CN105582976A - Hydrocracking catalyst composition and preparation method thereof - Google Patents
Hydrocracking catalyst composition and preparation method thereof Download PDFInfo
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- CN105582976A CN105582976A CN201410603763.5A CN201410603763A CN105582976A CN 105582976 A CN105582976 A CN 105582976A CN 201410603763 A CN201410603763 A CN 201410603763A CN 105582976 A CN105582976 A CN 105582976A
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Abstract
The invention discloses a hydrocracking catalyst composition and a preparation method thereof. The catalyst composition includes the following components: 55-85% of a silicon-aluminum carrier containing modified Y-type molecular sieve, and 15-45% of active metals, wherein the modified Y-type molecular sieve accounts for 15-90% by mass of the silicon-aluminum carrier with the balanced being amorphous silicon-aluminum and/or alumina. The Si/Al ratio of a body phase in the modified Y-type molecular sieve is 10-90, and the Si/Al ratio of a surface layer is 6-30. The specific surface area is 650-900 m<2>/g and pore capacity is 0.30-0.50 ml/g. The preparation method includes the steps of 1) uniformly mixing the modified Y-type molecular sieve, the amorphous silicon-aluminum and/or the alumina, and adding dilute nitric acid to obtain paste, and performing bar-extrusion moulding, and drying and roasting the moulded produce to prepare the silicon-aluminum carrier containing the modified Y-type molecular sieve; and 2) impregnating the carrier with an impregnation solution containing the active metal, and drying and roasting the carrier to prepare the hydrocracking catalyst. The hydrocracking catalyst has excellent temperature-increasing sensitivity and operation flexibility, and has a great application prospect in a hydrocracking reaction process.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst composition and preparation method thereof.
Background technology
The features such as hydrocracking technology has that adaptability to raw material is strong, production operation and product solution flexibility is large, good product quality, various heavy inferior chargings can be converted into high-quality jet fuel, diesel oil, lube basestocks and chemical industry naphtha and the tail oil preparing ethylene by steam cracking raw material of market in urgent need, become one of modern oil refining and the most important heavy oil deep processing of petro chemical industry technique, obtained increasingly extensive application at home and abroad. the core of hydrocracking process is hydrocracking catalyst. hydrocracking catalyst is typical bifunctional catalyst, has hydrogenation and cracking dual-use function. wherein hydrogenating function has the sulphided state form of W, Mo, Ni isoreactivity metal to provide conventionally, and cracking function is provided by molecular sieve. at China's hydrocracking technology because its raw material adapts to strong, the feature that product adjustability is large, therefore, usually adapted to the changes in demand in market as a kind of regulating measure by oil refining enterprise, when between Ru Dang city field alignment, distillate is in great demand, can fecund some midbarrels, can voluminous heavy naphtha when market is in great demand to heavy naphtha, therefore, air speed on hydrocracking unit, in the relatively-stationary situation of the operating conditions such as pressure, the temperature raising sensitiveness of hydrocracking catalyst is particularly important for device flexible operating, in addition, for setter, because hydrogen supply is relatively fixing, therefore, thereby the fluctuation that should reduce as much as possible hydrogen gas consumption in device temperature raising process is more conducive to device even running in flexible operating, these are all that the research and development of hydrocracking catalyst are had higher requirement.
At present, hydrocracking process is the most widely used is modified Y molecular sieve, the inside and outside Distribution of silicon and aluminium of conventional processing method molecular sieve is even, acid centre is uniformly distributed, and in the time reducing Y molecular sieve silica alumina ratio, has improved Y molecular sieve acid site density, temperature raising sensitiveness is improved, but meanwhile, second pyrolysis also significantly increases, hydrogen consumption significantly promotes. And when Y molecular sieve is carried out to advanced treating, when sour density is too low, catalyst temperature raising sensitiveness is poor again.
CN200710158784.0 discloses a kind of hydrocracking catalyst containing Y molecular sieve and preparation method thereof, in this invention, Y zeolite is to obtain after processing hydrothermal treatment consists with aluminium salt and sour mixed aqueous solution, the catalyst temperature raising sensitiveness making is higher, but simultaneously, temperature raising process second pyrolysis obviously increases, hydrogen consumption significantly rises, and is unfavorable for the even running of industrial hydrocracking unit temperature raising process apparatus.
CN200810012212.6 discloses a kind of carrier of hydrocracking catalyst and preparation method thereof, and hydrocracking catalyst temperature raising sensitiveness prepared by this invention is poor.
Summary of the invention
For the deficiencies in the prior art, the present invention carries a kind of hydrocracking catalyst composition and preparation method thereof hydrocracking catalyst of the present invention and has good temperature raising sensitiveness and operating flexibility, in hydrocracking reaction process, has broad application prospects.
Hydrocracking catalyst composition of the present invention, in total catalyst weight, comprises following component: containing the silica-alumina supports 55% ~ 85% of modified Y molecular sieve, and active metal 15% ~ 45%, wherein active metal is in metal oxide; Described active metal is selected from group VIII and/or the group vib metallic element in the periodic table of elements, and group VIII active metal can be Ni and/or Co, and group vib active metal can be W and/or Mo;
The mass percent of wherein said modified Y molecular sieve in silica-alumina supports is 15% ~ 90%, preferably 30% ~ 70%, and surplus is amorphous aluminum silicide 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) be 10 ~ 90, preferably 20 ~ 60, superficial layer silica alumina ratio 6 ~ 30, preferably 8 ~ 20, superficial layer silica alumina ratio is lower than body phase silica alumina ratio 5 ~ 40, and wherein said superficial layer refers to the thickness range of molecular sieve outer surface to inner 5 ~ 400nm, preferably 10 ~ 200nm, more preferably 50 ~ 190nm, the former Y molecular sieve crystal grain of being born in before modification of superficial layer; Sodium oxide molybdena quality percentage composition is less than 1.0%, is preferably less than 0.5%; Modified Y molecular sieve specific area 650 ~ 900m2/ g; Pore volume 0.30 ~ 0.50ml/g; Meleic acid content 0.3 ~ 1.0mmol/g, preferably 0.4 ~ 0.8mmol/g; Relative crystallinity 90 ~ 130%.
The specific area of described catalyst is 200 ~ 400m2/ g, pore volume is 0.2 ~ 0.5ml/g.
The preparation method of hydrocracking catalyst composition of the present invention, comprises following content:
One, modified Y molecular sieve, amorphous silicon aluminium and/or aluminium oxide are mixed according to a certain ratio, add extruded moulding after rare nitric acid pulping, dry, roasting obtains the silica-alumina supports containing modified Y molecular sieve; Wherein the concentration of rare nitric acid is 3wt% ~ 30wt%; Described drying condition is: at 80 ~ 120 DEG C, be dried 1 ~ 5 hour; Roasting condition is: roasting 1 ~ 5 hour at 400 ~ 700 DEG C;
Two, adopt containing the maceration extract of active metal the carrier of step 1 is flooded, the carrier drying after dipping, roasting, obtain hydrocracking catalyst; Described active metal is selected from group VIII and/or the group vib metallic element in the periodic table of elements, and group VIII active metal can be Ni and/or Co, and group vib active metal can be W and/or Mo; Wherein the liquid-solid ratio of dipping is 1.5:1 ~ 3:1, adopt the mode of saturated dipping well known in the art to carry out, in maceration extract, the content of group vib metallic compound is counted 20 ~ 60g/100ml by corresponding oxide, the content of group VIII metallic compound is counted 3 ~ 20g/100ml by corresponding oxide, and in maceration extract, the concentration of metallic compound can adjust accordingly according to product needed; Wherein said drying condition is: at 90 ~ 150 DEG C, be dried 2 ~ 8 hours; Roasting condition is: roasting 1 ~ 5 hour at 400 ~ 700 DEG C;
The preparation method of modified Y molecular sieve of the present invention, comprises following content:
(1) in ammonium salt aqueous solution, carry out ammonium salt ion-exchange taking NaY zeolite as former powder;
(2) Y molecular sieve after the ammonium exchange obtaining in step (1) carries out dealumination complement silicon processing;
(3) step (2) Y molecular sieve after treatment is carried out to hydrothermal treatment consists;
(4) to the Y molecular sieve aluminum salt solution processing after step (3) hydrothermal treatment consists;
(5) process the Y molecular sieve of step (4) gained is dry;
(6) unsaturated olefin of liquid state or gaseous state is fully contacted with the Y molecular sieve of step (5) aluminum salt solution, then in oxygen-containing atmosphere, carry out carbon deposit reaction;
(7) the carbon deposit Y molecular sieve quick high-temp calcination process of being prepared by step (6);
(8) molecular sieve step (7) being obtained carries out alkali desiliconization processing;
(9) step (8) through alkali desiliconization Y molecular sieve after treatment after filtration, dry after, the processing of making charcoal, obtains modified Y molecular sieve.
Described in step (1), ammonium salt ion exchange process is as follows: taking NaY zeolite as raw material is in ammonium salt aqueous solution, at 60 ~ 120 DEG C, preferably at 60 ~ 90 DEG C, exchange 1 ~ 3 hour, exchange times is 1 ~ 4 time, obtains the NaY zeolite after exchange, Na2O content is less than 3.0%; The wherein SiO of NaY zeolite raw material2/Al2O3Mol ratio is 3 ~ 6, sodium oxide molybdena quality 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, preferably 1.0 ~ 3.0mol/L.
The described dealumination complement silicon of step (2) is treated to method well known to those skilled in the art, can adopt conventional ammonium fluosilicate dealumination complement silicon method, general process is: the Y molecular sieve that step (1) is obtained adds water and is made into the mixed sample of water of liquid-solid mass ratio 3:1 ~ 6:1, then, adding concentration is 0.8 ~ 2.0mol/L ammonium fluosilicate aqueous solution, in 70 ~ 120 DEG C of processing 1 ~ 4 hour, wherein ammonium fluosilicate solution addition need to be deposited ammonium fluosilicate 9 ~ 30g meter according to every 100g molecular sieve. Other are as SiCl4The methods such as gas phase dealumination complement silicon are also suitable for.
The described hydrothermal treatment consists process of step (3) is at self steam or passes under the condition of steam, and hydrothermal treatment consists condition is: temperature is 500 ~ 600 DEG C, and pressure is 0.01 ~ 0.5MPa, and the processing time is 1.0 ~ 6.0 hours.
The described aluminium salt processing procedure aluminium salt used of step (4) is one or more in aluminium chloride, aluminum sulfate or aluminum nitrate, and aluminium salinity is 0.05 ~ 2mol/L, and treatment temperature is 50 ~ 120 DEG C, and the processing time is 0.5 ~ 3 hour.
The dry processing procedure that step (5) is described: 90 ~ 300 DEG C are dried 2 ~ 10 hours.
The described unsaturated olefin of step (6) is that charcoal atomicity is 2 ~ 10 positive structure or isomeric olefine, alkadienes; Wherein said alkene fully contacts and refers to that unsaturated olefin diffuses into molecular sieve inside with molecular sieve; In the time using gaseous state unsaturated olefin, gaseous state unsaturated olefin and molecular sieve contact conditions are: pressure 0.1 ~ 1.0MPa, 0.1 ~ 2 hour time of contact; In the time using liquid unsaturated hydrocarbons, liquid unsaturated olefin and molecular sieve contact conditions are: pressure 0.1 ~ 1.0MPa, 0.5 ~ 4 hour time of contact, molecular sieve answers thorough impregnation in liquefied olefines. Described alkene fully contacts generally and carries out at normal temperatures with molecular sieve, and described unsaturated hydrocarbons state phase is phase under normal temperature.
The described oxygen-containing atmosphere of step (6) is the one in the mixture of air, oxygen and nitrogen or the mixture of oxygen and inert gas, and the volume fraction of oxygen in gas phase is 10% ~ 100%, is preferably air; Carbon deposit reaction condition is: 50 ~ 500 DEG C of reaction temperatures, preferably 100 ~ 400 DEG C, the reaction time is 1 ~ 50 hour, preferably 2 ~ 40 hours.
The described quick high-temp calcination process condition of step (7) is: sintering temperature is 400 ~ 600 DEG C, roasting time 2 ~ 50 minutes, preferably 5 ~ 20 minutes. General roasting process is: the Y molecular sieve of carbon deposit is directly added to roasting in the Muffle furnace that is warming up in advance sintering temperature.
The aqueous solution that the alkali lye that alkali desiliconization processing procedure described in step (8) is used is NaOH or potassium hydroxide, wherein the concentration of alkali lye is 0.1wt% ~ 2wt%. 50 ~ 100 DEG C of alkali lye treatment temperatures, the processing time is 0.5 ~ 4 hour, the liquid-solid mass ratio of alkali lye/molecular sieve is 5:1 ~ 10:1.
The described treatment conditions of making charcoal of step (9) are: roasting 2 ~ 4 hours at 400 ~ 600 DEG C, removes carbon deposit residual on molecular sieve.
Hydrocracking catalyst composition of the present invention can be applicable to produce flexibly industrial chemicals or intermediate oil etc. different hydrocracking reaction processes, general operational requirement(GOR) is: reaction pressure 6.0 ~ 20.0MPa, 350 ~ 420 DEG C of reaction temperatures, 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 superficial layer and body phase silica alumina ratio.
In the inventive method, the Y molecular sieve that hydrocracking catalyst is used carries out specially treated, first in air atmosphere, under heating condition, make to be adsorbed in the alkene on Y molecular sieve, the unsaturated hydrocarbons such as alkadienes are abundant carbon deposit inside and outside molecular sieve, then, burn the charcoal depositing on molecular sieve surface by the method for quick high-temp roasting, like this molecular sieve inside by carbon deposit covering protection, therefore, in follow-up alkali liquor desiliconization processing procedure, mainly carry out on the outer surface, after alkali treatment, the inner residual carbon deposit of molecular sieve is removed in high-temperature roasting again, recover the acid sites position of molecular sieve inside. the inventive method is by optionally carrying out alkali desiliconization processing to Y molecular sieve outer surface, in retaining the inner high silica alumina ratio of molecular sieve, optionally reduce the silica alumina ratio of Y molecular sieve outer surface, improve the acid centre of molecular sieve outer surface, the hydrocracking catalyst of preparing than conventional method modified molecular screen can significantly improve temperature raising sensitiveness, the operating flexibility of catalyst, and same conversion lower device liquid is received and chemical hydrogen consumption all makes moderate progress.
Brief description of the drawings
Fig. 1 is transmission electron microscope (TEM) photo of the modified Y molecular sieve prepared of embodiment 1.
Detailed description of the invention
Below by embodiment, the present invention is further described, but therefore do not limit the present invention.
Embodiment 1
Molecular sieve modified processing procedure:
(1) get NaY molecular screen primary powder 200g prepared by laboratory, the ammonium nitrate that is 0.5mol/L by concentration mixes according to liquid-solid ratio 3:1, and 70 DEG C exchange 3 hours, repeat this process 3 times, and in the Y molecular sieve after exchange, Na content is with Na2O counts 2.5%;
(2) molecular sieve of step (1) gained mixes with distilled water according to liquid-solid ratio 5:1, and then, adding concentration is the ammonium fluosilicate solution 200ml of 0.9mol/L, processes 2 hours for 80 DEG C;
(3) 540 DEG C of Y molecular sieves step (2) being obtained, hydrothermal treatment consists 1.5 hours under 0.1MPa;
(4) step (3) gained molecular sieve is uniformly mixed according to liquid-solid ratio 7:1 and distilled water, is then warming up to 80 DEG C, adds the aluminum sulfate solution 400ml of 0.5mol/L, isothermal reaction 2 hours in the process stirring.
(5) dry 8 hours of 150 DEG C, step (4) gained molecular sieve;
(6) molecular sieve of getting step (5) gained is positioned in the closed container that is full of butadiene atmosphere, and controlled pressure 0.3MPa fully contacts 20 minutes, then, at air atmosphere 200 DEG C of heating 15 hours;
(7) step (6) molecular sieve after treatment is directly put into the Muffle furnace that is heated in advance 450 DEG C, roasting 12 minutes;
(8) Y molecular sieve of step (7) gained mixes with 0.7% sodium hydroxide solution according to liquid-solid ratio 5:1, processes 2 hours for 90 DEG C;
(9) Y molecular sieve after step (8) alkali treatment, 120 DEG C are dried 2 hours, and 550 DEG C of roastings, after 2 hours, obtain modified Y molecular sieve, are numbered Y-1.
Y-1 molecular sieve transmission electron microscope EDAX results is measured its outer surface to 80nm thickness, the SiO of superficial layer2/Al2O3Mol ratio is 13, molecular sieve SiO2/Al2O3Mol ratio is 29. XRD analysis result shows that its lattice constant is 2.434nm, relative crystallinity 106%. Pore volume 0.37ml/g, specific area 810m2/ g, it is 0.65mmol/g that infrared analysis result is measured Y-1 meleic acid amount.
Hydrocracking catalyst preparation process:
(1) configuration W-Ni dipping solution: get after ammonium metatungstate 430g and nickel nitrate 440g are dissolved in water and configure 1000ml dipping solution, in gained dipping solution, active metal is with WO3Cubage is respectively 36g/100ml and 11g/100ml with NiO, solution numbering RY-1;
(2) get Y-165g and mix with 35g macroporous aluminium oxide, add the rare nitric acid of 4g/100ml to mix in blender and roll to extruding shape, on banded extruder, extruded moulding obtains carrier T-1;
(3) get T-160g and add 120mlRY-1 maceration extract dipping 2 hours, then 120 DEG C dry 4 hours, 500 DEG C of roastings 3 hours, obtain hydrocracking catalyst, are numbered Cat-1.
Embodiment 2
Molecular sieve modified processing procedure:
(1) get NaY molecular screen primary powder prepared by laboratory, the ammonium nitrate that is 0.8mol/L by concentration mixes according to liquid-solid ratio 3:1, and 70 DEG C exchange 3 hours, repeat this process 3 times, and in the Y molecular sieve after exchange, Na content is with Na2O counts 2.0%.
(2) molecular sieve of step (1) gained mixes with distilled water according to liquid-solid ratio 5:1, and then, adding concentration is the ammonium fluosilicate solution 300ml of 1.5mol/L, processes 2 hours for 90 DEG C;
(3) 550 DEG C of Y molecular sieves step (2) being obtained, hydrothermal treatment consists 2 hours under 0.1MPa;
(4) step (3) gained molecular sieve is uniformly mixed according to liquid-solid ratio 6:1 and distilled water, is then warming up to 90 DEG C, adds the aluminum sulfate solution 600ml of 0.8mol/L, isothermal reaction 2 hours in the process stirring.
(5) dry 6 hours of 200 DEG C, step (4) gained molecular sieve;
(6) get the molecular sieve 4 hours of heptene soaking step (5) gained, then, 180 DEG C of heating 20 hours under air atmosphere;
(7) step (6) molecular sieve after treatment is directly put into the Muffle furnace that is heated in advance 500 DEG C, roasting 28 minutes;
(8) molecular sieve of step (7) gained mixes with 1.2% sodium hydroxide solution according to liquid-solid ratio 6:1, processes 3 hours for 80 DEG C;
(9) Y molecular sieve after step (8) alkali treatment, 120 DEG C are dried 2 hours, and 550 DEG C of roastings, after 2 hours, obtain modified Y molecular sieve, are numbered Y-2.
Hydrocracking catalyst preparation process:
(1) configuration W-Ni dipping solution: get after ammonium metatungstate 480g and nickel nitrate 480g are dissolved in water and configure 1000ml dipping solution, in gained dipping solution, active metal is with WO3Cubage is respectively 40g/100ml and 12g/100ml with NiO, solution numbering RY-2;
(2) get Y-250g and mix with 50g macroporous aluminium oxide, add the rare nitric acid of 4g/100ml to mix in blender and roll to extruding shape, on banded extruder, extruded moulding obtains carrier T-2;
(3) get T-260g and add 120mlRY-2 maceration extract dipping 2 hours, then 120 DEG C dry 4 hours, 500 DEG C of roastings 3 hours, obtain hydrocracking catalyst, are numbered Cat-2.
Y-2 molecular sieve transmission electron microscope EDAX results is measured its outer surface to 180nm thickness, the SiO of superficial layer2/Al2O3Mol ratio is 7.0, molecular sieve SiO2/Al2O3Mol ratio is 41. XRD analysis result shows that its lattice constant is 2.427nm, relative crystallinity 101%. Pore volume 0.38ml/g, specific area 770m2/ g, it is 0.49mmol/g that infrared analysis result is measured Y-2 meleic acid amount.
Embodiment 3
Molecular sieve modified processing procedure:
(1) get NaY molecular screen primary powder prepared by laboratory, the ammonium nitrate that is 0.8mol/L by concentration mixes according to liquid-solid ratio 3:1, and 70 DEG C exchange 3 hours, repeat this process 3 times, and in the Y molecular sieve after exchange, Na content is with Na2O counts 2.0%.
(2) molecular sieve of step (1) gained mixes with distilled water according to liquid-solid ratio 5:1, and then, adding concentration is the ammonium fluosilicate solution 250ml of 1.0mol/L, processes 2 hours for 95 DEG C;
(3) 540 DEG C of Y molecular sieves step (2) being obtained, hydrothermal treatment consists 1.5 hours under 0.1MPa;
(4) step (3) gained molecular sieve is uniformly mixed according to liquid-solid ratio 6:1 and distilled water, is then warming up to 90 DEG C, adds the aluminum sulfate solution 600ml of 0.8mol/L, isothermal reaction 1.5 hours in the process stirring.
(5) dry 3 hours of 250 DEG C, step (4) molecular sieve after treatment;
(6) get the molecular sieve 3 hours of hexadiene soaking step (5) gained, then, 180 DEG C of heating 25 hours under air atmosphere;
(7) step (6) molecular sieve after treatment is directly put into the Muffle furnace that is heated in advance 500 DEG C, roasting 15 minutes;
(8) molecular sieve of step (7) gained mixes with 1.0% sodium hydroxide solution according to liquid-solid ratio 6:1, processes 2 hours for 75 DEG C;
(9) Y molecular sieve after step (8) alkali treatment, 120 DEG C are dried 2 hours, and 550 DEG C of roastings, after 2 hours, obtain modified Y molecular sieve, are numbered Y-3.
Hydrocracking catalyst preparation process:
(1) configuration W-Ni dipping solution: get after ammonium metatungstate 480g and nickel nitrate 480g are dissolved in water and configure 1000ml dipping solution, in gained dipping solution, active metal is with WO3Cubage is respectively 40g/100ml and 12g/100ml with NiO, solution numbering RY-3;
(2) get Y-350g and mix with 50g macroporous aluminium oxide, add the rare nitric acid of 4g/100ml to mix in blender and roll to extruding shape, on banded extruder, extruded moulding obtains carrier T-3;
(3) get T-360g and add 120mlRY-3 maceration extract dipping 2 hours, then 120 DEG C dry 4 hours, 500 DEG C of roastings 3 hours, obtain hydrocracking catalyst, are numbered Cat-3.
Y-3 molecular sieve transmission electron microscope EDAX results is measured its outer surface to 130nm thickness, the SiO of superficial layer2/Al2O3Mol ratio is 9.0, molecular sieve SiO2/Al2O3Mol ratio is 39. XRD analysis result shows that its lattice constant is 2.435nm, relative crystallinity 103%. Pore volume 0.38ml/g, specific area 800m2/ g, it is 0.50mmol/g that infrared analysis result is measured Y-3 meleic acid amount.
Embodiment 4
Molecular sieve modified processing procedure:
(1) get NaY molecular screen primary powder 200g prepared by laboratory, the ammonium nitrate that is 0.6mol/L by concentration mixes according to liquid-solid ratio 3:1, and 80 DEG C exchange 3 hours, repeat this process 3 times, and in the Y molecular sieve after exchange, Na content is with Na2O counts 2.0%;
(2) molecular sieve of step (1) gained mixes with distilled water according to liquid-solid ratio 5:1, and then, adding concentration is the ammonium fluosilicate solution 100ml of 0.8mol/L, processes 1.5 hours for 80 DEG C;
(3) 550 DEG C of Y molecular sieves step (2) being obtained, hydrothermal treatment consists 1.0 hours under 0.1MPa;
(4) step (3) gained molecular sieve is uniformly mixed according to liquid-solid ratio 5:1 and distilled water, is then warming up to 80 DEG C, adds the aluminum sulfate solution 400ml of 0.5mol/L, isothermal reaction 2 hours in the process stirring.
(5) step (4) molecular sieve after treatment is dried 8 hours in 150 DEG C;
(6) molecular sieve of getting step (5) gained is positioned in the closed container that is full of propylene atmosphere, and controlled pressure 0.2MPa fully contacts 25 minutes, then, at air atmosphere 250 DEG C of heating 10 hours;
(7) step (6) molecular sieve after treatment is directly put into the Muffle furnace that is heated in advance 470 DEG C, roasting 10 minutes;
(8) Y molecular sieve of step (7) gained mixes with 0.6% sodium hydroxide solution according to liquid-solid ratio 5:1, processes 2 hours for 95 DEG C;
(9) Y molecular sieve after step (8) alkali treatment, 120 DEG C are dried 2 hours, and 550 DEG C of roastings, after 2 hours, obtain modified Y molecular sieve, are numbered Y-4.
Y-4 molecular sieve transmission electron microscope EDAX results is measured its outer surface to 90nm thickness, the SiO of superficial layer2/Al2O3Mol ratio is 15, molecular sieve SiO2/Al2O3Mol ratio is 28. XRD analysis result shows that its lattice constant is 2.437nm, relative crystallinity 105%. Pore volume 0.37ml/g, specific area 820m2/ g, it is 0.66mmol/g that infrared analysis result is measured Y-4 meleic acid amount.
Hydrocracking catalyst preparation process:
(1) configuration W-Ni dipping solution: get after ammonium metatungstate 430g and nickel nitrate 440g are dissolved in water and configure 1000ml dipping solution, in gained dipping solution, active metal is with WO3Cubage is respectively 36g/100ml and 11g/100ml with NiO, solution numbering RY-4;
(2) get Y-465g and mix with 35g macroporous aluminium oxide, add the rare nitric acid of 4g/100ml to mix in blender and roll to extruding shape, on banded extruder, extruded moulding obtains carrier T-4;
(3) get T-460g and add 120mlRY-4 maceration extract dipping 2 hours, then 120 DEG C dry 4 hours, 500 DEG C of roastings 3 hours, obtain hydrocracking catalyst, are numbered Cat-4.
Comparative example 1
Use a kind of hydrocracking catalyst of industrial extensive use, meter is made 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 B Cat-1 uses is as follows: molecular sieve SiO2/Al2O3Mol ratio is 23. XRD analysis result shows that its lattice constant is 2.441nm, relative crystallinity 88%, pore volume 0.36ml/g, specific area 720m2/ g, meleic acid amount is 0.73mmol/g.
Comparative example 2
Use a kind of hydrocracking catalyst of industrial extensive use, meter is made 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 B Cat-2 uses is as follows: molecular sieve SiO2/Al2O3Mol ratio is 32. XRD analysis result shows that its lattice constant is 2.426nm, relative crystallinity 92%, pore volume 0.39ml/g, specific area 690m2/ g, meleic acid amount is 0.55mmol/g.
Embodiment 5
In order to investigate the reactivity worth of embodiment 1 ~ 4 and comparative example 1 ~ 2 Kaolinite Preparation of Catalyst, catalyst is carried out on midget plant to evaluation test, evaluating apparatus adopts single hop series connection once to pass through flow process, the conventional catalyst for refining of one anti-filling, two instead load respectively the hydrocracking catalyst of preparing according to embodiment 1 ~ 4 and comparative example 1 ~ 2 method, and feedstock oil character, appreciation condition and evaluation result are listed in table 1 ~ table 5.
Table 1 feedstock oil character.
| Feedstock oil | Feedstock oil |
| Density, g/cm3 | 0.9164 |
| Boiling range, DEG C | 328～531 |
| C，m% | 86.68 |
| H，m% | 12.30 |
| S，m% | 1.54 |
| N，% | 1138 |
| BMCI value | 48.2 |
Table 2 appreciation condition.
| Catalyst | Cat-1 | Cat-2 | Cat-3 | Cat-4 | BCat-1 | BCat-2 |
| Reaction temperature, DEG C | 376 | 376 | 376 | 376 | 376 | 376 |
| Reaction pressure, MPa | 15.0 | 15.0 | 15.0 | 15.0 | 15.0 | 15.0 |
| Cracking zone volume space velocity, h-1 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Hydrogen to oil volume ratio | 1200 | 1200 | 1200 | 1200 | 1200 | 1200 |
| Refining stage generates oily nitrogen content, ppm | 10 | 10 | 10 | 10 | 10 | 10 |
Table 2 appreciation condition.
| Catalyst | Cat-1 | Cat-2 | Cat-3 | Cat-4 | BCat-1 | BCat-2 |
| Reaction temperature, DEG C | 376 | 376 | 376 | 376 | 376 | 376 |
| Reaction pressure, MPa | 15.0 | 15.0 | 15.0 | 15.0 | 15.0 | 15.0 |
| Cracking zone volume space velocity, h-1 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Hydrogen to oil volume ratio | 1200 | 1200 | 1200 | 1200 | 1200 | 1200 |
| Refining stage generates oily nitrogen content, ppm | 10 | 10 | 10 | 10 | 10 | 10 |
Table 3 evaluation result.
| Catalyst | Cat-1 | Cat-2 | Cat-3 | Cat-4 | BCat-1 | BCat-2 |
| Product distributes, m% | ||||||
| Be less than 65 DEG C of light naphthars | 4.05 | 2.67 | 2.72 | 4.43 | 6.62 | 3.41 |
| 65 ~ 165 DEG C of heavy naphtha | 26.21 | 21.88 | 22.62 | 30.43 | 27.71 | 18.30 |
| 165 ~ 260 DEG C of boat coals | 28.01 | 25.05 | 25.24 | 27.88 | 28.15 | 25.22 |
| 260 ~ 350 DEG C of diesel oil | 18.47 | 19.54 | 20.53 | 16.34 | 17.50 | 19.20 |
| 350 DEG C of tail oils of > | 25.75 | 32.98 | 31.02 | 23.19 | 22.82 | 36.01 |
Table 4 embodiment 1 investigates test with comparative example 1 catalyst differential responses temperature.
Table 5 embodiment 2 investigates test with comparative example 2 catalyst differential responses temperature.
By adopting embodiment 1 and the contrast test of comparative example 1 catalyst on evaluating apparatus to show, the catalyst that adopts the inventive method to prepare has better operating flexibility, in temperature raising process, product changes in distribution amplitude is larger, can switch and carry out voluminous naphtha and produce less two kinds of pattern operations of naphtha, simultaneously, because the present invention adopts specific process modified Y molecular sieve, in improving the outside acid centre of molecular sieve, retain the high silica alumina ratio of molecular sieve inside, acid centre still less, the secondary cracking that temperature raising process causes significantly reduces, therefore, with respect to comparative example 1 catalyst, embodiment 1 catalyst hydrogen in temperature raising process consumes increase and liquid receipts fall is less, more be conducive to the quiet run of device. embodiment 2 shows with the contrast test of comparative example 2 catalyst, embodiment 2 catalyst have better temperature raising sensitiveness because the higher acid site quantity of molecular sieve outer surface makes embodiment 2 catalyst, when reaction temperature is increased to the process of 380 DEG C from 372 DEG C, be greater than 350 DEG C of cut conversion ratios and improve approximately 15 percentage points, and comparative example 2 only improves 6 percentage points, compare comparative example 2 catalyst, embodiment 2 catalyst show larger product distribution flexibility. therefore, all in all catalyst of the present invention shows good temperature raising sensitiveness, device operating flexibility and higher liquid yield.
Claims (22)
1. a hydrocracking catalyst composition, is characterized in that in total catalyst weight, comprises following component: containing the silica-alumina supports 55% ~ 85% of modified Y molecular sieve, and active metal 15% ~ 45%, active metal is in metal oxide; The mass percent of wherein said modified Y molecular sieve in silica-alumina supports is 15% ~ 90%, and surplus is amorphous aluminum silicide and/or aluminium oxide; Modified Y molecular sieve lattice constant is 2.425 ~ 2.455nm; Body phase silica alumina ratio is 10 ~ 90, superficial layer silica alumina ratio 6 ~ 30, and superficial layer silica alumina ratio is lower than body phase silica alumina ratio 5 ~ 40, and wherein said superficial layer refers to the thickness range of molecular sieve outer surface to inner 5 ~ 400nm, the former Y molecular sieve crystal grain of being born in before modification of superficial layer; Modified Y molecular sieve specific area 650 ~ 900m2/ g; Pore volume 0.30 ~ 0.50ml/g; Meleic acid content 0.3 ~ 1.0mmol/g; Relative crystallinity 90 ~ 130%.
2. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that: described active metal is selected from one or more in group VIII and/or the group vib metallic element in the periodic table of elements; Group VIII active metal is Ni and/or Co, and group vib active metal is W and/or Mo.
3. according to the carbon monoxide-olefin polymeric described in claim 1 or 2, it is characterized in that: the specific area of described catalyst is 200 ~ 400m2/ g, pore volume is 0.2 ~ 0.5ml/g.
4. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that: the preparation method of described modified Y molecular sieve, comprises following content: (1) carries out ammonium salt ion-exchange in ammonium salt aqueous solution taking NaY zeolite as former powder; (2) Y molecular sieve after the ammonium exchange obtaining in step (1) carries out dealumination complement silicon processing; (3) step (2) Y molecular sieve after treatment is carried out to hydrothermal treatment consists; (4) to the Y molecular sieve aluminum salt solution processing after step (3) hydrothermal treatment consists; (5) process the Y molecular sieve of step (4) gained is dry; (6) unsaturated olefin of liquid state or gaseous state is fully contacted with the Y molecular sieve of step (5) aluminum salt solution, then in oxygen-containing atmosphere, carry out carbon deposit reaction; (7) the carbon deposit Y molecular sieve quick high-temp calcination process of being prepared by step (6); (8) molecular sieve step (7) being obtained carries out alkali desiliconization processing; (9) step (8) through alkali desiliconization Y molecular sieve after treatment after filtration, dry after, the processing of making charcoal, obtains modified Y molecular sieve.
5. according to carbon monoxide-olefin polymeric claimed in claim 4, it is characterized in that: described in step (1), ammonium salt ion exchange process is as follows: taking NaY zeolite as raw material is in ammonium salt aqueous solution, at 60 ~ 120 DEG C, preferably at 60 ~ 90 DEG C, exchange 1 ~ 3 hour, exchange times is 1 ~ 4 time, obtains the NaY zeolite after exchange, Na2O content is less than 3.0%.
6. according to carbon monoxide-olefin polymeric claimed in claim 4, it is characterized in that: the described dealumination complement silicon process of step (2) is: the Y molecular sieve that step (1) is obtained adds water and is made into the mixed sample of water of liquid-solid mass ratio 3:1 ~ 6:1, then, adding concentration is 0.8 ~ 2.0mol/L ammonium fluosilicate aqueous solution, in 70 ~ 120 DEG C of processing 1 ~ 4 hour, wherein ammonium fluosilicate solution addition need to be deposited ammonium fluosilicate 9 ~ 30g meter according to every 100g molecular sieve.
7. according to carbon monoxide-olefin polymeric claimed in claim 4, it is characterized in that: the described hydrothermal treatment consists process of step (3) is at self steam or passes under the condition of steam, hydrothermal treatment consists condition is: temperature is 500 ~ 600 DEG C, and pressure is 0.01 ~ 0.5MPa, and the processing time is 1.0 ~ 6.0 hours.
8. according to carbon monoxide-olefin polymeric claimed in claim 4, it is characterized in that: the described aluminium salt processing procedure aluminium salt used of step (4) is one or more in aluminium chloride, aluminum sulfate or aluminum nitrate, and aluminium salinity is 0.05 ~ 2mol/L; Treatment temperature is 50 ~ 120 DEG C, and the processing time is 0.5 ~ 3 hour.
9. according to carbon monoxide-olefin polymeric claimed in claim 4, it is characterized in that: the dry processing procedure that step (5) is described: 90 ~ 300 DEG C are dried 2 ~ 10 hours.
10. according to carbon monoxide-olefin polymeric claimed in claim 4, it is characterized in that: the described unsaturated olefin of step (6) is that charcoal atomicity is 2 ~ 10 positive structure or isomeric olefine, alkadienes.
11. according to the carbon monoxide-olefin polymeric described in claim 4 or 10, it is characterized in that: described gaseous state unsaturated olefin and the molecular sieve contact conditions of step (6) is: pressure 0.1 ~ 1.0MPa, 0.1 ~ 2 hour time of contact; Liquid unsaturated olefin and molecular sieve contact conditions are: pressure 0.1 ~ 1.0MPa, 0.5 ~ 4 hour time of contact, molecular sieve answers thorough impregnation in liquefied olefines.
12. according to carbon monoxide-olefin polymeric claimed in claim 4, it is characterized in that: the described oxygen-containing atmosphere of step (6) is the one in the mixture of air, oxygen and nitrogen or the mixture of oxygen and inert gas, and the volume fraction of oxygen in gas phase is 10% ~ 100%.
13. according to carbon monoxide-olefin polymeric claimed in claim 4, it is characterized in that: the described carbon deposit reaction condition of step (6) is: 50 ~ 500 DEG C of reaction temperatures, the reaction time is 1 ~ 50 hour.
14. according to carbon monoxide-olefin polymeric claimed in claim 4, it is characterized in that: the described quick high-temp calcination process condition of step (7) is: sintering temperature is 400 ~ 600 DEG C, roasting time 2 ~ 50 minutes.
15. according to carbon monoxide-olefin polymeric claimed in claim 4, it is characterized in that: the aqueous solution that the alkali lye that the alkali desiliconization processing procedure described in step (8) is used is NaOH or potassium hydroxide, wherein the concentration of alkali lye is 0.1wt% ~ 2wt%.
16. according to the carbon monoxide-olefin polymeric described in claim 15, it is characterized in that: 50 ~ 100 DEG C of step (8) alkali lye treatment temperatures, and the processing time is 0.5 ~ 4 hour, the liquid-solid mass ratio of alkali lye/molecular sieve is 5:1 ~ 10:1.
17. according to carbon monoxide-olefin polymeric claimed in claim 4, it is characterized in that: the described treatment conditions of making charcoal of step (9) are: roasting 2 ~ 4 hours at 400 ~ 600 DEG C.
The preparation method of the carbon monoxide-olefin polymeric described in 18. 1 kinds of claims 1 or 2, it is characterized in that comprising following content: one, modified Y molecular sieve, amorphous silicon aluminium and/or aluminium oxide are mixed according to a certain ratio, add extruded moulding after rare nitric acid pulping, dry, roasting obtains the silica-alumina supports containing modified Y molecular sieve; Two, adopt containing the maceration extract of active metal the carrier of step 1 is flooded, the carrier drying after dipping, roasting, obtain hydrocracking catalyst.
19. in accordance with the method for claim 18, it is characterized in that: the drying condition described in step 1 is: at 80 ~ 120 DEG C, be dried 1 ~ 5 hour; Roasting condition is: roasting 1 ~ 5 hour at 400 ~ 700 DEG C.
20. in accordance with the method for claim 18, it is characterized in that: the drying condition described in step 2 is: at 90 ~ 150 DEG C, be dried 2 ~ 8 hours; Roasting condition is: roasting 1 ~ 5 hour at 400 ~ 700 DEG C.
Hydrocracking catalyst composition described in 21. 1 kinds of claims 1 or 2 is applied to the hydrocracking reaction process of flexible production industrial chemicals or intermediate oil.
22. according to the application described in claim 21, it is characterized in that operating condition is: reaction pressure 6.0 ~ 20.0MPa, 350 ~ 420 DEG C of reaction temperatures, feed volume air speed 0.1 ~ 2.0h-1, hydrogen to oil volume ratio is 500:1 ~ 2000:1.
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