A kind of preparation method of catalytic diesel oil hydrogenation conversion catalyst
Technical field
The invention belongs to hydrotreating techniques fields, relate in particular to a kind of system of catalytic diesel oil hydrogenation conversion catalyst
Preparation Method.
Background technology
Since the new century, with being increasingly enhanced of people's environmental consciousness, national environmental protection regulation increasingly stringent and
The fast development of national economy, demand of the countries in the world to cleaning automotive fuel are all being continuously increased.Catalytic cracking(FCC)Technology
It is one of the main technique means of heavy oil lighting, important status is all occupied in the oil refining enterprise of countries in the world.I
State's catalytic cracking unit annual working ability alreadys exceed 100,000,000 tons at present, is only second to the U.S..In petrol and diesel oil product composition, catalysis is split
Change gasoline and account for 80% or so, catalytic diesel oil accounts for 30% or so.In recent years, with the increasingly heaviness of domestic processed crude quality,
The raw material that catalytic cracking is processed also heaviness and in poor quality increasingly, in addition many enterprises improve quality of gasoline or increasing to reach
The purpose for producing propylene has carried out catalytic cracking unit the operating severity for being transformed or improving catalytic cracking unit, has caused to be catalyzed
The product of cracking, especially catalytic diesel oil quality more deteriorate.
To improve the utilization rate of petroleum resources, the total quality level of vapour, diesel fuel is improved, realizes that product blending is optimal
Change and the maximized target of value of the product, satisfaction are domestic to clean fuel increasing need, high aromatics diesel hydro-conversion
The hydrocracking process technology for producing high added value naphtha component and low-sulfur cleaning diesel fuel has good application prospect.
Domestic and international researcher has also carried out a large amount of research work.Foreign countries are existing to use hydrocracking process technology by catalytic cracking
Light cycle oil is converted into the relevant report of ultra-low-sulphur diesel and high octane value gasoline blending component.
US2010116712 discloses a kind of catalytic diesel oil hydrogenating conversion process, and this method is using common process method and splits
Change catalyst, feedstock oil contacts after first passing around pretreatment with Cracking catalyst, production cleaning diesel oil and high-new alkane value gasoline.But
It is that the reduction gasoline component that this method can not be selective adds hydrogen saturation, and therefore, gasoline products loss of octane number is larger.
EP20110834653 discloses a kind of preparation method of polycyclic aromatic hydrocarbon hydrogenation conversion catalyst, the catalyst carrier
It is made of beta-molecular sieve and boehmite, using conventional method addition group VIB and group VIII active metal component, but
Catalyst is equally stronger to gasoline component saturability, is unfavorable for catalytic diesel oil hydro-conversion production high-knock rating gasoline process.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of preparation method of catalytic diesel oil hydrogenation conversion catalyst, this
Inventive method improves effective hydrogenation capability of catalyst activity component, improves the hydrogenation reaction selectivity of catalyst.
The preparation method of the catalytic diesel oil hydrogenation conversion catalyst of the present invention, including following content:(1)By aluminium oxide and liquid
State or gaseous unsaturated olefin come into full contact with, and carbon deposit reaction is then carried out in oxygen-containing atmosphere, obtains carbon deposit aluminium oxide;(2)
Carbon deposit aluminium oxide, Y molecular sieve are uniformly mixed with the compound containing group VIB and the hydrogenation active metals of group VIII, are added
Rear extruded moulding is slurried in dust technology, and dry, roasting obtains catalyst.
In the method for the present invention, step(1)The unsaturated olefin be carbon atom number be 2 ~ 10 positive structure or isomeric olefine,
Alkadienes;It refers to that unsaturated olefin diffuses into inside molecular sieve that wherein the alkene comes into full contact with molecular sieve;Work as use
When gaseous state unsaturated olefin, gaseous state unsaturated olefin is with molecular sieve contact conditions:0.1 ~ 1.0MPa of pressure, time of contact 0.1 ~
2 hours;When using liquid unsaturated hydrocarbons, liquid unsaturated olefin is with molecular sieve contact conditions:0.1 ~ 1.0MPa of pressure, connects
0.5 ~ 4 hour time is touched, molecular sieve answers thorough impregnation in liquefied olefines.The alkene comes into full contact with molecular sieve generally to exist
It is carried out under room temperature, the unsaturated hydrocarbons state phase is phase under room temperature.
Step(1)The oxygen-containing atmosphere is the mixing of air, the mixture of oxygen and nitrogen or oxygen and inert gas
One kind in object, the volume fraction of oxygen in the gas phase are 10% ~ 100%, preferably air;Carbon deposit reaction condition is:Reaction temperature
50 ~ 500 DEG C of degree, preferably 100 ~ 400 DEG C, the reaction time is 1 ~ 200 hour, preferably 10 ~ 100 hours.
Step(1)In the carbon deposit aluminium oxide, on the basis of carbon deposit alumina weight, carbon content be 0.5wt% ~
The Kong Rong ratios of 20wt%, preferably 2wt ~ 15wt%, carbon deposit aluminium oxide and aluminium oxide before non-carbon deposit are 1:10~1:1.5.
In the method for the present invention, step(2)The group VIB active metal is selected from W and/or Mo, group VIII activity gold
Belong to and be selected from Ni and/or Co, the content of group vib metallic compound accounting based on corresponding oxide is 4 wt% ~ 20 in mixture
Wt%, the content of the group VIII metallic compound accounting based on corresponding oxide is the wt% of 2 wt% ~ 15.The dust technology it is dense
Degree is 3wt% ~ 30wt%.
In the method for the present invention, step(2)The drying condition is:It is 2 ~ 8 hours dry at 90 ~ 150 DEG C;
In the method for the present invention, step(2)After the drying process, the carbon distribution in aluminium oxide can roast in oxygen-containing atmosphere
Removing is burnt, reservation can also be roasted in an inert atmosphere in the catalyst;Roasting condition is:Roasting 1 ~ 5 is small at 300 ~ 600 DEG C
When.The inert atmosphere is selected from N2, helium, one or more of neon or argon gas.The oxygen-containing atmosphere be air,
One kind in the mixture or oxygen of oxygen and nitrogen and the mixture of inert gas, the volume fraction of oxygen in the gas phase are
10% ~ 100%, preferably air.
The mode of loading of active metal can also use saturation infusion process in the method for the present invention.I.e. carbon distribution treated oxidation
Aluminium powder body with the carrier that is mixed with of Y molecular sieve, then uses the aqueous solution containing group VIII and group vib salt to carrier first
Carry out saturation dipping;Wherein group VIB active metal is selected from W and/or Mo, and group VIII active metal is selected from Ni and/or Co, leaching
The content of group vib metallic compound is calculated as 10 ~ 40g/100ml by corresponding oxide in stain liquid, group VIII metallic compound
Content is calculated as 3 ~ 20g/100ml by corresponding oxide, and the concentration of metallic compound can need to carry out according to product in maceration extract
Corresponding adjustment.
Catalytic diesel oil hydrogenation conversion catalyst prepared by the method for the present invention, on the basis of catalyst weight, vib metals
Content is calculated as 4wt%~20wt% with oxide, and group viii metal content is calculated as 2wt%~15wt%, Y molecular sieve content with oxide
It is 30% ~ 84%, preferably 40% ~ 80%, alumina content is 10% ~ 64%, preferably 20% ~ 60%, carbon content 0.2% ~ 12%, preferably 2% ~
5%。
Prepared by the method for the present invention urges bavin reforming catalyst to can be applied to catalytic diesel oil hydro-conversion production high-octane rating vapour
Oil reaction, general operational requirement(GOR) are:Reaction temperature is 340~440 DEG C, preferably 360~430 DEG C;Reaction pressure be 4.0~
15.0MPa, preferably 6.0~12.0MPa;Volume space velocity is 0.2~6.0h when liquid-1, preferably 0.5~3.0h-1;Hydrogen to oil volume ratio
It is 100~2000, preferably 500~1500.
The reaction process process of catalytic diesel oil hydro-conversion production high-knock rating gasoline is typically catalytic diesel oil raw material through adding
After hydrogen denitrogenation, denitrification reaction generates oil and carries out hydrocracking reaction generation high octane gasoline component.Hydrocracking reaction adds
For hydrogen Cracking catalyst usually using Y molecular sieve and aluminium oxide as carrier, W-Ni or Mo-Ni are active metal component.Add for conventional
Aluminium oxide in the hydrocracking catalyst of the hydrogen cracking reaction process both matrix as dispersion Y molecular sieve, decentralized cracking center,
Meanwhile better hydrogenation active metals dispersion performance on aluminium oxide, be also beneficial to cracked product further adds hydrogen saturation, improves
Cracked product property.But high-knock rating gasoline technology is produced for catalytic diesel oil hydro-conversion, it is desirable that Cracking catalyst has one
Fixed hydrogenation capability terminates carbonium ion, inhibits excessive fragmentation, improves catalyst stability, load on molecular sieve plus hydrogen is lived
Property metal be conducive to improve plus hydrogen and acid centre matching, reduce excessive fragmentation, this partial hydrogenation activity belong to effectively plus hydrogen
Activity, the excessively high hydrogenation activity of active metal, be easy to cause the saturation of aromatic hydrocarbons in gasoline products on aluminium oxide, reduces gasoline production
Product octane number is unfavorable for improving gasoline products octane number, this is catalytic diesel oil hydro-conversion production high-knock rating gasoline technology institute
It is undesirable.Conventional preparation method, generally directly prepares aluminium oxide and molecular sieve complex carrier, is then soaked by infusion process
Stain active component, active component in the two synchronizes when increasing or decreasing, if improving the hydrogenation activity on molecular sieve,
Excessively high hydrogenation activity on aluminium oxide is easy to cause excessive hydrogenation saturation, if reducing the hydrogenation activity on aluminium oxide, reduces
Add hydrogen to be saturated, then can influence the normal hydrogenation activity of Y molecular sieve, lead to excessive fragmentation.So how in equilibrium catalyst it is living
Property component is on aluminium oxide and molecular sieve between hydrogenation capability, and there is insoluble contradiction, the two is difficult to take into account.
For the method for the present invention by carrying out carbon distribution processing to alumina powder in advance, the carbon distribution of formation is filled with the part of aluminium oxide
Duct and surface have obtained the alumina support of reasonable coke content, in this way during subsequently dipping hydrogenation active component, reduce
The load capacity of active component on alumina, while not influencing the hydrogenation activity of active metal on Y molecular sieve, it is suppressed that
The hydrogenation activity of active metal on alumina is loaded, therefore, catalyst has better hydrogenation reaction selectivity, can reduce
The excessive hydrogenation of the gasoline component that cracking generates on alumina, improves gasoline products octane number, while improving catalyst
Effective hydrogenation capability, active component is easier to be supported on molecular sieve surface in dipping process, reduces activity component impregnation liquid
Usage amount.
Specific implementation mode
Below by embodiment, the present invention is further described, but is not so limited the present invention.Involved by embodiment
Percentage is mass percent(Except relative crystallinity), the liquid-solid ratio is that liquid consolidates mass ratio.
Embodiment 1
(1)Industrial production macroporous aluminium oxide 200g is taken to be positioned in the closed container full of butadiene atmosphere, control pressure
0.3MPa comes into full contact with 20 minutes, then, is heated 80 hours at 200 DEG C in air atmosphere,;
(2)Take step(1)Obtained aluminium oxide 50g, Commercial modified Y molecular sieve 80g, MoO3 15g and nickel nitrate 20g mixing, add
Enter 4g/100ml dust technologies mix in a mixer roll to extrudable shape after extruded moulding;
(3)Step(2)After the dry 4h of lower 120 DEG C of sample air atmosphere, 500 DEG C of roasting 3h in nitrogen atmosphere are transferred to, are catalyzed
Agent C1.
Embodiment 2
(1)Heptene is taken to impregnate industrial production macroporous aluminium oxide 200g 4 hours, then, 180 DEG C of heating 150 are small in air atmosphere
When;
(2)Take step(1)Obtained aluminium oxide 50g, Commercial modified Y molecular sieve 100g mixing, is added 4g/100ml dust technologies and exists
120 DEG C of dry 4h obtain 2 carrier of embodiment after mixing rolls extruded moulding in mixer;
(3)Mo-Ni dipping solutions are configured, by MoO3, basic nickel carbonate be added in distilled water and prepare inclined Mo-Ni dipping solutions,
MoO is adjusted in mixed solution in terms of the oxide of metal salt3 30g/100ml, nickel oxide 10g/100ml;
(4)Take step(3)The Mo-Ni dipping solutions of acquisition, according to liquid-solid ratio 3:1 impregnation steps(2)The catalyst carrier of acquisition
Then 2h after the dry 2h of lower 150 DEG C of air atmosphere, is transferred to 400 DEG C of roasting 4h in helium atmosphere, obtains catalyst C2.
Embodiment 3
(1)Heptene is taken to impregnate industrial production macroporous aluminium oxide 200g 2 hours, then, 300 DEG C of heating 200 are small in air atmosphere
When;
(2)Take step(1)Obtained aluminium oxide 80g, Commercial modified Y molecular sieve 80g, ammonium metatungstate 22g and nickel nitrate 20g is mixed
It closes, 4g/100ml dust technologies are added mix in a mixer and roll to extrudable shape, extruded moulding after shape;
(3)Step(2)After the dry 4h of lower 120 DEG C of sample air atmosphere, 550 DEG C of roasting 3h in nitrogen atmosphere are transferred to, are catalyzed
Agent C3.
Embodiment 4
(1)Hexadiene is taken to impregnate industrial production macroporous aluminium oxide 200g 2 hours, then, 400 DEG C of heating 120 in air atmosphere
Hour;
(2)Take step(1)Obtained aluminium oxide 50g, modified Y molecular sieve 100g, ammonium metatungstate 30g and nickel nitrate 60g mixing, adds
Enter 4g/100ml dust technologies mix in a mixer roll to extrudable shape after extruded moulding;
(3)Step(2)After the dry 4h of lower 120 DEG C of sample air atmosphere, 450 DEG C of roasting 3h in nitrogen atmosphere are transferred to, are catalyzed
Agent C4.
Embodiment 5
With embodiment 1, only by step(3)Calcination atmosphere be changed to air, obtain catalyst C5
Embodiment 6
With embodiment 2, only by step(3)Calcination atmosphere be changed to air, obtain catalyst C6
Comparative example 1
Example 1 handles the modified Y molecular sieve directly used with embodiment 1 using industry macroporous aluminium oxide 50g without carbon distribution
80g、MoO3 15g and nickel nitrate 20g mixing, addition 4g/100ml dust technologies mix in a mixer to roll to extrudable shape,
Extruded moulding on banded extruder, 120 DEG C of dry 4h in air atmosphere, 500 DEG C of roasting 4h obtain catalyst B1.
Comparative example 2
Example 2 handles the modified Y molecular sieve directly used with embodiment 2 using industrial macroporous aluminium oxide 50g without carbon distribution
100g is mixed, and addition 4g/100ml dust technologies mix in a mixer to roll to extrudable shape, and the extruded moulding on banded extruder is empty
120 DEG C of dry 4h in gas atmosphere, 500 DEG C of roasting 4h obtain 2 catalyst carrier of comparative example, the leaching for then using embodiment 2 to use
Stain solution is prepared for catalyst B2 according to identical dipping method.
Embodiment 1 ~ 4 and the main physico-chemical property of 1 ~ 2 aluminium oxide of comparative example such as table 1.
Embodiment 1 ~ 4 and 1 ~ 2 catalyst physico-chemical property of comparative example are as shown in table 2.
2 embodiment of table and comparative example catalyst physico-chemical property.
Table 2(It is continuous)Embodiment and comparative example catalyst physico-chemical property.
Embodiment 5
In order to investigate the reactivity worth that Examples and Comparative Examples prepare catalyst, catalyst is evaluated on midget plant
It tests, evaluating apparatus is connected using single hop once by flow, and an anti-filling is industrially widely applied to be hydrocracked pretreatment
Catalyst FF-36(Sinopec Fushun Petrochemical Research Institute), two it is anti-load respectively according to embodiment 1 and embodiment 2 with than
It is arranged with comparative example raw material property, evaluation condition and evaluation result compared with example 1 and the hydrocracking catalyst embodiment of comparative example 2
In 3 ~ table of table 6.
3 raw material oil nature of table.
4 embodiment catalyst operating condition of table.
5 comparative example catalyst operating condition of table.
6 embodiment evaluating catalyst result of table.
Table 6(It is continuous)Comparative example evaluating catalyst result.
Embodiment shows the catalyst prepared using the method for the present invention and technique skill with comparative example engineer testing comparing result
Art significantly improves effective hydrogenation capability of catalyst, can increase substantially gasoline products octane number.