CN102786064B - Hydrocracking catalyst carrier and preparation method thereof - Google Patents
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Abstract
The invention discloses a hydrocracking catalyst carrier and a preparation method of the hydrocracking catalyst carrier. The hydrocracking catalyst carrier is prepared by using modified Y zeolite, aluminum oxide and amorphous silicon-aluminum. The modified Y zeolite has the following physiochemical properties: the mole ratio of SiO2 to Al2O3 is 30-120; the lattice constant is 2.420-2.435nm; the relative crystallinity is more than or equal to 90%; the specific surface area is 750-850m<2>/g; the secondary pore with 1.7-10nm accounts for more than 50% of the total pore volume; the infrared acidity is 0.10-0.50mmol/g; the ion exchange capacity is less than or equal to 0.10%; and the water adsorption quantity is less than 5.0% in percentage by weight at 25 DEG C and P/P0 of 1.0. The preparation method of the catalyst carrier provided by the invention comprises the following steps: mechanically mixing the modified Y zeolite, aluminum oxide, amorphous silicon-aluminum and adhesive, grinding, extrusion-moulding, drying and calcining to obtain the catalyst carrier. The catalyst carrier prepared by using the modified (deeply dealuminated) Y zeolite as the acidic cracking component is suitable to be used as the hydrocracking catalyst for middle distillates oil.
Description
Technical field
The present invention relates to oil type hydrocracking catalyst carrier and preparation method thereof in one.
Background technology
Hydrocracking is a kind of conversion process that heavy raw oil carries out the reactions such as hydrogenation, desulfurization, denitrogenation, the rearrangement of hydrocarbon molecule recurring structure and cracking under HTHP faces hydrogen and catalyst exists.Hydrocracking technology be make full use of petroleum resources, improve petroleum product-quality, guarantee source green and environment-friendly, meet the effective means of energy market demand.The core of hydrocracking technology is hydrocracking catalyst.People are devoted to carry out modification with the physico-chemical property of modulation carrier to meet the needs of catalyst at hydrocracking process to acidic components or matrix always.
US4,894,142 disclose a kind of hydrocracking catalyst, this catalyst contains the Y zeolite of amorphous silicon aluminium and a kind of Low acid, the feature of this molecular sieve at high temperature processes raw molecule sieve, comprise 680 ~ 780 DEG C hydrothermal treatment consists or higher than the dry type heat treatment passing into inert gas of 700 DEG C.This catalyst is mainly used in the technical process of voluminous intermediate oil, but due to this molecular sieve acidity lower, cause the activity of catalyst lower, this just requires to improve hydrocracking reaction temperature, the thermal cracking trend of molecular sieve is made to strengthen and inhibit hydrogenation reaction, the middle distillates oil selectivity of catalyst is improved not obvious, product quality is also affected.
US5,190,903 disclose a kind of Low acid zeolite for voluminous intermediate oil hydrocracking catalyst, and object is the middle distillates oil selectivity improving catalyst, is characterized in have chosen NH
4the modified zeolite of Y-type of-TPD acidity <1.5mmol/g, SiO
2/ Al
2o
3mol ratio <6, lattice constant is at 2.420 ~ 2.440nm.The main preparation characteristic of this zeolite be to hydrothermal treatment consists after low sodalite carry out dry type roasting dehydroxylation, dehydroxylation temperature is higher than 426 DEG C, with a kind of VGO of hydrocracking catalyst process that this zeolite is prepared as acidic cleavage component, conversion rate control is 85% time, reaction temperature is up to 405 ~ 425 DEG C, middle distillates oil selectivity only has 55 ~ 63%, and the middle distillates oil selectivity of catalyst improves not obvious.
CN200710012769.5 relates to a kind of carrier of hydrocracking catalyst and preparation method thereof, and this carrier is containing a kind of Modified Zeolite Y.This modified molecular screen is with NH
4naY molecular sieve is raw material, and with ammonium hexafluorosilicate liquid phase dealumination complement silicon, the molecular sieve obtained, through hydrothermal treatment consists, finally uses aluminium salt and inorganic acid or the process of organic acid mixed aqueous solution.The silica alumina ratio of this modified molecular screen up to 30 ~ 100, infrared acidity 0.3 ~ 0.8mmol/g, and B acid/L acid is greater than 8.0.Be applied to hydrocracking process process after this catalyst carrier carried metal component, reactivity is higher, and middle distillates oil selectivity is undesirable, and produces fluorine-containing sewage when producing modified Y molecular sieve, to environment, is unfavorable for environmental protection.
Summary of the invention
The object of this invention is to provide oil type hydrocracking catalyst carrier and preparation method thereof in one, hydrogenation metal component in described catalyst carrier load is applied to hydrocracking heavy oil technical process, there is higher middle distillates oil selectivity and good lytic activity.
A kind of modified Y zeolite provided by the present invention, has following physicochemical property:
SiO
2/ Al
2o
3mol ratio is 30 ~ 120; Lattice constant is 2.420 ~ 2.435nm; Relative crystallinity>=90%; Specific area is 750 ~ 850m
2/ g; The secondary pore of 1.7 ~ 10nm accounts for more than 50% of total pore volume; Infrared acidity is 0.10 ~ 0.50mmol/g; Ion exchange capacity≤0.10% is mass percentage; At 25 DEG C, P/P
0be under 1.0 conditions, the adsorbance <5.0% of water is mass percentage.
The SiO of above-mentioned modified Y zeolite
2/ Al
2o
3mol ratio specifically can be 50 ~ 120,53.0,57.7 or 113.0; Lattice constant specifically can be 2.428nm, 2.429nm or 2.425nm; Relative crystallinity specifically can be 93%, 96% or 100%; Specific area specifically can be 800 ~ 850m
2/ g, 824m
2/ g, 829m
2/ g or 846m
2/ g; The secondary pore of 1.7 ~ 10nm accounts for total pore volume and specifically can be 50% ~ 60%, 52.4%, 55.1% or 55.6%; Infrared acidity is 0.10 ~ 0.30mmol/g, 0.17mmol/g, 0.23mmol/g or 0.29mmol/g; At 25 DEG C, P/P
0be under 1.0 conditions, the adsorbance of water specifically can be 2.4%, 2.7% or 3.2%, is mass percentage.
Invention further provides the preparation method of above-mentioned modified Y zeolite, comprise the steps:
(1) by NH
4naY zeolite carries out hydrothermal treatment consists;
(2) zeolite that step (1) obtains is carried out low pH ammonium to exchange;
(3) filter cake obtained in step (2) is carried out hydrothermal treatment consists;
(4) described modified Y zeolite is namely obtained with the non-framework aluminum that acid removes in the zeolite that step (3) obtains.
In above-mentioned preparation method, in step (1), described NH
4the physicochemical property of NaY zeolite is as follows: degree of crystallinity>=90%, as 95%; Lattice constant is 2.468 ~ 2.472nm, as 2.470nm; SiO
2/ Al
2o
3mol ratio is 4.5 ~ 5.5, as 5.1; Na
2o content≤3.5%, as 2.3%, is mass percentage;
The temperature of described hydrothermal treatment consists can be 500 ~ 700 DEG C, specifically can be 560 ~ 650 DEG C, 560 DEG C, 600 DEG C or 650 DEG C, water vapor pressure can be 0.01 ~ 1.0MPa, specifically can be 0.1 ~ 0.15MPa, 0.10MPa or 0.15MPa, time can be 1.0 ~ 10.0 hours, specifically can be 2 ~ 3.5 hours, 2 hours, 3 hours or 3.5 hours.
In above-mentioned preparation method, low pH ammonium described in step (2) exchanges containing NH
4 +and H
+mixed aqueous solution in carry out; In described mixed aqueous solution, NH
4 +molar concentration can be 0.5 ~ 3.0mol/L, as 2.0mol/L or 1.2mol/L, H
+molar concentration can be 0.05 ~ 0.6mol/L, specifically can be 0.15mol/L, 0.2mol/L or 0.15mol/L;
The temperature that described low pH ammonium exchanges can be 70 ~ 120 DEG C, and specifically can be 90 ~ 120 DEG C, 90 DEG C or 120 DEG C, the time can be 0.5 ~ 3.0 hour, specifically can be 1 ~ 2 hour, 1 hour, 1.5 hours or 2 hours;
1 ~ 3 described low pH ammonium can be comprised in step (2) exchange.
In above-mentioned preparation method, in step (3), the temperature of described hydrothermal treatment consists can be 500 ~ 800 DEG C, specifically can be 650 DEG C or 680 DEG C, water vapor pressure can be 0.01 ~ 1.0MPa, specifically can be 0.1MPa or 0.2MPa, the time can be 1.0 ~ 10.0 hours, specifically can be 2 ~ 4 hours, 2 hours, 3 hours or 4 hours;
The temperature of hydrothermal treatment consists described in step (3) is higher 10 ~ 200 DEG C than the temperature of hydrothermal treatment consists described in step (1), as 50 DEG C or 120 DEG C.
In above-mentioned preparation method, in step (4), described acid can be hydrochloric acid or nitric acid etc.; The concentration of described acid can be 0.1 ~ 3mol/L, specifically can be 0.4mol/L or 0.5mol/L;
The described temperature removed can be 60 ~ 120 DEG C, and specifically can be 80 DEG C, 90 DEG C or 95 DEG C, the time can be 0.5 ~ 5 hour, specifically can be 1 hour, 1.5 hours or 2 hours.
A kind of carrier of hydrocracking catalyst provided by the present invention, is made up of above-mentioned modified Y zeolite, aluminium oxide and amorphous aluminum silicide;
In described catalyst carrier, the quality proportioning of described modified Y zeolite, aluminium oxide and amorphous aluminum silicide can be: (5 ~ 40): (30 ~ 75): (5 ~ 40), specifically can be (30 ~ 40): (30 ~ 36): (30 ~ 42), 40:30:30,30:42:38 or 30:36:34.
In above-mentioned catalyst carrier, the specific area of described catalyst carrier can be 280 ~ 450m
2/ g, specifically can be 316m
2/ g, 332m
2/ g or 308m
2/ g; Pore volume can be 0.28 ~ 0.52mL/g, specifically can be 0.345mL/g, 0.367mL/g or 0.399mL/g;
The pore volume of described aluminium oxide can be 0.8 ~ 1.2mL/g, and as 1.0mL/g, specific area can be 300 ~ 500m
2/ g, as 400m
2/ g;
In described amorphous aluminum silicide, SiO
2mass percentage can be 10 ~ 90%, as 50%, specific area can be 200 ~ 450m
2/ g, as 370m
2/ g, pore volume can be 0.5 ~ 0.9mL/g, as 0.85mL/g.
Present invention also offers the preparation method of said catalyst carrier, comprise the steps: above-mentioned modified Y zeolite, described aluminium oxide, described amorphous aluminum silicide and adhesive to carry out that mechanical mixture rolls, extruded moulding, then namely drying and roasting obtain described catalyst carrier.
In above-mentioned preparation method, described adhesive is for be formed by nitric acid and alumina peptization; Described aperture aluminium oxide pore volume can be 0.3 ~ 0.6mL/g, and as 0.46mL/g, specific area can be 200 ~ 350m
2/ g, as 280m
2/ g;
The temperature of described drying can be 80 ~ 150 DEG C, and as 105 DEG C, the time can be 2 ~ 6 hours, as 4 hours or 5 hours;
The temperature of described roasting can be 500 ~ 700 DEG C, and as 550 DEG C, the time can be 2 ~ 6 hours, as 3 hours or 4 hours.
Tool of the present invention has the following advantages:
The effect of catalyst carrier is generally carrying active material, active component can be made to be dispersed on carrier surface, improve the catalytic efficiency of unit mass active component, stops active component in use to sinter, improves the heat resistance of catalyst.For carrier of hydrocracking catalyst, it is the carrier of hydrogenation metal, is again cracking component donor.Modification of the present invention (deep sealumination modified) Y zeolite has dealumination depth and can choose at random, SiO
2/ Al
2o
3mol ratio reaches the crystal structure that 120 do not destroy zeolite yet, and it is high to have degree of crystallinity, and surface area is large, and silica alumina ratio is high, and hydrophobicity is good, and secondary pore enriches, and acid site density is low, middle strong acid ratio high.Modification (deep sealumination modified) Y zeolite is used for high voluminous intermediate oil hydrocracking catalyst, high-ratio surface and flourishing secondary pore not only facilitate the performance of hydrogenation activity, and be conducive to the diffusion of product, hold charcoal ability also greatly to strengthen, secondary pore is many, acid site density is low, reduce excessive fragmentation and second pyrolysis occurrence probability, thus catalyst can be made to have excellent middle distillates oil selectivity, degree of crystallinity is high, the acid site ratio height of moderate strength then makes catalyst have good activity, silica alumina ratio is high, lattice constant is little, Stability Analysis of Structures, heat and good hydrothermal stability, catalyst is then made to have good stability.Be prepared into catalyst carrier using modification (deep sealumination modified) Y zeolite as acidic cleavage component, be suitable as the hydrocracking catalyst of voluminous intermediate oil.
Detailed description of the invention
The experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
The preparation of embodiment 1, deep sealumination modified Y zeolite A
1. 250 grams of NH are got
4naY zeolite (produce, SiO by Wenzhou catalyst plant
2/ Al
2o
3mol ratio is 5.1, lattice constant a
0=2.470nm, degree of crystallinity is 95%, Na
2o is 2.3w%, and butt is 70w%) be placed in heat-treatment furnace, control the heating rate of 500 DEG C/h, temperature is risen to 600 DEG C, the water vapor pressure simultaneously maintaining system is 0.15MPa, processes 2.0 hours, cooling, takes out sample.
2. with containing NH
4 +and H
+concentration be respectively solution (ammonium chloride and the mixed in hydrochloric acid aqueous solution) 1500mL of 2.0mol/L and 0.2mol/L and sample contacts and stir, maintain slurry temperature at 90 DEG C, constant temperature 1.5 hours, the same terms reprocessing 1 time, filter cake washes with water;
3. wet cake is placed in heat-treatment furnace, temperature is risen to 650 DEG C, control water vapor pressure is 0.20MPa, constant temperature 3 hours, cooling, takes out sample;
4. final sample 1000mL concentration is the non-framework aluminum that the hydrochloric acid of 0.5mol/L removes in sample, and dealuminzation condition is that obtain deep sealumination modified Y zeolite A, its physico-chemical property was in table 1 80 DEG C of process 2 hours.
The preparation of embodiment 2, deep sealumination modified Y zeolite B
1. by 2kg NH
4naY zeolite (physical and chemical parameter is with embodiment 1) is placed in heat-treatment furnace, in 2 hours, temperature is risen to 630 DEG C, inject water vapour (logical steam rate 3.0kg/h), and keeping system pressure is at 0.1MPa, constant temperature 3.5 hours at 650 DEG C, cooling, takes out sample;
2. in autoclave, water 15kg is added, industrial NH
4nO
32.4kg, HNO
30.2kg and first time heat treatment after zeolite sample (in mixed solution, NH
4 +and H
+concentration be respectively 1.2mol/L and 0.25mol/L), sealing, start stirring, temperature is risen to 120 DEG C, constant temperature process 1 hour, filter cake the same terms reprocessing 1 time, elimination mother liquor, is dried to cake moisture ≯ 25%.
3. sample is placed in heat-treatment furnace, and 1. conditional synchronization carries out intermediate water heat treatment suddenly, and wherein hydrothermal treatment consists temperature is 650 DEG C, and hydrothermal conditions is 2 hours.
4. the zeolite sample HCl of 14 liters of 0.4mol/L carries out chemical dealuminization 1.5 hours, elimination mother liquor at 90 DEG C, and filter cake spends deionized water to can't detect Cl
-, obtain deep sealumination modified Y zeolite B, its physico-chemical property is in table 1.
The preparation of embodiment 3, deep sealumination modified Y zeolite C
1. 300g NH
4naY zeolite (physical and chemical parameter is with embodiment 1) is placed in heat-treatment furnace, at 1 hour, temperature is risen to 560 DEG C, maintains pressure at 0.1MPa, constant temperature 3 hours, cooling, take out zeolite sample by zeolite self water vapour.
2. with containing NH
4 +and H
+concentration be respectively solution (ammonium nitrate and the nitric acid mixed solution) 200mL of 2.0mol/L and 0.15mol/L and sample contacts and stir, temperature is risen to 90 DEG C, and maintain 2 hours, repeat 2 times, filter cake water purification washs, dry.
3. zeolite sample is placed in heat-treatment furnace, at 1.5 hours, temperature is raised to 680 DEG C, passes into water vapour 300g/h simultaneously, and control system pressure is at 0.1 ± 0.02MPa, and control system temperature, at 680 DEG C, keeps 4 hours, then lowers the temperature, and takes out sample.
4. the HCl200mL of zeolite sample 0.5mol/L removes non-framework aluminum 1 hour at 95 DEG C, and dealuminzation step repeats 2 times, obtains deep sealumination modified Y zeolite C, and its physico-chemical property is in table 1.
The preparation of comparative example 1, modified zeolite D
1. (the NH of NaY zeolite 100g 2mol/L
4)
2sO
41000mL carries out ammonium and exchanges 3 times at 90 DEG C, and each 2 hours, filter cake finally spent deionized water, dry.
2. dried sample is placed in heat-treatment furnace, in 1.5 hours, temperature is risen to 700 DEG C, and passes into water vapour (250g/h), and constant temperature 2.0 hours, then lowers the temperature, and takes out sample.
3. (the NH of sample 2mol/L
4)
2sO
41000mL carries out ammonium and exchanges 2 times at 90 DEG C, and each 2 hours, filter cake finally spent deionized water, dry.
4. dried sample is placed in heat-treatment furnace, in 1.5 hours, temperature is risen to 700 DEG C, and passes into water vapour (250g/h), and constant temperature 2.0 hours, then lowers the temperature, and takes out sample.
5. the H of sample 0.4mol/L
2sO
4750mL dealuminzation at 90 DEG C obtains modified zeolite D in 1.0 hours, and its physico-chemical property is in table 1.
The preparation of comparative example 2, modified molecular screen E
The method provided according to CN200710012769.5 prepares modified Y molecular sieve: get 2000gNa
2o content is 2.8wt%(butt 70.3wt%) raw material NH
4naY, put into reflux and flask that can be airtight, pull an oar by 7800mL deionized water, and stir condition under rapid temperature increases to 95 DEG C, then in 2 hours, drip the aqueous solution configured by 453g ammonium hexafluorosilicate and 3000mL deionized water with uniform speed, add rear slurry constant temperature 2 hours under 95 DEG C of stirring conditions.Stop stirring, leave standstill 10 minutes, isolate the molecular sieve on flask top with decantation, after filtration, wash, wet cake puts into pipe type water heat-treatment furnace, temperature programming, to 600 DEG C, processes 2.5 hours under gauge pressure 0.2MPa, then puts into reflux and flask that can be airtight, add the mixed aqueous solution 1800mL containing concentration 0.8mol/L aluminum sulfate and 0.3mol/L sulfuric acid, at 90 DEG C, constant temperature stirs 2 hours, and filtration, washing, drying obtain modified zeolite E, and its physico-chemical property is in table 1.
The physico-chemical property of modified Y zeolite prepared by table 1 embodiment 1-3 and comparative example 1-2
Modified Y zeolite has high silica alumina ratio, degree of crystallinity and specific area as can be seen from the table, particularly to account for the ratio of total pore volume high for the secondary pore of 1.7 ~ 10nm, be conducive to reactant and contact the diffusion with product with acidic site, make carrier obtain high object product selectivity for catalyst.
The preparation of embodiment 4, catalyst carrier ZA
By modified Y zeolite A50 gram (butt 80wt%), amorphous aluminum silicide (SiO
2content 50wt%, pore volume 0.85mL/g, specific area 370m
2/ g, butt 75wt%) 13.4 grams, macroporous aluminium oxide (pore volume 1.0mL/g, specific area 400m
2/ g, butt 75wt%) 40 grams, (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3 to adhesive, and the pore volume of little porous aluminum oxide is 0.46mL/g, and specific area is 280m
2/ g) 66.5 grams be placed in roller mixed grind, be pressed into paste, extruded moulding, and 105 DEG C of dryings 4 hours, then 550 DEG C of roastings 3 hours, obtain catalyst carrier ZA, its physico-chemical property was in table 2.
In catalyst carrier ZA prepared by the present embodiment, the mass percentage of modified Y zeolite, macroporous aluminium oxide and amorphous aluminum silicide is respectively 40%, 30% and 30%.
The preparation of embodiment 5, catalyst carrier ZB
By modified Y zeolite A50 gram (butt 80wt%), amorphous aluminum silicide (SiO
2content 50wt%, pore volume 0.85mL/g, specific area 370m
2/ g, butt 75wt%) 48 grams, macroporous aluminium oxide (pore volume 1.0mL/g, specific area 400m
2/ g, butt 75wt%) 112 grams, (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3 to adhesive, and the pore volume of little porous aluminum oxide is 0.46mL/g, and specific area is 280m
2/ g) 133 grams be placed in roller mixed grind, be pressed into paste, extruded moulding, and 105 DEG C of dryings 4 hours, then 550 DEG C of roastings 3 hours, obtain catalyst carrier ZB, its physico-chemical property was in table 2.
In catalyst carrier ZB prepared by the present embodiment, the mass percentage of modified Y zeolite, macroporous aluminium oxide and amorphous aluminum silicide is respectively 20%, 42% and 38%.
The preparation of embodiment 6, catalyst carrier ZC
By modified Y zeolite C75 gram (butt 80wt%), amorphous aluminum silicide (SiO
2content 50wt%, pore volume 0.85mL/g, specific area 370m
2/ g, butt 75wt%) 37.5 grams, macroporous aluminium oxide (pore volume 1.0mL/g, specific area 400m
2/ g, butt 75wt%) 96 grams, (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3 to adhesive, and the pore volume of little porous aluminum oxide is 0.46mL/g, and specific area is 280m
2/ g) 133 grams be placed in roller mixed grind, be pressed into paste, extruded moulding, and 105 DEG C of dryings 5 hours, then 550 DEG C of roastings 4 hours, obtain catalyst carrier ZC, its physico-chemical property was in table 2.
In catalyst carrier ZC prepared by the present embodiment, the mass percentage of modified Y zeolite, macroporous aluminium oxide and amorphous aluminum silicide is respectively 30%, 36% and 34%.
The preparation of comparative example 3, catalyst carrier ZD
Change modified Y zeolite A in embodiment 4 into zeolite D, other condition is identical, and obtained catalyst carrier ZD, its physico-chemical property is in table 2.
The preparation of comparative example 4, catalyst carrier ZE
Change the modified Y zeolite A of embodiment 4 into zeolite E, other condition is identical, and obtained catalyst carrier ZE, its physico-chemical property is in table 2.
The physico-chemical property of table 2 catalyst carrier
Embodiment 7, catalyst carrier catalytic performance test result
Catalyst carrier ZA, ZB, ZC, ZD and ZE being crushed to 20 orders, being contained in high pressure microreactor, take hexadecane as model reaction thing, at reaction temperature 355 DEG C, reaction pressure 80.0MPa, air speed 1.0h
-1condition under react.Carry out active comparative evaluation's test, the results are shown in table 3.
Evaluation result shows: catalyst carrier of the present invention has higher lytic activity and selective preferably.
Table 3 catalyst carrier lytic activity
| Carrier | ZA | ZB | ZC | ZD | ZE |
| Hexadecane conversion ratio, w% | 63.2 | 56.6 | 52.4 | 32.3 | 57.4 |
| Octane is selective, w% | 51.2 | 49.3 | 53.1 | 46.6 | 47.2 |
Claims (5)
1. a carrier of hydrocracking catalyst, is made up of modified Y zeolite, aluminium oxide and amorphous aluminum silicide;
In described catalyst carrier, the quality proportioning of described modified Y zeolite, aluminium oxide and amorphous aluminum silicide is: (5 ~ 40): (30 ~ 75): (5 ~ 40);
Described modified Y zeolite has following physicochemical property:
SiO
2/ Al
2o
3mol ratio is 50 ~ 120; Lattice constant is 2.420 ~ 2.435nm; Relative crystallinity>=90%; Specific area is 800 ~ 850m
2/ g; The secondary pore of 1.7 ~ 10nm accounts for more than 50% of total pore volume; Infrared acidity is 0.10 ~ 0.30mmol/g; Ion exchange capacity≤0.10%; At 25 DEG C, P/P
0be under 1.0 conditions, the adsorbance <5.0% of water, in mass;
The preparation method of described modified Y zeolite, comprises the steps:
(1) by NH
4naY zeolite carries out hydrothermal treatment consists;
(2) zeolite that step (1) obtains is carried out low pH ammonium to exchange;
(3) filter cake obtained in step (2) is carried out hydrothermal treatment consists;
(4) described modified Y zeolite is namely obtained with the non-framework aluminum that acid removes in the zeolite that step (3) obtains;
In step (1), described NH
4the physicochemical property of NaY zeolite is as follows: degree of crystallinity>=90%; Lattice constant is 2.468 ~ 2.472nm; SiO
2/ Al
2o
3mol ratio is 4.5 ~ 5.5; Na
2o content≤3.5% is mass percentage;
The temperature of described hydrothermal treatment consists is 500 ~ 700 DEG C, and water vapor pressure is 0.01 ~ 1.0MPa, and the time is 1.0 ~ 10.0 hours;
Low pH ammonium described in step (2) exchanges containing NH
4 +and H
+mixed aqueous solution in carry out; In described mixed aqueous solution, NH
4 +molar concentration be 0.5 ~ 3.0mol/L, H
+molar concentration be 0.05 ~ 0.6mol/L;
The temperature that described low pH ammonium exchanges is 70 ~ 120 DEG C, and the time is 0.5 ~ 3.0 hour;
Step (2) comprises 1 ~ 3 described low pH ammonium and exchanges;
In step (3), the temperature of described hydrothermal treatment consists is 500 ~ 800 DEG C, and water vapor pressure is 0.01 ~ 1.0MPa, and the time is 1.0 ~ 10.0 hours;
The temperature of hydrothermal treatment consists described in step (3) is higher 10 ~ 200 DEG C than the temperature of hydrothermal treatment consists described in step (1).
2. catalyst carrier according to claim 1, is characterized in that: the specific area of described catalyst carrier is 280 ~ 450m
2/ g, pore volume is 0.28 ~ 0.52mL/g;
The pore volume of described aluminium oxide is 0.8 ~ 1.2mL/g, and specific area is 300 ~ 500m
2/ g;
In described amorphous aluminum silicide, SiO
2mass percentage be 10 ~ 90%, specific area is 200 ~ 450m
2/ g, pore volume is 0.5 ~ 0.9mL/g.
3. catalyst carrier according to claim 1, is characterized in that: in step (4), and described acid is hydrochloric acid or nitric acid; The concentration of described acid is 0.1 ~ 3mol/L;
The described temperature removed is 60 ~ 120 DEG C, and the time is 0.5 ~ 5 hour.
4. the preparation method of arbitrary described catalyst carrier in claim 1-3, comprise the steps: described modified Y zeolite, described aluminium oxide, described amorphous aluminum silicide and adhesive to carry out that mechanical mixture rolls, extruded moulding, then namely drying and roasting obtain described catalyst carrier.
5. preparation method according to claim 4, is characterized in that: described adhesive is for be formed by nitric acid and aperture alumina peptization; Described aperture aluminium oxide pore volume is 0.3 ~ 0.6mL/g, and specific area is 200 ~ 350m
2/ g;
The temperature of described drying is 80 ~ 150 DEG C, and the time is 2 ~ 6 hours;
The temperature of described roasting is 500 ~ 700 DEG C, and the time is 2 ~ 6 hours.
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| CN104549431B (en) * | 2013-10-23 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of preparation method containing sour modified molecular screen hydrocracking catalyst |
| CN104588076B (en) * | 2013-11-03 | 2017-02-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
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| CN1096296C (en) * | 1998-11-13 | 2002-12-18 | 中国石油化工集团公司 | Hydrocracking catalyst for producing middle distillate and its preparation method |
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Effective date of registration: 20170221 Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee after: China National Offshore Oil Corporation Patentee after: China National Offshore Oil Corporation Patentee after: CNOOC Refining & Chemical Research Institute (Beijing) Co., Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: China National Offshore Oil Corporation Patentee before: China National Offshore Oil and Gas Development and Utilization Co., Ltd. |
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Address after: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee after: China National Offshore Oil Corporation Patentee after: China Offshore Oil Group Co., Ltd. Co-patentee after: CNOOC Refining & Chemical Research Institute (Beijing) Co., Ltd. Address before: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee before: China National Offshore Oil Corporation Patentee before: China National Offshore Oil Corporation Co-patentee before: CNOOC Refining & Chemical Research Institute (Beijing) Co., Ltd. |