CN105618113A - Method for preparing hydro-cracking catalyst composition - Google Patents
Method for preparing hydro-cracking catalyst composition Download PDFInfo
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Abstract
The invention discloses a method for preparing a hydro-cracking catalyst composition. The method comprises the following steps: 1, modified Y type 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 the modified Y type molecular sieve is obtained; and 2, the carrier obtained in the step 1 is impregnated with an impregnation solution containing active metals; after impregnation, the carrier is dried and the dried carrier is roasted, such that the hydro-cracking catalyst is obtained. A preparation method of the modified Y type molecular sieve comprises the following steps: NaY zeolite is adopted as raw powder; ammonium salt ion exchange, ammonium fluorosilicate dealumination and silicon reinsertion treatment, hydrothermal treatment, and aluminum salt solution treatment are carried out; impregnation is carried out in organic solvents; and fast drying, alkali desilication, drying and roasting treatments are carried out, such that the modified Y type molecular sieve is obtained. The hydro-cracking catalyst composition provided by the invention has good temperature increase sensitivity and operation flexibility. The composition can be widely used in hydro-cracking reaction processes.
Description
Technical field
The present invention relates to a kind of method preparing hydrocracking catalyst composition.
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, and cracking function is then provided by molecular sieve. at China's hydrocracking technology owing to its raw material adapts to strong, the feature that product adjustability is big, 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, market to heavy naphtha in great demand time then can fecund heavy naphtha, therefore, air speed on hydrocracking unit, in the relatively-stationary situation of the operating conditions such as pressure, the temperature raising sensitivity of hydrocracking catalyst is particularly important for device flexible operating, in addition, for setter, owing to hydrogen supply is relatively fixed, therefore, device temperature raising process should reduce the fluctuation of hydrogen gas consumption as much as possible thus being more beneficial for device even running while 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, inside and outside conventional processing method molecular sieve, Distribution of silicon and aluminium is uniform, acid centre is uniformly distributed, and when reducing Y molecular sieve silica alumina ratio, improves Y molecular sieve acid site density, temperature raising sensitivity is improved, but meanwhile, second pyrolysis is also significantly increased, hydrogen consumption is substantially improved. And when Y molecular sieve carries out advanced treating, when acid density is too low, catalyst temperature raising sensitivity is poor again.
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 temperature raising sensitivity prepared is higher, but simultaneously, temperature raising process second pyrolysis substantially increases, hydrogen consumption is notable to rise, and is unfavorable for industrial hydrocracking unit temperature raising process apparatus even running.
CN200810012212.6 discloses a kind of carrier of hydrocracking catalyst and preparation method thereof, and hydrocracking catalyst temperature raising sensitivity prepared by this invention is poor.
Summary of the invention
For the deficiencies in the prior art, the present invention puies forward a kind of method preparing hydrocracking catalyst composition, hydrocracking catalyst prepared by the inventive method has good temperature raising sensitivity and operating flexibility, has broad application prospects in hydrocracking reaction process.
The method preparing hydrocracking catalyst composition 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; Modified Y molecular sieve mass percent in silica-alumina supports is 15% ~ 90%, it is preferable that 30% ~ 70%.
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; Described active metal group VIII in the periodic table of elements and/or one or more in vib metals element; 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;
The preparation method of wherein said 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) carries out dealumination complement silicon process; (3) Y molecular sieve after step (2) being processed carries out hydrothermal treatment consists; (4) the Y molecular sieve aluminum salt solution after step (3) hydrothermal treatment consists is processed; (5) the Y molecular sieve dried to step (4) gained; (6) Y molecular sieve that step (5) obtains impregnates in organic solvent, then rapid draing; (7) molecular sieve that step (6) obtains is carried out alkali desiliconization process; (8) step (7) Y molecular sieve after alkali desiliconization processes through filtering, dry, calcination process 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%; 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.
Dealumination complement silicon described in step (2) processes as method well known to those skilled in the art, conventional ammonium fluosilicate dealumination complement silicon method can be adopted, general process is: being added water by the Y molecular sieve that step (1) obtains is made into the water sample mixing of liquid-solid mass ratio 3:1 ~ 6:1, then, adding concentration is 0.8 ~ 2.0mol/L ammonium fluosilicate aqueous solution, processing 1 ~ 4 hour in 70 ~ 120 DEG C, wherein ammonium fluosilicate solution addition needs to deposit ammonium fluosilicate 9 ~ 30g meter according to every 100g molecular sieve; Other are such as SiCl4The methods such as gas phase dealumination complement silicon are also suitable.
When step (3) 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 (4) is one or more in aluminum chloride, aluminum sulfate or aluminum nitrate, and 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.
Dried process described in step (5): 90 ~ 300 DEG C dry 2 ~ 10 hours.
One or more in alkane, petroleum ether, carbon tetrachloride, benzene, toluene, ethylbenzene, dimethylbenzene, ethylbenzene of organic solvent described in step (6), impregnation method adopts supersaturation dipping, and dip time is 1 ~ 5 hour; 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.
The aqueous solution that alkali liquor is sodium hydroxide or potassium hydroxide that alkali desiliconization processing procedure described in step (7) uses, wherein the concentration of alkali liquor is 0.1 ~ 2%. Base extraction temperature 50 ~ 100 DEG C, the process time is 0.5 ~ 4 hour, and the liquid-solid mass ratio of alkali liquor/molecular sieve is 5:1 ~ 10:1.
Step (8) described baking temperature is 90 DEG C ~ 120 DEG C, and drying time is 2 ~ 4 hours; Sintering temperature is 400 ~ 600 DEG C, and roasting time is 2 ~ 4 hours.
Hydrocracking catalyst composition 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 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; 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 10 ~ 90, preferably 20 ~ 60, surface layer silica alumina ratio 6 ~ 30, preferably 8 ~ 20, surface layer silica alumina ratio is lower than body phase silica alumina ratio 5 ~ 40, 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 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 650 ~ 900m2/ g; Pore volume 0.30 ~ 0.50ml/g; Meleic acid content 0.3 ~ 1.0mmol/g, it is preferable that 0.4 ~ 0.8mmol/g; Relative crystallinity 90% ~ 130%.
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, 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 by being modified process to Y molecular sieve, 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, therefore, in follow-up alkali liquor desiliconization processing procedure, mainly carry out on the outer surface, after alkali-treated, the dry organic solvent removed within molecular sieve. The inventive method by optionally carrying out alkali desiliconization process to Y molecular sieve outer surface, while retaining the internal 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 prepared compared to conventional method modified molecular screen can significantly improve the temperature raising sensitivity of catalyst, operating flexibility, and under same conversion, device liquid receipts and chemical hydrogen consumption all make moderate progress.
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) molecular sieve of step (1) gained mixes with distilled water according to liquid-solid ratio 5:1, then, adds the ammonium fluosilicate solution 200ml that concentration is 1.0mol/L, and 75 DEG C process 2 hours;
(3) Y molecular sieve 540 DEG C that step (2) is obtained, hydrothermal treatment consists 1.5 hours under 0.1MPa;
(4) step (3) gained molecular sieve mixes with distilled water stirring according to liquid-solid ratio 7:1, 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.
(5) 150 DEG C of dry 4h of step (4) gained molecular sieve;
(6) molecular sieve 2 hours of normal heptane solvent soaking step (5) gained is taken;
(7) molecular sieve after step (6) process dries 10 minutes in 130 DEG C;
(8) Y molecular sieve of step (7) gained mixes according to the sodium hydroxide solution of liquid-solid ratio 5:1 and 0.7%, and 90 DEG C process 2 hours;
(9) Y molecular sieve after step (8) alkali processes, 120 DEG C dry 2 hours, after 550 DEG C of roastings 2 hours, obtains modified Y molecular sieve, is numbered Y-1.
Y-1 molecular sieve transmission electron microscope EDAX results measures its outer surface to 100nm thickness, and the silica alumina ratio of surface layer is 13, and molecular sieve phase silica alumina ratio is 30. XRD analysis result shows that its lattice constant is 2.433nm, relative crystallinity 108%. Pore volume 0.37ml/g, specific surface area 805m2/ g, it is 0.64mmol/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-165g and 35g 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) molecular sieve of step (1) gained mixes with distilled water according to liquid-solid ratio 5:1, then, adds the ammonium fluosilicate solution 300ml that concentration is 1.3mol/L, and 90 DEG C process 2 hours;
(3) Y molecular sieve 550 DEG C that step (2) is obtained, hydrothermal treatment consists 2 hours under 0.1MPa;
(4) step (3) 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.
(5) 200 DEG C of dry 6h of step (4) gained molecular sieve;
(6) molecular sieve 3 hours of toluene solvant soaking step (5) gained is taken;
(7) dry 35 minutes of 160 DEG C of molecular sieve after step (6) process;
(8) molecular sieve of step (7) gained mixes according to the sodium hydroxide solution of liquid-solid ratio 6:1 and 1.3%, and 80 DEG C process 3 hours;
(9) Y molecular sieve after step (8) alkali 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-250g and 50g 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, and the silica alumina ratio of surface layer is 7.0, and molecular sieve phase silica alumina ratio is 42. XRD analysis result shows that its lattice constant is 2.427nm, relative crystallinity 101%. Pore volume 0.38ml/g, specific surface area 770m2/ g, it is 0.49mmol/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 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) molecular sieve of step (1) gained mixes with distilled water according to liquid-solid ratio 5:1, then, adds the ammonium fluosilicate solution 250ml that concentration is 1.0mol/L, and 95 DEG C process 2 hours;
(3) Y molecular sieve 530 DEG C that step (2) is obtained, hydrothermal treatment consists 1.5 hours under 0.1MPa;
(4) step (3) 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 1.5 hours in the process of stirring.
(5) 250 DEG C of dry 3h of molecular sieve after step (4) process;
(6) molecular sieve 4 hours of xylene solvent soaking step (5) gained is taken;
(7) dry 35 minutes of 200 DEG C of molecular sieve after step (6) process;
(8) molecular sieve of step (7) gained mixes according to the sodium hydroxide solution of liquid-solid ratio 6:1 and 1.2%, and 75 DEG C process 2 hours;
(9) Y molecular sieve after step (8) alkali 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-350g and 50g 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 200nm thickness, and the silica alumina ratio of surface layer is 8.5, and molecular sieve phase silica alumina ratio is 40. XRD analysis result shows that its lattice constant is 2.435nm, relative crystallinity 103%. Pore volume 0.39ml/g, specific surface area 805m2/ g, it is 0.51mmol/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 0.6mol/L, 80 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) molecular sieve of step (1) 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 1.5 hours;
(3) Y molecular sieve 550 DEG C that step (2) is obtained, hydrothermal treatment consists 1.0 hours under 0.1MPa;
(4) step (3) 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.
(5) molecular sieve after step (4) process dries 6 minutes in 150 DEG C;
(6) molecular sieve 2 hours of normal octane solvent soaking step (5) gained is taken;
(7) molecular sieve after step (6) process dries 12 minutes in 140 DEG C;
(8) Y molecular sieve of step (7) gained mixes according to the sodium hydroxide solution of liquid-solid ratio 5:1 and 0.6%, and 95 DEG C process 2 hours;
(9) Y molecular sieve after step (8) alkali processes, 120 DEG C dry 2 hours, after 550 DEG C of roastings 2 hours, obtains modified Y molecular sieve, is numbered Y-4.
Y-4 molecular sieve transmission electron microscope EDAX results measures its outer surface to 100nm thickness, and surface layer silica alumina ratio is 15, and molecular sieve phase silica alumina ratio is 29. XRD analysis result shows that its lattice constant is 2.438nm, relative crystallinity 105%. Pore volume 0.38ml/g, specific surface area 810m2/ g, it is 0.66mmol/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-465g and 35g 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 silica alumina ratio is 23. XRD analysis result shows that its lattice constant is 2.441nm, relative crystallinity 88%, pore volume 0.36ml/g, specific surface area 720m2/ g, meleic acid amount is 0.73mmol/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 silica alumina ratio is 32. XRD analysis result shows that its lattice constant is 2.426nm, relative crystallinity 92%, pore volume 0.39ml/g, specific surface area 690m2/ g, meleic acid amount is 0.55mmol/g.
Embodiment 5
In order to investigate embodiment 1 ~ 4 and comparative example 1 ~ 2 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 instead loads regular refiner catalyst, two instead load the hydrocracking catalyst prepared according to embodiment 1 ~ 4 and comparative example 1 ~ 2 method respectively, and evaluation result is listed in table 1 ~ table 5.
Table 1 raw oil character.
Table 2 appreciation condition.
Table 3 evaluation result.
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 comparative example 1 catalyst contrast test on evaluating apparatus to show, catalyst prepared by the inventive method is adopted to have better operating flexibility, in temperature raising process, product slates amplitude of variation is bigger, can switch and carry out fecund Petroleum and produce the operation of Petroleum both of which less, simultaneously, owing to the present invention adopts specific process modified Y molecular sieve, while improving the outside acid centre of molecular sieve, remain the high silica alumina ratio within molecular sieve, acid centre is less, the secondary cracking that temperature raising process causes significantly reduces, therefore, relative to comparative example 1 catalyst, embodiment 1 catalyst hydrogen consumption in temperature raising process increases and liquid receipts fall is less, it is more beneficial for the quiet run of device. the contrast test of embodiment 2 and comparative example 2 catalyst then shows, embodiment 2 catalyst makes embodiment 2 catalyst have better temperature raising sensitivity due to the acid site quantity that molecular sieve outer surface is higher, about 15 percentage points are improved more than 350 DEG C of fraction conversion ratios when reaction temperature is increased to the process of 380 DEG C from 372 DEG C, and comparative example 2 only improves 6 percentage points, comparing comparative example 2 catalyst, embodiment 2 catalyst shows bigger product slates motility. therefore, all in all catalyst of the present invention shows good temperature raising sensitivity, device operating flexibility and higher liquid yield.
Claims (18)
1. the method preparing hydrocracking catalyst composition, 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 the preparation method of the modified Y molecular sieve described in step one is as follows: (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) carries out ammonium fluosilicate dealumination complement silicon process; (3) Y molecular sieve after step (2) being processed carries out hydrothermal treatment consists; (4) the Y molecular sieve aluminum salt solution after step (3) hydrothermal treatment consists is processed; (5) the Y molecular sieve dried to step (4) gained; (6) Y molecular sieve that step (5) obtains impregnates in organic solvent, then rapid draing; (7) molecular sieve that step (6) obtains is carried out alkali desiliconization process; (8) step (7) Y molecular sieve after alkali desiliconization processes through filtering, dry, calcination process obtain modified Y molecular sieve.
2. in accordance with the method for claim 1, it is characterised in that: 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.
3. in accordance with the method for claim 1, it is characterised in that: modified Y molecular sieve mass percent in silica-alumina supports is 15% ~ 90%.
4. in accordance with the method for claim 1, it is characterised in that: the group VIII in the periodic table of elements of the active metal described in step 2 and/or one or more in vib metals element; Group VIII active metal is Ni and/or Co, and vib active metal is W and/or Mo.
5. 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.
6. in accordance with the method for claim 1, it is characterized in that: in the preparation method of described modified Y molecular sieve, step (1) described Ammonium Salt Ionic exchange process 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, 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.
7. in accordance with the method for claim 1, it is characterized in that: in the preparation method of described modified Y molecular sieve, the ammonium fluosilicate dealumination complement silicon process described in step (2) is: being added water by the Y molecular sieve that step (1) obtains is made into the water sample mixing of liquid-solid mass ratio 3:1 ~ 6:1, being subsequently adding concentration is 0.8 ~ 2.0mol/L ammonium fluosilicate aqueous solution, processes 1 ~ 4 hour in 70 ~ 120 DEG C; Wherein ammonium fluosilicate solution addition needs to deposit ammonium fluosilicate 9 ~ 30g meter according to every 100g molecular sieve.
8. in accordance with the method for claim 1, it is characterised in that: in the preparation method of described modified Y molecular sieve, step (3) 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.
9. in accordance with the method for claim 1, it is characterized in that: in the preparation method of described modified Y molecular sieve, the aluminium salt used by aluminium salt processing procedure described in step (4) is one or more in 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.
10. in accordance with the method for claim 1, it is characterised in that: dried process described in step (5) in the preparation method of described modified Y molecular sieve: 90 ~ 300 DEG C dry 2 ~ 10 hours.
11. in accordance with the method for claim 1, it is characterised in that: in the preparation method of described modified Y molecular sieve, the organic solvent described in step (6) is selected from one or more in alkane, petroleum ether, carbon tetrachloride, benzene, toluene, ethylbenzene, dimethylbenzene or ethylbenzene.
12. the method described in claim 1 or 11, it is characterised in that: in the preparation method of described modified Y molecular sieve, step (6) impregnation method adopts supersaturation dipping, and dip time is 1 ~ 5 hour.
13. in accordance with the method for claim 1, it is characterised in that: in the preparation method of described modified Y molecular sieve, the baking temperature described in step (6) is 50 ~ 300 DEG C, and drying time is 1 ~ 60 minute.
14. in accordance with the method for claim 13, it is characterised in that: the baking temperature described in step (6) is higher than the boiling point of organic solvent.
15. in accordance with the method for claim 1, it is characterized in that: the aqueous solution that alkali liquor is sodium hydroxide or potassium hydroxide that in the preparation method of described modified Y molecular sieve, the alkali desiliconization processing procedure described in step (7) uses, wherein the concentration of alkali liquor is 0.1 ~ 2%; Base extraction temperature 50 ~ 100 DEG C, the process time is 0.5 ~ 4 hour, and the liquid-solid mass ratio of alkali liquor/molecular sieve is 5:1 ~ 10:1.
16. in accordance with the method for claim 1, it is characterised in that: in the preparation method of described modified Y molecular sieve, step (8) described baking temperature is 90 DEG C ~ 120 DEG C, and drying time is 2 ~ 4 hours; Sintering temperature is 400 ~ 600 DEG C, roasting time 2 ~ 4 hours.
17. hydrocracking catalyst composition prepared by the method described in claim 1 ~ 11 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 active metal is selected from the group VIII in the periodic table of elements and/or vib metals element; 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 10 ~ 90, surface layer silica alumina ratio 6 ~ 30, and surface layer silica alumina ratio is lower than body phase silica alumina ratio 5 ~ 40, and wherein said surface layer refers to the molecular sieve outer surface thickness range to internal 10 ~ 200nm, and surface layer is primary in Y molecular sieve crystal grain before modified; Sodium oxide weight/mass percentage composition is less than 1.0%; Modified Y molecular sieve specific surface area 650 ~ 900m2/ g; Pore volume 0.30 ~ 0.50ml/g; Meleic acid content 0.3 ~ 1.0mmol/g; Relative crystallinity 90% ~ 130%.
18. hydrocracking catalyst composition prepared by the method described in claim 1 ~ 11 any claim be applied to produce flexibly industrial chemicals or intermediate oil etc. different hydrocracking reaction processes, 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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