CN103506149A - Preparation method of hydrocracking catalyst controlling active metal distribution - Google Patents

Abstract

The invention relates to a preparation method of a hydrocracking catalyst controlling active metal distribution. The preparation method is characterized by comprising the steps of dipping a porous material such as amorphous aluminum silicon or a Y-shaped molecular sieve for certain quantity and energy, respectively changing substances (including fluoride and boride ingredients), in different acidoid electron cloud structures, of the porous material, adding an adhesive for kneading and rolling agglomeration after dryness, then performing band extrusion forming on a band extrusion machine to form a carrier, loading an active metal ingredient (from Mo and/or W, or from Co and/or Ni) by a kneading method and a dipping method, drying and roasting at a certain temperature for a certain time, and obtaining the final catalyst.

Description

A kind of preparation method who controls the hydrocracking catalyst of active metal distribution

Technical field

The present invention relates to catalysis technical field, be specially a kind of preparation method who controls the hydrocracking catalyst of active metal distribution, especially treatment of heavy hydrocarbon class raw material, produces intermediate oil, and can regulate the preparation method of the hydrocracking catalyst of the distribution of metal in duct.

Background technology

Hydrocracking technology, as solving the gentle major programme of separating environment stress problems of crude quality variation, is more and more subject to the attention of Petrochemical Enterprises.The core of hydrocracking is hydrocracking catalyst, and hydrocracking catalyst is a kind of bifunctional catalyst, and it contains acidic components and hydrogenation component simultaneously.Hydrogenation activity is generally selected from periodic table of elements ZhongⅥ B family and group VIII metal provides; And acid source comprises the carriers such as zeolite and inorganic oxide, the carrier of hydrocracking catalyst also needs to provide specific surface and pore volume with carrying hydrogenation metal and reaction compartment simultaneously.In the catalyst adopting conventional method to prepare, active component is uncontrollable at the different aluminium oxide of pore structure and the dispersion in molecular sieve, cause more active component to be dispersed in the interval that can not touch reactant, caused the great waste of active metal.And along with the quickening of crude oil heaviness, the technology of finding suitable control hydrocracking reaction activity is very urgent.

In carrier, add the material that can change surface electronic cloud structure to have good effect, F loads to Al ₂o ₃behind surface, can make Al ₂o ₃the Al on surface ³⁺upper generation OH ^- _(S), with the AlOH effect closing on, produced AlO ^-ion, thereby reduce Al ₂o ₃isoelectric point.F-Al ₂o ₃middle F content is more, AlO ^-ion is more, Al ₂o ₃isoelectric point with F content, increase and to reduce, when dipping, be conducive to cation absorption.Therefore can utilize the material that can change carriers electron cloud, change the isoelectric point of carrier, cause the change of carrier to the absorption of specific ion.

CN102861591A discloses a kind of method of boracic hydrogenation catalyst and preparation thereof.This catalyst contains carrier, load on that at least one on this carrier is selected from the non-noble metal slaine of VIII family and at least one is selected from the slaine of group vib metal, in oxide and take catalyst as benchmark, the mass fraction of VIII family metal is 2-10%, the mass fraction of group vib metal is 15-45%, wherein, the hydrated alumina forming matter that described carrier is boracic.Hydrogenating catalyst composition provided by the invention not only has the refining performance of excellent hydrocarbon oil hydrogenation, and preparation method is simple simultaneously, production cost is low.But it can only change the Cloud Distribution of the carrier of a type, change metal that can not be more purposive mates with acidic site.

CN102861592A discloses a kind of boracic hydrogenation catalyst of active metal component non-uniform Distribution and the method for preparation thereof.The boracic hydration alumina support that contains moulding, load on that at least one on this carrier is selected from the non-noble metal slaine of VIII family and at least one is selected from the slaine of group vib metal, wherein, along catalyst radial section, distribute, the outer surface concentration of described group VIII metal component is 0.1-0.9 with the ratio of centre concentration; The outer surface concentration of described group vib metal component is 0.1-0.8 with the ratio of centre concentration.Catalyst provided by the invention not only has the refining performance of excellent hydrocarbon oil hydrogenation, and preparation method is simple simultaneously, production cost is low.But the non-uniform Distribution of its metal is not for various different acidic sites in catalyst carrier, can not well accomplish acid to coordinate with the effective of metal active, so there is its limitation.

CN102861598A discloses hydrogenation catalyst of containing fluorin of a kind of active metal component non-uniform Distribution and preparation method thereof.The fluorine-containing hydration alumina support that this catalyst contains moulding, load on that at least one on this carrier is selected from the non-noble metal slaine of VIII family and at least one is selected from the slaine of group vib metal, wherein, along catalyst radial section, distribute, the outer surface concentration of described group VIII metal component is 0.1-0.9 with the ratio of centre concentration; The outer surface concentration of described group vib metal component is 0.1-0.8 with the ratio of centre concentration.Catalyst provided by the invention not only has the refining performance of excellent hydrocarbon oil hydrogenation, and preparation method is simple simultaneously, production cost is low.Its shortcoming is equally also well to accomplish that different acid materials coordinate with the effective of metal active.

Summary of the invention

For overcoming the deficiencies in the prior art, the invention provides a kind of method that in hydrocracking catalyst, different acidic materials mate with metal of controlling.The method can, according to the pore structure of the heterogeneity of oil product and molecular sieve and other porous masses, be controlled the distribution of metal component in catalyst carrier.Make different hydrocracking catalysts be suitable for processing various oil products, the catalyst of high aromatic hydrocarbons hydrocarbon material inferior particularly, to produce to greatest extent intermediate oil.

The present invention is a kind of preparation method who controls the hydrocracking catalyst of active metal distribution, it is characterized in that:

Technical process comprises: one or several in conventional aluminium oxide, Y molecular sieve, mesoporous material, modified aluminas, SAPO molecular sieve, β zeolite, amorphous silicon aluminium porous material are first flooded to a certain amount of material composition that can change respectively its different acidic materials electron cloud structures, then dry, roasting at a certain temperature; Then adopt kneading method, a certain amount of active metal component of infusion process load, then dry, the roasting of process uniform temperature and time, final catalyst prod obtained;

Described hydrocracking catalyst, the weight of catalyst of take is benchmark, and composition comprises: the Y molecular sieve of 20wt%～60wt% amorphous aluminum silicide, 5～25wt%, in the group VIB metal of oxide 10wt%～30wt% with in the group VIII metal of oxide 3wt%～10wt%;

Described group VIB metal used is selected from Mo and/or W, and group VIII metal is selected from Co and/or Ni, wherein, VI B/(VI B+ VIII) atomic ratio is 0.30～0.70;

The described material that can change different acidic materials electron cloud structures comprises fluoride, boride; Fluoride has the effect that cloud density is reduced, boride has the effect that cloud density is increased, according to the acid feature of different acidic materials, and pore passage structure feature, according to increase with the effect of metal, or reduce with metal be used for selecting to add fluoride or boride; Wherein fluoride is one or more in hydrogen fluoride, ammonium fluoride, tetrabutyl ammonium fluoride, fluosilicic acid, prodan, fluoroacetic acid; Boride is one or more in boric acid, phenyl boric acid, metaboric acid, dipotassium tetraborate, methyl-boric acid; The amount that described fluoride, boride add is 0.1wt%～3wt%;

Described Y zeolite is sodium type Y molecular sieve, or be the Y zeolite after modification, method of modifying comprises the method that adopts Molecular regulator sieve acidity, pore structure, silica alumina ratio, non-framework aluminum parameters, is selected from one or more in hydro-thermal treatment method and ion-exchange process; Y zeolite after modification is one or more in super steady Y molecule-type USY, low-Na and high-Si Y molecular sieve SSY, the high Y molecular sieve of resistance to nitrogen NTY, FY-1, UDY, MUY; The particle diameter of described Y zeolite is 200nm～5000nm;

Described mesopore molecular sieve is one or more in SBA series, MCM Series Molecules sieve, and mesoporous aperture is 5nm～20nm;

Described modified aluminas is a kind of in conventional alumina modified of silicon modification, titanium modification, and in modified aluminas, modifying element proportion is 0.5%～5%;

Described amorphous aluminum silicide is prepared by coprecipitation or grafting copolymerization process, SiO in the amorphous aluminum silicide of gained ₂weight content be 20%～50%;

Described drying condition is as follows: temperature is 50～300 ℃, and the time is 6～12 hours; Described roasting condition is as follows: temperature is 450～650 ℃, and the time is 4～12 hours;

The carrying method of described catalyst activity metal, adopt kneading method, infusion process routine techniques to prepare, first by one or several active metals in group VIB metal and group VIII metal, according to pore structure, load on amorphous aluminum silicide, Y zeolite or aluminium oxide, then drying, add appropriate nitric acid peptizing agent, kneading or be rolled into paste, extruded moulding is the cylindrical bars of 3～8 millimeters of diameters; Then after drying, roasting, make product catalyst.

According to the method described in the present invention, it is characterized in that: described group VIB metal used is selected from Mo and/or W, and its content is counted 10wt%～25wt% with oxide; Group VIII metal is selected from Co and/or Ni, and its content is counted 3wt%～7wt% with oxide; Wherein, VI B/(VI B+ VIII) atomic ratio is 0.45～0.50;

The described material that can change different acidic materials electron cloud structures comprises fluoride, boride; Wherein fluoride is ammonium fluoride; Boride dipotassium tetraborate; The amount that described fluoride, boride add is 0.3wt%～1.5wt%;

Y zeolite after modification is NTY, USY; The particle diameter of the Y zeolite after described modification is 800nm～1200nm;

Described amorphous aluminum silicide is prepared by coprecipitation, SiO in the amorphous aluminum silicide of gained ₂weight content be 30%～45%;

The carrying method of described catalyst activity metal, adopt infusion process to prepare, infusion process adopts saturated or excessive impregnation technology, first group VIB metal is selected to the active metal that Mo and/or W and group VIII metal are selected from Co and/or Ni, according to pore structure, load on amorphous aluminum silicide, Y zeolite or aluminium oxide, then through 100～130 ℃ dry 4～14 hours, add appropriate nitric acid peptizing agent, kneading or be rolled into paste, extruded moulding is the cylindrical bars of 5～6 millimeters of diameters; Then through 100～130 ℃ dry 4～14 hours, 450～550 ℃ of roastings, after 3～10 hours, make product catalyst.

The specific embodiment

Below in conjunction with embodiment, the invention will be further described.

Embodiment 1

Carrier A involved in the present invention and catalyst catA.Adopt equi-volume impregnating to be impregnated in 200g amorphous aluminum silicide 1g ammonium fluoride, then through 120 ℃, within dry 2 hours, obtain fluorine-containing amorphous aluminum silicide; Adopt equi-volume impregnating to be impregnated in 90g USY molecular sieve 0.5g boric acid, then through 300 ℃ of USY molecular sieves that obtain boracic for dry 2 hours.Get amorphous aluminum silicide 100g after modification and the USY molecular sieve 45g after modification and 310g by nitric acid and SB aluminium oxide peptization and the adhesive of making, kneading, rolls, make can extrusion paste, extruded moulding.110 ℃ dry 6 hours, 550 ℃ of roastings 4 hours, make carrier A.By the 200ml excessive dipping of W-Ni co-impregnated solution 80g carrier A 2 hours, 110 ℃ were dried 6 hours again, and 500 ℃ of roastings 4 hours, make catalyst catA.

Embodiment 2

Carrier B involved in the present invention and catalyst catB.Adopt equi-volume impregnating to be impregnated in 200g amorphous aluminum silicide 1g boric acid, then through 300 ℃ of amorphous aluminum silicides that obtain boracic for dry 2 hours; Adopt equi-volume impregnating to be impregnated in 90g USY molecular sieve 0.5g ammonium fluoride, then through 120 ℃, within dry 2 hours, obtain fluorine-containing USY molecular sieve.Get amorphous aluminum silicide 100g after modification and the USY molecular sieve 45g after modification and 310g by nitric acid and SB aluminium oxide peptization and the adhesive of making, kneading, rolls, make can extrusion paste, extruded moulding.110 ℃ dry 6 hours, 550 ℃ of roastings 4 hours, make carrier B.By the 200ml excessive dipping of W-Ni co-impregnated solution 80g carrier B 2 hours, 110 ℃ were dried 6 hours again, and 500 ℃ of roastings 4 hours, make catalyst catB.

Comparative example 1

Reference support C and reference catalyst catC.Get amorphous aluminum silicide 100g, USY molecular sieve 45g and 310g, by nitric acid and SB aluminium oxide peptization and the adhesive of making, kneading, rolls, make can extrusion paste, extruded moulding.110 ℃ dry 6 hours, 550 ℃ of roastings 4 hours, make carrier A.By the 200ml excessive dipping of W-Ni co-impregnated solution 80g support C 2 hours, 110 ℃ were dried 6 hours again, and 500 ℃ of roastings 4 hours, make catalyst catC.

The physico-chemical property of table 1 catalyst

Catalyst numbering	catA	catB	catC
				WO 3，wt％	23.5	23.4	23.1
NiO，wt%	7.0	6.7	6.7
				Specific area, m 2/g	245	235	274
Pore volume, ml/g	0.56	0.52	0.46
				Average pore diameter, nm	5.83	5.68	5.34
Infrared total acidity, mmol/g	0.395	0.382	0.364

The invention described above catalyst catA, catB and comparative example catalyst catC are carried out to active evaluation test.Test is carried out on 200ml small hydrogenation device, and raw materials used oil nature is in Table 2.Operating condition is as follows: hydrogen dividing potential drop 14.7MPa, hydrogen to oil volume ratio 1500:1, volume space velocity 1.5h during liquid ^-1.Catalyst activity result of the test is in Table 3.

Table 2 feedstock oil character

Feedstock oil title	Iran VGO
		Density (20 ℃), g ∕ cm 3	0.9164
Boiling range, ℃	528～531
		Viscosity (50 ℃), mm 2∕s	33.69
Viscosity (100 ℃), mm 2∕s	6.944
		Condensation point, ℃	34

[0036]?

Acid number, mgKOH ∕ g	0.49
		Carbon residue, wt%	0.32
S，μg/g	16000
		N，μg/g	1475
C，wt%	85.25
		H，wt%	11.96
BMCI value	48.2
		Refractive power/n D 70	1.4899

Table 3 catalyst activity evaluation result

Catalyst numbering	catA	catB	catC
				Reaction temperature, ℃	385	385	385
Product distributes	?	?	?
				< 370 ℃ of conversion ratios, wt%	64.8	64.6	64.9
Middle distillates oil selectivity, %(132～370 ℃)	85.6	85.2	84.3
				Major product character	?	?	?
Jet fuel (132～282 ℃)	?	?	?
				Freezing point, ℃	<－60	<－60	<－60
Aromatic hydrocarbons, wt%	4.0	4.1	4.1
				Smoke point, mm	29	28	27
Diesel oil (282～350 ℃)	?	?	?
				Cetane number	61	60	59
Condensation point, ℃	-8	-9	-8

[0039] evaluation result by catalyst can find out, the prepared catalyst of the present invention, on the basis of greater activity, has well selective.

Claims (2)

1. a preparation method who controls the hydrocracking catalyst of active metal distribution, is characterized in that:

Technical process comprises: one or several in conventional aluminium oxide, Y molecular sieve, mesoporous material, modified aluminas, SAPO molecular sieve, β zeolite, amorphous silicon aluminium porous material are first flooded to a certain amount of material composition that can change respectively its different acidic materials electron cloud structures, then dry, roasting at a certain temperature; Then adopt kneading method, a certain amount of active metal component of infusion process load, then dry, the roasting of process uniform temperature and time, final catalyst prod obtained;

Described hydrocracking catalyst, the weight of catalyst of take is benchmark, and composition comprises: the Y molecular sieve of 20wt%～60wt% amorphous aluminum silicide, 5～25wt%, in the group VIB metal of oxide 10wt%～30wt% with in the group VIII metal of oxide 3wt%～10wt%;

Described group VIB metal used is selected from Mo and/or W, and group VIII metal is selected from Co and/or Ni, wherein, VI B/(VI B+ VIII) atomic ratio is 0.30～0.70;

The described material that can change different acidic materials electron cloud structures comprises fluoride, boride; Fluoride has the effect that cloud density is reduced, boride has the effect that cloud density is increased, according to the acid feature of different acidic materials, and pore passage structure feature, according to increase with the effect of metal, or reduce with metal be used for selecting to add fluoride or boride; Wherein fluoride is one or more in hydrogen fluoride, ammonium fluoride, tetrabutyl ammonium fluoride, fluosilicic acid, prodan, fluoroacetic acid; Boride is one or more in boric acid, phenyl boric acid, metaboric acid, dipotassium tetraborate, methyl-boric acid; The amount that described fluoride, boride add is 0.1wt%～3wt%;

Described Y zeolite is sodium type Y molecular sieve, or be the Y zeolite after modification, method of modifying comprises the method that adopts Molecular regulator sieve acidity, pore structure, silica alumina ratio, non-framework aluminum parameters, is selected from one or more in hydro-thermal treatment method and ion-exchange process; Y zeolite after modification is one or more in super steady Y molecule-type USY, low-Na and high-Si Y molecular sieve SSY, the high Y molecular sieve of resistance to nitrogen NTY, FY-1, UDY, MUY; The particle diameter of described Y zeolite is 200nm～5000nm;

Described mesopore molecular sieve is one or more in SBA series, MCM Series Molecules sieve, and mesoporous aperture is 5nm～20nm;

Described modified aluminas is a kind of in conventional alumina modified of silicon modification, titanium modification, and in modified aluminas, modifying element proportion is 0.5%～5%;

Described amorphous aluminum silicide is prepared by coprecipitation or grafting copolymerization process, and in the amorphous aluminum silicide of gained, the weight content of SiO2 is 20%～50%;

Described drying condition is as follows: temperature is 50～120 ℃, and the time is 6～12 hours; Described roasting condition is as follows: temperature is 450～650 ℃, and the time is 4～12 hours;

The carrying method of described catalyst activity metal, adopt kneading method, infusion process routine techniques to prepare, first by one or several active metals in group VIB metal and group VIII metal, according to pore structure, load on amorphous aluminum silicide, Y zeolite or aluminium oxide, then drying, add appropriate nitric acid peptizing agent, kneading or be rolled into paste, extruded moulding is the cylindrical bars of 3～8 millimeters of diameters; Then after drying, roasting, make product catalyst.

2. in accordance with the method for claim 1, it is characterized in that: described group VIB metal used is selected from Mo and/or W, and its content is counted 10wt%～25wt% with oxide; Group VIII metal is selected from Co and/or Ni, and its content is counted 3wt%～7wt% with oxide; Wherein, VI B/(VI B+ VIII) atomic ratio is 0.45～0.50;

The described material that can change different acidic materials electron cloud structures comprises fluoride, boride; Wherein fluoride is ammonium fluoride; Boride dipotassium tetraborate; The amount that described fluoride, boride add is 0.3wt%～1.5wt%;

Y zeolite after modification is NTY, USY; The particle diameter of the Y zeolite after described modification is 800nm～1200nm;

Described amorphous aluminum silicide is prepared by coprecipitation, and in the amorphous aluminum silicide of gained, the weight content of SiO2 is 30%～45%;

The carrying method of described catalyst activity metal, adopt infusion process to prepare, infusion process adopts saturated or excessive impregnation technology, first group VIB metal is selected to the active metal that Mo and/or W and group VIII metal are selected from Co and/or Ni, according to pore structure, load on amorphous aluminum silicide, Y zeolite or aluminium oxide, then through 100～130 ℃ dry 4～14 hours, add appropriate nitric acid peptizing agent, kneading or be rolled into paste, extruded moulding is the cylindrical bars of 5～6 millimeters of diameters; Then through 100～130 ℃ dry 4～14 hours, 450～550 ℃ of roastings, after 3～10 hours, make product catalyst.