with H+It is calculated as 0.3 ~ 2mol/L, it is preferable that 0.6 ~ 1.5mol/L; Gu the liquid/mass ratio of acid dealumination treatment process is 3:1 ~ 30:1; Treatment temperature 60 ~ 120 DEG C; The process time is 0.5 ~ 3 hour.
Treatment conditions of making charcoal described in step (8) are: roasting 2 ~ 4 hours at 400 ~ 600 DEG C, the carbon deposit of residual on elimination molecular sieve.
The preparation method of the anti-nitrogen 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;
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; In the inventive method, the concentration of the dust technology described in step one 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.
In the inventive method, the liquid-solid ratio of the dipping to step one carrier described in step 2 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.
In the inventive method, the described 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.
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.
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.
The present invention by being modified process to Y molecular sieve; namely first in air atmosphere; unsaturated hydrocarbons abundant carbon deposits inside and outside molecular sieve such as alkene, the alkadienes making under heating condition to be adsorbed on Y molecular sieve; then; carbon deposit on molecular sieve surface is removed by quick high-temp roasting; aluminum position within molecular sieve is by carbon deposit covering protection; follow-up acid dealumination treatment process mainly carries out on the outer surface; after acid-treated; the carbon deposit of molecular sieve internal residual is removed in high-temperature roasting again, recovers the acid sites position within molecular sieve. The inventive method by optionally carrying out acid dealumination treatment 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. In addition, selective to Y molecular sieve outer surface dealumination treatment, add molecular sieve outer surface secondary pore quantity, be conducive to the diffusion of the macromole raw material haptoreaction at molecular sieve surface and a pyrolysis product, avoid excessive second pyrolysis to occur, improve liquid yield.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) photo of the modified Y molecular sieve of embodiment 3 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 that step (1) is obtained is at 540 DEG C, hydrothermal treatment consists 2 hours under 0.1Mpa;
(3) (concentration is with H according to the citric acid solution of liquid-solid ratio 5:1 and 0.3mol/L for step (2) gained molecular sieve+Meter) 300ml mixing, then heat to 40 DEG C, isothermal reaction 2 hours;
(4) dry 8 hours of 150 DEG C of step (3) gained molecular sieve;
(5) molecular sieve taking step (4) gained is positioned in the hermetic container of full butylene atmosphere, controls pressure 0.3MPa and is fully contacted 20 minutes, then, heats 15 hours at 200 DEG C at air atmosphere;
(6) molecular sieve after step (5) process is directly placed in the Muffle furnace being previously heated to 450 DEG C, roasting 10 minutes;
(7) (concentration is with H according to the hydrochloric acid solution of liquid-solid ratio 10:1 Yu concentration 0.6mol/L for the molecular sieve of step (6) gained+Meter) mixing, at 80 DEG C, constant temperature processes 2 hours;
(8) Y molecular sieve after step (7) acid treatment, 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 40 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 phase is 10. XRD analysis result shows that its lattice constant is 2.448nm, relative crystallinity 90%, specific surface area 740m2/ g, pore volume 0.45ml/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) (concentration is with H according to the citric acid solution of liquid-solid ratio 8:1 and 0.5mol/L for step (2) sieve+Meter) 400ml mixing, then heat to 50 DEG C, isothermal reaction 2 hours;
(4) dry 4 hours of 200 DEG C of step (3) gained molecular sieve;
(5) taking the molecular sieve 4 hours of heptene soaking step (4) gained, then in air atmosphere, 200 DEG C are heated 22 hours;
(6) molecular sieve after step (5) process is directly placed in the Muffle furnace being previously heated to 500 DEG C, roasting 12 minutes;
(7) molecular sieve of step (6) gained is according to liquid-solid ratio 7:1 and H+Concentration is the hydrochloric acid mixed solution mixing of 1.0mol/L, and 95 DEG C process 2 hours;
(8) Y molecular sieve after step (7) acid treatment, 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.
It is 60 that Y-2 molecular sieve transmission electron microscope EDAX results measures its outer surface to the silica alumina ratio of 120nm thickness, and the silica alumina ratio of molecular sieve phase is 13. XRD analysis result shows that its lattice constant is 2.434nm, relative crystallinity 87%, specific surface area 680m2/ g, pore volume 0.50ml/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 5:1 with the ammonium nitrate that concentration is 0.5mol/L, 90 DEG C exchange 1.5 hours, repeat this process 2 times, and in the Y molecular sieve after exchange, Na content is calculated as 1.8% with Na2O.
(2) Y molecular sieve 550 DEG C that step (1) is obtained, hydrothermal treatment consists 2 hours under 0.1Mpa;
(3) (concentration is with H according to the citric acid solution of liquid-solid ratio 8:1 and 0.5mol/L for step (2) sieve+Meter) 400ml mixing, then heat to 60 DEG C, isothermal reaction 2 hours;
(4) 250 DEG C of dry 2h of step (3) gained molecular sieve;
(5) taking the molecular sieve 4 hours of heptene soaking step (4) gained, then in air atmosphere, 200 DEG C are heated 10 hours;
(6) molecular sieve after step (5) process is directly placed in the Muffle furnace being previously heated to 500 DEG C, roasting 30 minutes;
(7) molecular sieve of step (6) gained is according to liquid-solid ratio 7:1 and H+Concentration is the hydrochloric acid mixed solution mixing of 1.0mol/L, and 80 DEG C process 2 hours;
(8) Y molecular sieve after step (7) acid treatment, 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.
It is 56 that Y-3 molecular sieve transmission electron microscope EDAX results measures its outer surface to the silica alumina ratio of 190nm thickness, and the silica alumina ratio of molecular sieve phase is 14. XRD analysis result shows that its lattice constant is 2.433nm, relative crystallinity 85%, specific surface area 680m2/ g, pore volume 0.52ml/g, it is 0.69mmol/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, 75 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 2.2%;
(2) Y molecular sieve that step (1) is obtained is at 550 DEG C, hydrothermal treatment consists 2 hours under 0.1Mpa;
(3) (concentration is with H according to the citric acid solution of liquid-solid ratio 5:1 and 0.3mol/L for step (2) gained molecular sieve+Meter) 300ml mixing, then heat to 40 DEG C, isothermal reaction 2 hours;
(4) 100 DEG C of dry 9h of step (3) gained molecular sieve;
(5) take the molecular sieve 2 hours of hexadiene soaking step (4) gained, then in air atmosphere 150 DEG C heat 15 hours;
(6) molecular sieve after step (5) process is directly placed in the Muffle furnace being previously heated to 400 DEG C, roasting 10 minutes;
(7) (concentration is with H according to the hydrochloric acid solution of liquid-solid ratio 15:1 Yu concentration 0.6mol/L for the molecular sieve of step (6) gained+Meter) mixing, at 90 DEG C, constant temperature processes 2 hours;
(8) Y molecular sieve after step (7) acid treatment, 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 43 that Y-4 molecular sieve transmission electron microscope EDAX results measures its outer surface to the silica alumina ratio of 50nm thickness, and the silica alumina ratio of molecular sieve phase is 10.5. XRD analysis result shows that its lattice constant is 2.445nm, relative crystallinity 89%, specific surface area 720m2/ g, pore volume 0.47ml/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-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-4.
Comparative example 1
Comparative example 1 uses 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 catalyst BCat-1 uses modified Y molecular sieve character as follows: the silica alumina ratio of molecular sieve is 11. XRD analysis result shows that its lattice constant is 2.446nm, relative crystallinity 89%, pore volume 0.42ml/g, specific surface area 720m2/ g, meleic acid amount is 1.0mmol/g.
Comparative example 2
Comparative example 2 uses 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 catalyst BCat-2 uses modified Y molecular sieve character as follows: the silica alumina ratio of molecular sieve is 13. XRD analysis result shows that its lattice constant is 2.433nm, relative crystallinity 87%. Pore volume 0.46ml/g, specific surface area 700m2/ g, meleic acid amount is 0.68mmol/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 50ppm, 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 (19)
1. an anti-nitrogen hydrocracking catalyst, it is characterised in that: with overall catalyst weight gauge, including following component: the silica-alumina supports 55% ~ 85% containing modified Y molecular sieve, active metal is calculated as 15% ~ 45% with metal-oxide; Described active metal group VIII in the periodic table of elements and/or one or more in vib metals element; Described modified Y molecular sieve mass percent in silica-alumina supports is 15% ~ 90%, and surplus is amorphous silica-alumina and/or aluminium oxide; Modified Y molecular sieve lattice constant is 2.425 ~ 2.455nm; Body phase silica alumina ratio is 8 ~ 30, and wherein surface layer silica alumina ratio is 20 ~ 80, and surface layer silica alumina ratio is higher by 20 ~ 70 than body phase silica alumina ratio, and wherein said surface layer refers to the molecular sieve outer surface thickness range to internal 5 ~ 400nm, and surface layer is primary in Y molecular sieve before modified; Modified Y molecular sieve specific surface area 600 ~ 800m2/ g; Pore volume 0.40 ~ 0.70ml/g; Meleic acid content 0.3 ~ 1.5mmol/g; Relative crystallinity 70 ~ 110%.
2. the catalyst described in claim 1, it is characterised in that: the surface layer of described modified Y molecular sieve refers to the molecular sieve outer surface thickness range to internal 10 ~ 200nm.
3. the catalyst described in claim 1, it is characterised in that: the surface layer of described modified Y molecular sieve refers to the molecular sieve outer surface thickness range to internal 50 ~ 190nm.
4. the catalyst described in claim 1, it is characterised in that: the specific surface area of catalyst is 200 ~ 400m2/ g, pore volume is 0.2 ~ 0.5ml/g.
5. the catalyst described in claim 1, it is characterized in that: group VIII active metal is Ni and/or Co, vib active metal is W and/or Mo, and group VIII active metallic content is 3% ~ 15%, vib active metallic content is 10% ~ 40%, in metal-oxide.
6. the catalyst described in claim 1, it is characterised in that: the preparation method of described modified Y molecular sieve, 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) Y molecular sieve that step (2) is obtained carries out low concentration acid treatment; (4) the Y molecular sieve dried to step (3) gained; (5) Y molecular sieve after step (4) acid treatment is fully contacted with gaseous state or liquid unsaturated olefin, then carries out carbon deposit reaction in oxygen-containing atmosphere; (6) the carbon deposit Y molecular sieve quick high-temp calcination process prepared by step (5); (7) Y molecular sieve after roasting step (6) obtained carries out acid dealumination treatment; (8) step (7) through the Y molecular sieve of acid dealumination treatment through filtering, dried, carry out process of making charcoal, obtain modified Y molecular sieve.
7. the catalyst described in claim 6, it is characterized in that: 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.
8. the catalyst described in claim 6, it is characterised in that: the acid used in the described low concentration acid treatment process of step (3) is mineral acid and/or organic acid, one or more in sulphuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid or acetic acid; Mineral acid and/or organic acid concentration are with H+It is calculated as 0.1 ~ 0.7mol/L; Gu low concentration acid treatment process liquid/mass ratio be 3:1 ~ 30:1, treatment temperature 30 ~ 80 DEG C, the process time is 0.5 ~ 3 hour.
9. the catalyst described in claim 6, it is characterised in that: the baking temperature described in step (4) is 90 ~ 300 DEG C, and drying time is 2 ~ 10 hours.
10. the catalyst described in claim 6, it is characterised in that: the unsaturated olefin described in step (5) is charcoal atomic number be 2 ~ 10 positive structure or the alkene of isomery, alkadienes.
11. the catalyst described in claim 6 or 10, it is characterised in that: the described gaseous state unsaturated olefin of step (5) and molecular sieve contact conditions be: pressure 0.1 ~ 1.0MPa; 0.1 ~ 2 hour time of contact.
12. the catalyst described in claim 6 or 10, it is characterised in that: the described liquid unsaturated olefin of step (5) and molecular sieve contact conditions be: pressure 0.1 ~ 1.0MPa, 0.5 ~ 4 hour time of contact, molecular sieve thorough impregnation is in liquefied olefines.
13. the catalyst described in claim 6, it is characterised in that: the mixture that oxygen-containing atmosphere is air, oxygen and nitrogen described in step (5) or the one in the mixture of oxygen and noble gas, oxygen volume fraction in the gas phase is 10% ~ 100%.
14. the catalyst described in claim 6, it is characterised in that: the carbon deposit reaction condition described in step (5) is: reaction temperature 50 ~ 500 DEG C, and the response time is 1 ~ 50 hour.
15. the catalyst described in claim 6, it is characterised in that: the quick high-temp roasting condition described in step (6) is: sintering temperature is 400 ~ 600 DEG C, and roasting time is 2 ~ 50 minutes.
16. the catalyst described in claim 6, it is characterised in that: the mineral acid of step (7) acid treatment process use or organic acid are one or more in sulphuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid or acetic acid, and mineral acid and/or organic acid concentration are with H+It is calculated as 0.3 ~ 2mol/L; Gu the liquid/mass ratio of acid dealumination treatment process is 3:1 ~ 30:1; Treatment temperature 60 ~ 120 DEG C, the process time is 0.5 ~ 3 hour.
17. the catalyst described in claim 6, it is characterised in that: the treatment conditions of making charcoal described in step (8) are: roasting 2 ~ 4 hours at 400 ~ 600 DEG C.
18. the preparation method of the anti-nitrogen hydrocracking catalyst described in a claim 1, 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 1 ~ 5 hour at 80 ~ 120 DEG C, then roasting 1 ~ 5 hour at 400 ~ 700 DEG C, obtains the silica-alumina supports containing modified Y molecular sieve; Two, adopting the impregnation liquid containing active metal that the carrier of step one is impregnated, the carrier after dipping dries 2 ~ 8 hours at 90 ~ 150 DEG C, and then roasting 1 ~ 5 hour at 400 ~ 700 DEG C, obtains hydrocracking catalyst.
19. the application in the hydrocracking reaction process of high-yield diesel oil, more producing chemical industry raw material and catalytic diesel oil hydro-conversion of the hydrocracking catalyst described in a claim 1, 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111097508A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing composite Beta molecular sieve and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5030780A (en) * | 1990-07-26 | 1991-07-09 | Union Oil Company Of California | Aromatic saturation process with a silica-alumina and zeolite catalyst |
| CN101134567A (en) * | 2007-07-26 | 2008-03-05 | 复旦大学 | High-stability large aperture ordered meso-porous carbon material and preparation method thereof |
| US20080128324A1 (en) * | 2004-12-17 | 2008-06-05 | Hansen Jens A | Hydrocracking Process |
| CN101450319A (en) * | 2007-12-04 | 2009-06-10 | 中国石油化工股份有限公司 | Hydrocracking catalyst for moderate oil and preparation thereof |
| CN101543783A (en) * | 2008-03-27 | 2009-09-30 | 中国石油化工股份有限公司 | Suspension bed hydrocracking catalyst and preparation method and application thereof |
-
2014
- 2014-11-03 CN CN201410603903.9A patent/CN105618122B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5030780A (en) * | 1990-07-26 | 1991-07-09 | Union Oil Company Of California | Aromatic saturation process with a silica-alumina and zeolite catalyst |
| US20080128324A1 (en) * | 2004-12-17 | 2008-06-05 | Hansen Jens A | Hydrocracking Process |
| CN101134567A (en) * | 2007-07-26 | 2008-03-05 | 复旦大学 | High-stability large aperture ordered meso-porous carbon material and preparation method thereof |
| CN101450319A (en) * | 2007-12-04 | 2009-06-10 | 中国石油化工股份有限公司 | Hydrocracking catalyst for moderate oil and preparation thereof |
| CN101543783A (en) * | 2008-03-27 | 2009-09-30 | 中国石油化工股份有限公司 | Suspension bed hydrocracking catalyst and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111097508A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing composite Beta molecular sieve and preparation method and application thereof |
| CN111097508B (en) * | 2018-10-26 | 2023-02-21 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing composite Beta molecular sieve and preparation method and application thereof |
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