CN1164719C - Cracking catalyst with hydrogen being added for noble metal and its prepn. method - Google Patents
Cracking catalyst with hydrogen being added for noble metal and its prepn. method Download PDFInfo
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- CN1164719C CN1164719C CNB011333685A CN01133368A CN1164719C CN 1164719 C CN1164719 C CN 1164719C CN B011333685 A CNB011333685 A CN B011333685A CN 01133368 A CN01133368 A CN 01133368A CN 1164719 C CN1164719 C CN 1164719C
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Abstract
The present invention discloses a catalyst for the hydrogenation cracking of noble metal and a preparation method thereof. The catalyst takes aluminum oxide made from modified Y zeolite as a carrier and takes VIII group of noble metals in the periodic table as active constituents for hydrogenation. A unit cell parameter of the modified Y zeolite is from 2.420 to 2.450 nm, the ratio of SiO2 to Al2O3 is 10 to 100, the crystallinity is greater than 95%, the specific surface area is from 700 to 90 0m<2>/g, the pore volume is from 0.35 to 0.55 ml/g, the infrared acidity is from 0.2 to 2.0 m mol/g, and the weight content of Na2O is less than 0.20%. The modified Y zeolite is processed by secondary water-heating treatment and acid treatment, so the catalyst of the present invention has the characteristics of good thermal stability, good medium oil selectivity, high sulfur resistance performance, high nitrogen resistance ability, etc. The catalyst can be used for the hydrogenation cracking, hydrogenation treatment and hydrogenation modification of distillate oil, and is especially suitable for the deep hydrogenation cracking reaction of heavy distillate oil.
Description
1, technical field
The invention belongs to the hydrocracking technology in the oil refining process, relate to a kind of loaded noble metal catalyst that is used for distillate hydrocracking and preparation method thereof.
2, background technology
Hydrocracking is meant stock oil in the presence of certain temperature and pressure, hydrogen and catalyzer, carries out hydrogenation, desulfurization, denitrogenation, the carbon atom skeleton rearranges and reactions such as cracking, thereby high-boiling hydrocarbons is changed into the process of small molecules lower boiling purpose product.
Hydrocracking catalyst is generally dual-function catalyst.Catalyzer cracking function is provided by acid carrier, and acid carrier can be unformed aluminum oxide (Al
2O
3), the oxidation sial is (as SiO
2-Al
2O
3) or crystalline molecular sieve (being generally modified Y zeolite), or their combination; Hydrogenation-dehydrogenation functionality is then provided by metal component, mainly is VI family and VIII family metal, reaches precious metals pt, Pd as base metal Mo, W, Co, Ni etc.Usually precious metal has higher hydrogenation activity than base metal, is particularly useful for handling hydrocracking tail oil and the intermediate oil process is produced in the heavy distillate hydrocracking to greatest extent.
U.S. Pat 6174430 has been introduced a kind of Nobel metal hydrogen cracking catalyst, has higher naphtha selective.Catalyzer consists of the USY zeolite of 70w%～90w%, the aluminum oxide of 10w%～30w% and the precious metal of 0.5w%～1.0w%, wherein USY prepare zeolite method is: the NaY zeolite is carried out ion-exchange make sodium oxide content drop to 3w%, carry out the exchange of hydrothermal treatment consists and ammonia more under certain condition, make Na
2O content is reduced to below the 0.2w%.This catalyzer is used for the heavy distillate hydrocracking process, and the product of production is mainly based on petroleum naphtha and rocket engine fuel, and wherein the selectivity of petroleum naphtha is about 32w%, and the selectivity of rocket engine fuel is about 40w%.
U.S. Pat 5366615 has been introduced a kind of Nobel metal hydrogen cracking catalyst of the USY of containing zeolite, is intended to improve the selectivity that rocket engine fuel is produced in the heavy distillate hydrocracking.The characteristics of this catalyzer are used USY zeolite SiO
2/ Al
2O
3(mol ratio) is 27～33, has certain anti-nitrogen, also contains a certain amount of aluminum oxide in the carrier.
U.S. Pat 4897178 has been introduced a kind of light oil type Nobel metal hydrogen cracking catalyst that is used for.Reactive metal is one or more in VI family and the VIII family in the periodic table of elements, the preparation method of its carrier handles the LZ-210 molecular sieve with silicofluoric acid (ammonia), be used for dealuminzation, and control pH value is between 5～7, and then carry out hydrothermal treatment consists, carry out NH at last again
4 +Exchange, make the SiO of product
2/ Al
2O
3Mol ratio 〉=9, a
0＜24.55 * 10
-10M.
The common drawback that above-mentioned patent exists is that used USY zeolite does not all carry out secondary hydrothermal treatment consists and acid treatment in preparation process, thereby the silica alumina ratio of zeolite is on the low side, acidity is bigger than normal, and when causing this catalyzer to be used for the heavy distillate hydrocracking process, the middle distillates oil selectivity of reaction product is lower.
3, summary of the invention
At above-mentioned the deficiencies in the prior art, the purpose of this invention is to provide with the modified Y zeolite is load-type nobel metal hydrocracking catalyst of carrier and preparation method thereof, further improves the selectivity of hydrocracking process reactive behavior and intermediate oil.
The carrier of noble metal catalyst of the present invention is made up of modified zeolite of Y-type and aluminum oxide, the hydrogenation activity component be selected from the periodic table of elements group VIII noble metals component one or more, weight percent with catalyzer is a benchmark, each components contents is: described modified zeolite of Y-type accounts for 18.2%～38.4%, described aluminum oxide accounts for 60.7%～80.9%, noble metal component 0.1%～2.0%, preferably 0.3%～1.2%.
The characteristics of above-mentioned noble metal catalyst are that the character of used modified zeolite of Y-type is: unit cell parameters 2.420～2.450nm, SiO
2/ Al
2O
3Value is 10～100 (SiO of the present invention
2/ Al
2O
3Be meant silica alumina ratio), degree of crystallinity is greater than 95%, specific surface area 700～900m
2/ g, pore volume 0.35～0.55ml/g, infrared acidity 0.2～2.0mmol/g, Na
2The O weight content is less than 0.20%.The character of described modified zeolite of Y-type is preferably: unit cell parameters 2.430～2.445nm, SiO
2/ Al
2O
3Value is 15～90, and degree of crystallinity is greater than 97%, specific surface area 750～850m
2/ g, pore volume 0.40～0.50ml/g.Infrared acidity 0.2～1.0mmol/g, Na
2The O weight content is less than 0.15%.
The specific surface area of catalyzer of the present invention is 300～400m
2/ g, pore volume are 0.50～0.65ml/g.
Described precious metal better is to be selected from one or more of Pt, Pd, Rh, Ir, preferably is selected among Pt, the Pd one or both.
Preparation of catalysts method of the present invention is, above-mentioned modified Y zeolite is mixed with aluminum oxide powder, after moulding, drying, roasting, make carrier, contact with one or more VIII family precious metal aqueous solution again, noble metal component is loaded on the described carrier, more after filtration, dry, roasting, make catalyzer of the present invention.
The preparation process of modified Y zeolite of the present invention can be: earlier NaY zeolite raw material is carried out the ammonium exchange, remove Na
+Ion carries out hydrothermal treatment consists and acid treatment then, carries out secondary hydrothermal treatment consists and acid treatment afterwards again, and the product that obtains after filtration, after the washing, drying, make modified Y zeolite of the present invention.
Described modified zeolite of Y-type can be directly mixed with aluminum oxide powder, and use sour peptization; Also can make tackiness agent with behind aluminum oxide powder and the sour peptization, mixed with modified Y zeolite again.Used acid can be mineral acid, also can be organic acid.Comprise hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid etc.The consumption of acid is with H in the acid
+Al in ion and the aluminum oxide powder
2O
3Mol ratio be 0.01～0.2 to add, used acid concentration is 0.1～1mol/l.
In described carrier moulding process, for the ease of moulding, the general material that needs to add an amount of water and help moulding, and mix.These materials comprise one or more of sesbania powder, citric acid, oxalic acid, Mierocrystalline cellulose, starch, polymeric surface active agent etc.
Material after the moulding needs 100～130 ℃ of dryings 2～5 hours, and carrier is made in 350～750 ℃ of roastings 2～4 hours.The profile of carrier can be cylindrical bar, sheet, spherical, special-shaped bar (cloverleaf pattern, Herba Galii Bungei shape) or other shape, preferably cylindrical bar or trifolium, Herba Galii Bungei shape bar.Its particle diameter is generally 0.5～3mm, preferably 1～2mm.
The carrier that aforesaid method is made contacts with the aqueous solution of VIII family precious metal, adopts ion exchange method or pickling process to introduce metal ion, preferably adopts ion exchange method.The introducing process is carried out under usual conditions, promptly under normal temperature, the normal pressure.VIII family precious metal comprises Pt, Pd, Rh, Ir etc., preferably Pt, Pd.Can be a kind of, also can be multiple.Strength of solution (by the metal quality) is 0.1～2.0w%, preferably 0.3～1.5w%.Adopt in the ion exchange method solutions employed precious metal and OH-, NH
3-group forms complex cation and exists, and allows other positively charged ion and exists, as H
+Ion, general H
+With the mol ratio of precious metal ion be 1: 1～50: 1.Negatively charged ion can be Cl
-, NO
3 -, SO
4 2-Deng; Adopt the pickling process solutions employed, precious metal can with Cl
-, NO
3 -, SO
4 2-Ion forms complexing ion, and positively charged ion is H
+, also can there be the acid of other positively charged ion and other type to exist, the acid here comprises various mineral acids and organic acid.
The aqueous solution of above-mentioned VIII family precious metal and the duration of contact of carrier are 2～10 hours, preferably 3～7 hours.Solidliquid mixture dried in the shade under room temperature 4～10 hours after filtering.And it is following dry 1～4 hour at 110～130 ℃.Then under 350～700 ℃, preferably under 400～600 ℃, loaded noble metal catalyst is made in roasting 2～5 hours.
The concrete preparation method of modified Y zeolite of the present invention can carry out according to following steps:
A. in the NaY zeolite, add ammonium salt solution, under 30～100 ℃, exchange 0.5～5 hour, and constantly stir.In the described ammonium salt solution H can be arranged
+Ion also can have other metallic cation to exist.H
+Ion is provided by acid, metallic cation can be Ni, Mo, Co, Ca, Fe ionic one or more.Used ammonium salt can be the inorganic salt or the organic salt of ammonium, as ammonium chloride, ammonium sulfate, ammonium nitrate, volatile salt, ammonium oxalate etc.NH
4 +Ionic concn is 0.5～5mol/l.Solution usage and zeolite weight ratio are 1～10.The character of described NaY zeolite generally is unit cell parameters 2.462～2.475nm, degree of crystallinity 90～105%, SiO
2/ Al
2O
3Be about 4～6, Na
2The O weight content is about 9%～11%.
B. the product that step a is obtained after filtration, after the washing, drying, put into the hydrothermal treatment consists stove and carry out steam-treated.Treatment temp is 250～850 ℃, and water partial pressure is 0.05～1.00MPa, and the treatment time is 0.5～10 hour, preferably 0.5～5 hour.
C. the product that step b is obtained places and contains H
+Carry out acid treatment in the ionic aqueous solution, in this solution NH can be arranged
4 +Positively charged ion exists, and also can have other metallic cation to exist.H wherein
+Ion is provided by acid, example hydrochloric acid, nitric acid, sulfuric acid etc.Used NH
4 +Can provide by the inorganic salt or the organic salt of ammonium, as ammonium chloride, ammonium sulfate, ammonium nitrate, volatile salt, ammonium oxalate etc., and metallic cation can be Ni, Mo, Co, Ca, Fe ionic one or more.The pH value of solution value should be 1～6, and preferably 2～5, the acid treatment temperature is for being generally 30～100 ℃, and the treatment time was generally 0.2～5 hour, preferably 0.5～3 hour, filtered after the processing.This step repeats 2～5 times.If add NH in the solution
4 +, it is 0.5～5mol/l that its ionic concn in solution is generally.
D. the product that step c is obtained is put into the hydrothermal treatment consists stove and is carried out steam-treated after washing, drying.Treatment temp is 250～850 ℃, and water partial pressure is 0.05～1.00MPa, and the treatment time is 0.5～10 hour, preferably 0.5～5 hour.
E. will be carried out acid treatment by the product that steps d obtains and filter 2～5 times, treatment process is with step 3.
F. the product that obtains of step e in 100～130 ℃ dry 1～3 hour down, make modified zeolite of Y-type.
Compared with prior art, the present invention has following beneficial effect:
Catalyzer of the present invention is owing to adopt modified zeolite of Y-type to do carrier, and this zeolite has high-crystallinity, characteristics such as low unit cell parameters, bigger serface and ideal acidity, thereby make the precious metal that is supported have very high anti-sulphur, simultaneously because through secondary hydrothermal treatment consists and acid treatment, the y-type zeolite of gained has Heat stability is good, middle distillates oil selectivity and reaches the high characteristics of anti-nitrogen ability well.Catalyzer of the present invention can be used for hydrocracking, hydrotreatment and the hydro-upgrading of distillate, is specially adapted to the overhydrocracking reaction of heavy distillate, and has certain anti-sulphur.
4, embodiment
Example 1
A. use NaY zeolite 100g (unit cell parameters 2.472nm, degree of crystallinity 100%, the Na of Wenzhou catalyst plant production
2O content 10w%, SiO
2/ Al
2O
3=5.1, butt 100%) is put in and is dissolved with 160gNH
4NO
3In 1 liter of the aqueous solution of 3ml concentrated nitric acid (65%), be warming up to 80 ℃, stir 1 hour after-filtration, washing, drying.
B. place in the sealed furnace after, handled 2 hours down for 620 ℃ in water partial pressure 0.2MPa, temperature.
C. product is put into the described 1 premium on currency solution of a, stirs 1 hour after-filtration down at 80 ℃, repeats once.
D. behind repeating step b, the c, product was made modified zeolite of Y-type in 120 ℃ times dry 2 hours.
E. resulting modified zeolite of Y-type is produced SB aluminum oxide powder (Al with Germany
2O
3Contents on dry basis 75w%) 300g mixes, and adds 7ml concentrated nitric acid (65%) and an amount of water, and adding 3g citric acid and 3g sesbania powder also mixes, on banded extruder, be extruded into Φ 1.5mm cylindrical bar, in 120 ℃ dry 3 hours down, carrier is made in 550 ℃ of following roastings 4 hours.
F. above-mentioned carrier is immersed the H of 500ml
2PdCl
4In the aqueous solution 4 hours, contain Pd 2.5g in the solution.Soak the dried solution of back filter, room temperature was dried in the shade 6 hours, and in 120 ℃ dry 2 hours down, catalyst A is made in 500 ℃ of following roastings 3 hours.
Example 2
A. the NaY zeolite 100g (with embodiment 1) that produces with Wenzhou catalyst plant is put in and is dissolved with 160g
NH
4NO
31 premium on currency solution in, be warming up to 80 ℃, stir 1 hour after-filtration, washing, drying.
B. place in the sealed furnace after, handled 2 hours down for 600 ℃ in water partial pressure 0.15MPa, temperature.
The c.b product is put into the described 1 premium on currency solution of a, stirs 1 hour after-filtration down at 80 ℃, and repeats once.
D. repeating step b, carry out the hydrothermal treatment consists second time after, product is put into the 1 premium on currency solution that is dissolved with 25ml concentrated nitric acid (65%), is warming up to 80 ℃, stirs 1 hour after-filtration, washing, drying, in 120 ℃ of dryings 2 hours, makes modified zeolite of Y-type.
E. resulting modified zeolite of Y-type is produced SB aluminum oxide powder (Al with Germany
2O
3Contents on dry basis 75w%) 350g mixes, and adds 7ml concentrated nitric acid (1.4g/ml, 65%) and an amount of water, and 3g citric acid and 3g sesbania powder and mix, on banded extruder, be extruded into Φ 1.5mm cylindrical bar, in 120 ℃ dry 3 hours down, carrier is made in 550 ℃ of following roastings 4 hours.
F. with resulting carrier, make catalyst B according to the method for f step among the embodiment 1.
Example 3
A. use NaY zeolite 100g (unit cell parameters 2.472nm, degree of crystallinity 100%, the Na of Wenzhou catalyst plant production
2O content 10w%, SiO
2/ Al
2O
3=5.1, butt 100%) is put in and is dissolved with 160gNH
4NO
3In 1 liter of the aqueous solution of 3ml concentrated nitric acid (1.4g/ml, 65%), be warming up to 80 ℃, stir 1 hour after-filtration, washing, drying.
The b.a product places in the sealed furnace, and at water partial pressure 0.3Mpa, temperature was handled 2 hours down for 650 ℃.
The c.b product is put into the described 1 premium on currency solution of a, stirs 1 hour after-filtration down at 80 ℃, repeats once.
D. repeating step b, carry out the hydrothermal treatment consists second time after, product is put into the 1 premium on currency solution that is dissolved with 40ml concentrated nitric acid (65%), is warming up to 80 ℃, stirs 1 hour after-filtration, washing, drying, in 120 ℃ of dryings 2 hours, makes modified zeolite of Y-type.
E. resulting modified zeolite of Y-type is produced SB aluminum oxide powder (Al with Germany
2O
3Contents on dry basis 75w%) 150g mixes, and adds 4ml concentrated nitric acid (65%) and an amount of water, and 1.5g citric acid and 1.5g sesbania powder and mix, on banded extruder, be extruded into Φ 1.5mm cylindrical bar, in 120 ℃ dry 3 hours down, carrier is made in 500 ℃ of following roastings 4 hours.
F. above-mentioned carrier is immersed the Pd (NH of 250ml
3)
4Cl
2Carry out ion-exchange 4 hours in the aqueous solution, contain Pd 1.3g in the solution.Soak the dried solution of back filter, room temperature was dried in the shade 6 hours, and in 120 ℃ dry 2 hours down, catalyzer C is made in 500 ℃ of following roastings 3 hours.
Embodiment 4
A. the NaY zeolite 100g that produces with Wenzhou catalyst plant is put in and is dissolved with 160gNH
4NO
3In 1 liter of the aqueous solution of 3ml concentrated nitric acid (1.4g/ml, 65%), be warming up to 80 ℃, stir 1 hour after-filtration, washing, drying.
B. place in the sealed furnace after, handled 2 hours down for 620 ℃ in water partial pressure 0.2MPa, temperature.
The c.b product is put into the described 1 premium on currency solution of a, stirs 1 hour after-filtration down at 80 ℃, repeats once.
D. behind repeating step b, the c, product was made modified zeolite of Y-type in 120 ℃ times dry 2 hours.
C. resulting modified zeolite of Y-type being produced SB aluminum oxide powder 250g with Germany mixes, and adding 5ml concentrated nitric acid (1.4g/ml, 65%), 3g citric acid, 3g sesbania powder and an amount of water, and mix, on banded extruder, be extruded into Φ 1.5mm cylindrical bar, in 120 ℃ dry 3 hours down, carrier is made in 550 ℃ of following roastings 4 hours.
F. above-mentioned carrier is immersed the H of 400ml
2PdCl
4With H
2PtCl
4Mixed aqueous solution in, flooded 4 hours, contain Pd 1.6g in the solution, containing Pt is 0.4g.Soak the dried solution of back filter, room temperature was dried in the shade 6 hours, and in 120 ℃ dry 2 hours down, catalyzer D is made in 500 ℃ of following roastings 3 hours.
Example 5
A. the NaY zeolite 100g that produces with Wenzhou catalyst plant is put in and is dissolved with 160gNH
4NO
3In 1 liter of the aqueous solution of 3ml concentrated nitric acid (65%), be warming up to 80 ℃, stir 1 hour after-filtration, washing, drying.The product that step 1 is obtained after filtration, after the washing, drying, put into the hydrothermal treatment consists stove and carry out steam-treated.Treatment temp is 250～850 ℃, and water partial pressure is 0.05～1.00MPa, and the treatment time is 0.5～10 hour, preferably 0.5～5 hour.
The b.a product places in the sealed furnace, and at water partial pressure 0.3Mpa, temperature was handled 2 hours down for 650 ℃.
The c.b product is put into the described 1 premium on currency solution of a, stirs 1 hour after-filtration down at 80 ℃, repeats once.
D. repeating step b, carry out the hydrothermal treatment consists second time after, product is put into the 1 premium on currency solution that is dissolved with 40ml concentrated nitric acid (65%), is warming up to 80 ℃, stirs 1 hour after-filtration, washing, drying, in 120 ℃ of dryings 2 hours, makes modified zeolite of Y-type.
E. resulting modified zeolite of Y-type being produced SB aluminum oxide powder 150g with Germany mixes, and adding 4ml concentrated nitric acid (65%) and an amount of water, and 1.5g citric acid and 1.5g sesbania powder and mix, on banded extruder, be extruded into Φ 1.5mm cylindrical bar, drying is 3 hours under 120 ℃, carrier is made in 500 ℃ of following roastings 4 hours.
F. above-mentioned carrier is immersed the H of 300ml
2PtCl
4Dipping is 4 hours in the aqueous solution, contains Pt2g in the solution.Soak the dried solution of back filter, room temperature was dried in the shade 6 hours, and in 120 ℃ dry 2 hours down, catalyzer E is made in 500 ℃ of following roastings 3 hours.
The character of table 1 catalyst A～E of the present invention and used molecular sieve thereof
A B C D E
Molecular sieve character
Degree of crystallinity, % 96 98 99 96 99
a
0，nm 2.432 2.433 2.431 2.432 2.431
Specific surface area, m
2/ g 780 770 810 780 810
Pore volume, ml/g 0.475 0.468 0.512 0.475 0.512
SiO
2/Al
2O
3 20.2 10.3 53.2 20.2 53.2
Na
2O，m％ 0.03 0.02 0.02 0.03 0.02
The meleic acid amount, mmol/g 0.322 0.425 0.301 0.322 0.301
Catalyzer is formed
Molecular sieve, w% 21.7 18.2 38.4 26.2 38.4
Aluminum oxide, w% 77.2 80.9 60.7 72.9 60.7
Pt，w％ - - - 0.14 0.78
Pd，w％ 0.77 0.82 0.79 0.70 -
Specific surface area, m
2/ g 315 307 322 337 318
Pore volume, ml/g 0.602 0.583 0.594 0.613 0.592
Example 6
Adopting catalyzer of the present invention, is raw material with the hydrocracking tail oil, carries out the hydrocracking reaction of distillate.Raw materials used oil nature sees Table 2, and reaction result sees Table 3.The evaluation method of catalyst hydrogenation cracking activity comparative product when per pass conversion reaches 60w% distributes.The result shows that the middle distillates oil selectivity of catalyzer is all more than 75%, and temperature of reaction is not higher than 350 ℃.
Table 2 stock oil character
Index stock oil
Density, d
4 200.8426
Boiling range
10％ 372.2
50％ 415.1
90％ 495.9
EBP 554.6
Yield, w% 98.0
Viscosity, 50 ℃ 13.81
100℃ 4.294
Flash-point, ℃ (opening) 210
Acid number mgKOH/100ml 0.03
Refractive index η
701.4476
S，μg/g 10
N，μg/g 1.0
C/H atomic ratio 84.85/13.81
Table 4 evaluation result
Catalyzer numbering A B C D E
Reaction conditions
The hydrogen dividing potential drop, MPa 14.7 14.7 14.7 14.7 14.7
Volume space velocity, h
-11.0 1.0 1.0 1.0 1.0
Hydrogen-oil ratio (v) 1,500 1,500 1,500 1,500 1500
Temperature of reaction, ℃ 340 342 339 327 336
Product selectivity, w%
C
1～C
4 5.7 8.3 5.6 11.2 7.3
C
5～132℃ 14.3 16.5 12.7 18.5 13.6
132～282℃ 32.4 33.7 33.3 36.2 35.6
282～370℃ 46.6 41.5 48.4 34.1 43.5
Claims (9)
1, a kind of Nobel metal hydrogen cracking catalyst, its carrier is made up of modified zeolite of Y-type and aluminum oxide, the hydrogenation activity component be selected from the periodic table of elements group VIII noble metals component one or more, weight percent with catalyzer is a benchmark, each components contents is: described modified zeolite of Y-type accounts for 18.2%～38.4%, described aluminum oxide accounts for 60.7%～80.9%, noble metal component 0.1%～2.0%; The character that it is characterized in that described modified zeolite of Y-type is: unit cell parameters 2.420～2.450nm, SiO
2/ Al
2O
3Value is 10～100, and degree of crystallinity is greater than 95%, specific surface area 700～900m
2/ g, pore volume 0.35～0.55ml/g, infrared acidity 0.2～2.0mmol/g, Na
2The O weight content is less than 0.20%.
2,, it is characterized in that the character of described modified zeolite of Y-type is: unit cell parameters 2.430～2.445nm, SiO according to the described Nobel metal hydrogen cracking catalyst of claim 1
2/ Al
2O
3Value is 15～90, and degree of crystallinity is greater than 97%, specific surface area 750～850m
2/ g, pore volume 0.40～0.50ml/g, infrared acidity 0.2～1.0mmol/g, Na
2The O weight content is less than 0.15%.
3, according to the described Nobel metal hydrogen cracking catalyst of claim 1, the specific surface area that it is characterized in that described catalyzer is 300～400m
2/ g, pore volume are 0.50～0.65ml/g.
4,, it is characterized in that described precious metal is to be selected from one or more of Pt, Pd, Rh, Ir according to the described Nobel metal hydrogen cracking catalyst of claim 1.
5,, it is characterized in that described precious metal is to be selected among Pt, the Pd one or both according to the described Nobel metal hydrogen cracking catalyst of claim 1.
6, according to the described Nobel metal hydrogen cracking catalyst of claim 1, the content that it is characterized in that described noble metal component is 0.3%～1.2%.
7, the preparation method of the described Nobel metal hydrogen cracking catalyst of a kind of claim 1, comprise: described modified Y zeolite is mixed with aluminum oxide powder, after moulding, drying, roasting, make carrier, contact with the aqueous solution of described precious metal again, noble metal component is loaded on the described carrier, then after filtration, dry, roasting, make described catalyzer; The preparation process of described modified Y zeolite is: earlier NaY zeolite raw material is carried out the ammonium exchange, remove Na
+Ion carries out hydrothermal treatment consists and acid treatment then, carries out hydrothermal treatment consists and the acid treatment second time afterwards again, and the product that obtains after filtration, after the washing, drying, make described modified Y zeolite.
8,, it is characterized in that the concrete preparation method of described modified Y zeolite comprises according to the preparation method of the described Nobel metal hydrogen cracking catalyst of claim 7:
A. in the NaY zeolite, add ammonium salt solution, under 30～100 ℃, exchange 0.5～5 hour, and constantly stir NH
4 +Ionic concn is 0.5～5mol/l, and solution usage and zeolite weight ratio are 1～10;
B. the product that step a is obtained after filtration, after the washing, drying, put into the hydrothermal treatment consists stove and carry out steam-treated, treatment temp is 250～850 ℃, water partial pressure is 0.05～1.00MPa, the treatment time is 0.5～10 hour;
C. the product that step b is obtained places and contains H
+Carry out acid treatment in the ionic aqueous solution, the pH value of solution value should be 1～6, and the acid treatment temperature is 30～100 ℃, after 0.2～5 hour treatment time, filters, and repeats acid treatment then and filters 1～4 time;
D. the product that step c is obtained is put into the hydrothermal treatment consists stove and is carried out the secondary steam-treated after washing, drying, and treatment temp is 250～850 ℃, and water partial pressure is 0.05～1.00MPa, and the treatment time is 0.5～10 hour;
E. will be carried out acid treatment by the product that steps d obtains and filter 2～5 times, treatment process is with step c;
F. the product that obtains of step e in 100～130 ℃ dry 1～3 hour down, make described modified zeolite of Y-type.
9. according to the preparation method of the described Nobel metal hydrogen cracking catalyst of claim 8, it is characterized in that the character of described NaY zeolite is: unit cell parameters 2.462～2.475nm, degree of crystallinity 90～105%, SiO
2/ Al
2O
3Be 4～6, Na
2The O weight content is 9%～11%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011333685A CN1164719C (en) | 2001-10-30 | 2001-10-30 | Cracking catalyst with hydrogen being added for noble metal and its prepn. method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011333685A CN1164719C (en) | 2001-10-30 | 2001-10-30 | Cracking catalyst with hydrogen being added for noble metal and its prepn. method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1415704A CN1415704A (en) | 2003-05-07 |
| CN1164719C true CN1164719C (en) | 2004-09-01 |
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| CNB011333685A Expired - Lifetime CN1164719C (en) | 2001-10-30 | 2001-10-30 | Cracking catalyst with hydrogen being added for noble metal and its prepn. method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100448535C (en) * | 2005-10-19 | 2009-01-07 | 中国石油化工股份有限公司 | Hydrogenation catalyst containing faujasite, its preparation method and application |
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| CN100345632C (en) * | 2004-10-29 | 2007-10-31 | 中国石油化工股份有限公司 | Alumina carrier containing compound zeolite and preparation method thereof |
| CN100360235C (en) * | 2004-10-29 | 2008-01-09 | 中国石油化工股份有限公司 | Alumina supporter containing composite zeolite and its preparation method |
| CN100360221C (en) * | 2004-10-29 | 2008-01-09 | 中国石油化工股份有限公司 | Alumina supporter containing modified gamma zeolite and its preparation method |
| CN100421795C (en) * | 2005-10-19 | 2008-10-01 | 中国石油化工股份有限公司 | Catalytic cracking catalyst containing faujasite and preparation method thereof |
| CN100406383C (en) * | 2005-10-19 | 2008-07-30 | 中国石油化工股份有限公司 | Deep sealumination modified Y zeolite preparation method |
| CN100422081C (en) * | 2005-10-19 | 2008-10-01 | 中国石油化工股份有限公司 | Modified Y zeolite and its preparation method |
| CN101239324B (en) * | 2007-02-09 | 2010-05-19 | 中国石油化工股份有限公司 | High activity, high medium oil selective hydrocracking catalyst and preparation thereof |
| CN102500413B (en) * | 2011-10-25 | 2013-04-17 | 洛阳市科创石化科技开发有限公司 | N-butane hydroisomerization catalyst, and preparation method and application thereof |
| EP3533856B1 (en) * | 2016-11-30 | 2022-04-27 | China Petroleum & Chemical Corporation | Method for preparing hexadecahydropyrene |
| CN108239557A (en) * | 2018-01-22 | 2018-07-03 | 中海油天津化工研究设计院有限公司 | A kind of coking gasoline and diesel and heavy aromatics hybrid process method |
| CN111097482B (en) * | 2018-10-26 | 2021-08-06 | 中国石油化工股份有限公司 | Phosphorus-containing high-silicon molecular sieve and preparation method and application thereof |
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2001
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100448535C (en) * | 2005-10-19 | 2009-01-07 | 中国石油化工股份有限公司 | Hydrogenation catalyst containing faujasite, its preparation method and application |
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