CN1094075C - Gamma-zeolite contained middle distillate type hydrocracking catalyst and its preparation - Google Patents

Abstract

The present invention relates to a hydrocracking catalyst for producing middle distillate, which uses a modified superhydrophobic Y zeolite as an acid cracking component. The mole ratio of SiO2/Al2O3 of the Y zeolite is 5.0 to 25; the unit cell constant is 2.420 to 2.440 nm; the specific area is 600 to 850 sq. m/g; the Na2O content is less than 0.2%; secondary pores greater than 2.0 nm account for more than 40%; non-skeletal aluminium accounts for 10 to 50% of total aluminium quantity; infrared acidity is from 0.20 to 0.60 mmol/g; under the condition of 25 DEG C and P/Po of 0.1, water adsorption quantity is less than 5w%. The catalyst of the present invention has excellent middle oil selectivity and activity when used for hydrocracking treatment of heavy hydrocarbon material.

Description

A kind of midbarrel oil type hydrocracking catalyst and preparation thereof that contains the Y zeolite

The present invention relates to a kind of hydrocracking catalyst that contains zeolite, handle the petroleum hydrocarbon material, produce intermediate oil.

Hydrocracking is a kind of important PETROLEUM PROCESSING means, especially for the secondary operations distillate, produces all kinds of oil products, hydrocracking especially aborning between the distillate aspect obtain more general application.Good several generations has been experienced in the development of hydrocracking technology, the use of zeolite in hydrocracking catalyst is a qualitative leap of hydrocracking technology, it has changed the shortcoming that amorphous in the past hydrocracking catalyst activity is low, service cycle is short, catalyst reaction temperatures is greatly reduced, not only reduced the severity of course of reaction and the operating flexibility of catalyst is strengthened, and make the stability of catalyst and life-span better, therefore present most hydrocracking commercial plant all uses the hydrocracking catalyst that contains zeolite.But for middle oil type hydrocracking catalyst, except considering activity, also need consider middle distillates oil selectivity, zeolite facies no doubt can increase the lytic activity of catalyst to the stronger acid centre of acid sial, but its strong cracking ability can cause the decline significantly of middle distillates oil selectivity, how when improving catalyst activity, but not sacrifice middle distillates oil selectivity in a large number, search out a kind of better balance in active and this a pair of contradiction of middle distillates oil selectivity, be an emphasis of middle oil type hydrocracking catalyst development and exploitation always.

US4894142 discloses a kind of hydrocracking catalyst, purpose is to provide the middle distillates oil selectivity of catalyst, be characterized in having used a kind of low acidity Y zeolite, these zeolite characteristics are that its TPD acidity is less than 2.0mmol/g, best 1.5mmol/g, in order to reduce acidity, the main preparation characteristic of the related zeolite of this patent is a heat treatment of raw materials zeolite at high temperature, be included in the dry type heat treatment of 676-788 ℃ of temperature hydrothermal treatment consists or best 704 ℃ feeding inert gas, because this zeolitic acid is spent low, when being used for catalytic component processing feedstock oil, although conversion ratio 85w%, reaction temperature is but up to more than 410 ℃, because the reaction temperature height has suppressed hydrogenation reaction, the thermal cracking performance trend of zeolite strengthens, make the middle distillates oil selectivity raising of catalyst not obvious, middle distillates oil selectivity is no more than 70%, solves not talkative a kind of better balance that searched out in active and this a pair of contradiction of middle distillates oil selectivity.

US5190903 discloses the low acidity zeolite that generally is used for oil type hydrocracking catalyst, and purpose is to improve the middle distillates oil selectivity of catalyst, is characterized in having used a kind of NH ₄-TPD acidity is preferably less than 1.5mmol/g low acidity Y zeolite, SiO ₂/ Al ₂O ₃Mol ratio is less than 6, and lattice constant is 2.420-2.440nm, and the main preparation characteristic of the related zeolite of this patent is that the low sodalite after the hydrothermal treatment consists is carried out dry type roasting dehydroxylation, and the dehydroxylation temperature is more than 426 ℃.Handle a kind of VGO with this zeolite as the hydrocracking catalyst of acidic cleavage component preparation, when conversion ratio was controlled at 85w%, reaction temperature was up to 405-425 ℃, and middle distillates oil selectivity has only 55-63%, and the middle distillates oil selectivity of catalyst improves not obvious.

The object of the present invention is to provide a kind of activity good, middle oil type hydrocracking catalyst that selectivity is high and preparation method thereof is used for the hydrocracking process treatment of heavy hydrocarbon material, produces intermediate oil more.The present invention also aims to provide a kind of novel low acidity modification super-hydrophobic Y zeolite to be used for hydrocracking catalyst of the present invention.

Catalyst of the present invention consists of Y zeolite 5-40w%, the group vib metal is selected from Mo and/or W, and by containing 10-40w% in the metal oxide catalyst, VIII family metal is selected from Co and/or Ni, by containing 1-10w% in the metal oxide catalyst, surplus is an inorganic metal refractory oxide carrier component.Above-mentioned inorganic metal refractory oxide carrier component comprises the mixture of aluminium oxide, sial or aluminium oxide and various sial, can also add titanium oxide, zirconia etc., to disperse zeolite component involved in the present invention and to support the hydrogenation metal component.Hydrocracking catalyst specific surface 150-300m of the present invention ²/ g, pore volume 0.25-0.45ml/g, infrared acidity 0.25-0.55mmol/g.

Catalyst of the present invention preferably contains super-hydrophobic Y zeolite component 10-30w% (by catalyst) involved in the present invention, the group vib metal is by containing 15-30w% in the metal oxide catalyst, VIII family metal is by containing 4-8w% in the metal oxide catalyst, and surplus is an inorganic metal refractory oxide carrier component.

The related super-hydrophobic Y zeolite of catalyst of the present invention has following feature: SiO ₂/ Al ₂O ₃Mol ratio is 5.0-25, and lattice constant is 2.420-2.440nm, and the secondary pore volume of＞2.0nm accounts for more than 40% of total pore volume, specific surface 600-850m ²/ g, infrared acidity 0.20-0.60mmol/g, Na ₂O content＜0.2w%, non-framework aluminum account for the 10-50w% of the total aluminium of zeolite, at 25 ℃, and P/P ₀Be 0.1 o'clock, water adsorption amount is less than 5w%, and n-butanol adsorption experiment residual value is less than 0.4, ion exchange capacity＜0.07.

The further feature of the super-hydrophobic Y zeolite that catalyst of the present invention is related is: SiO ₂/ Al ₂O ₃Mol ratio is 6.0-17, lattice constant 2.425-2.435nm, and＞2.0nm secondary micropore accounts for more than 50%, specific surface 700-800m ²/ g, infrared acidity 0.25-0.50mmol/g.

In the Preparation of catalysts process of the present invention, its forming method can adopt various known routine techniques, as balling-up or extrusion, but its various forming methods all are not construed as limiting the invention, purpose all is that the related zeolite of catalyst of the present invention is dispersed in the catalyst carrier component, and makes catalyst loading hydrogenation metal component.Moulding as catalyst of the present invention can be adopted first extruded moulding, the mode of impregnating metal component again, be about to Y zeolite involved in the present invention by 5-40w% (by catalyst) and inorganic metal refractory oxide carrier such as sial or/and macroporous aluminium oxide 10-50w% (by catalyst) dry powder blend evenly after, the adhesive that adding 10-40w% (by catalyst) aperture aluminium oxide makes through the nitric acid peptization mixes pinches or is rolled into paste, extruded moulding, be generally garden post bar, diameter 1.2-1.8mm also can adopt special-shaped bar such as clover or bunge bedstraw herb shape.Behind carrier strip drying, the calcination activation, adopt the saturated or excess solution dipping hydrogenation metal in hole, the hydrogenation metal dipping solution comprises at least a group vib and a kind of VIII family metal, after the carrier strip drying behind the carrying metal, the activation finished catalyst.

The super-hydrophobic Y zeolite preparation method's that catalyst of the present invention is related concrete steps are as follows:

1, Na ₂O content is less than the Y prepare zeolite of 0.2w%: Na ₂O content can prepare with following a or b method less than the Y zeolite of 0.2w%.

A, be raw material with the NaY zeolite, with concentration is 1.0-5.0M, preferably the ammonium salt solution of 2.0-3.0M is exchange liquid, zeolite concentration in the exchange slurries is 0.05-1.0g/ml, preferably 0.1-0.5g/ml at 70-150 ℃, preferably stirred 0.5-3 hour for 80-120 ℃ time, repeat above-mentioned ion-exchange repeatedly, up to making Na ₂The Y zeolite of O＜0.2w%.

B, be raw material with the NaY zeolite, with concentration is 1.0-5.0M, preferably the ammonium salt solution of 2.0-3.0M is exchange liquid, zeolite concentration in the exchange slurries is 0.05-1.0g/ml, 0.1-0.5g/ml preferably, under 70-150 ℃, preferably 80-120 ℃ was stirred 0.5-3 hour, ion-exchange 2-3 time makes Na ₂O content is less than the Y zeolite product I of 3.0w%.I places the high-temperature roasting stove with Y zeolite product, at self steam or feed steam, 450-600 ℃, under the 0.01-0.2MPa press water steam roasting 0.5-3.0 hour, makes product II.Product II by the ion-exchange process of preparation product I and ammonium salt solution ion-exchange 3-4 time, is made Na ₂O content is less than the Y zeolite of 0.2w%.

2, the Na that step 1 is prepared ₂O content places the high-temperature roasting stove less than the Y zeolite of 0.2w%, and at self steam or feeding steam, 550-700 ℃, 0.01-1.0MPa press water steam was handled 0.5-10 hour down, promptly got SiO ₂/ Al ₂O ₃Mol ratio is the super-hydrophobic Y zeolite of 5.2-6.0.

The super-hydrophobic Y zeolite that last step is obtained can get SiO with chemical method dealuminzation optionally ₂/ Al ₂O ₃Mol ratio is the super-hydrophobic Y zeolite of 6.5-25.

Above-mentioned chemical method optionally dealuminzation can use acid solution (hydrochloric acid, nitric acid, acetic acid, oxalic acid etc.) or organic complexing agent (as acetylacetone,2,4-pentanedione, ethylenediamine tetra-acetic acid etc.) optionally to remove the non-framework aluminum of zeolite.The concentration of above-mentioned acid solution or organic complexing agent is generally 0.1-1M, and the processing time is 1-4 hour.

Compared with prior art, super-hydrophobic Y zeolite preparation method involved in the present invention, the raw material Na of hydrothermal treatment consists ₂O content is strict controlled in below the 0.2w%, be preferably in below the 0.15w%, under lower temperature 550-700 ℃, prepare low acidity super-hydrophobic Y zeolite under the 0.01-1.0MPa pressure, prepare zeolite process energy consumption involved in the present invention is low, though the relative US4894142 zeolite treatment of treatment temperature temperature is low, get zeolite but still can obtain low acidity, the general 1.0-1.5mmol/g of zeolite TPD acidity involved in the present invention, zeolite acidity is low, its cracking is relaxed, guaranteed middle distillates oil selectivity; Though zeolite acidity involved in the present invention reduces by a relatively large margin, the acid centre that its acid strength characteristics make zeolite involved in the present invention have all kinds of intensity of proper proportion distribution, NH as shown in the table ₄-TPD acidity (weighing by desorption temperature) distributes and finds out, it mainly is 250-500 ℃ of represented middle strong acid center that its acidity distributes, its acidity accounts for 50.4% of total acidity, ℃ represented strong acid center simultaneously＞500, its acidity accounts for 21.1% of total acidity, thereby has also guaranteed the cracking activity to heavy hydrocarbon material when being used for catalyst.

NH ₄150-250 ℃ 250-400 ℃ 400-500 ℃ of-TPD acidity and varying strength acidity distribution acidity acidity distribution mmol/g thereof＞500 ℃ 1.21 28.5% 35.2% 15.2% 21.1%

Though some modified Y zeolite solid acid amounts of prior art are reduced to a certain extent, be not enough to significantly improve middle distillates oil selectivity, and strong acid center are too much, to getting the poisonous substance sensitivity in the feedstock oil.Super-hydrophobic Y zeolite during the catalyst that hydrocracking process of the present invention relates to is formed is that raw material Y zeolite is carried out pressurized thermal water processing and chemical after-treatment reason again after amine and acid treatment dealuminzation step are taken off in roasting, its modified Y zeolite sial molecular proportion improves, the solid acid amount further reduces, Y zeolite involved in the present invention is after deep sealumination modified, the acid site number reduces, infrared acidity is reduced to 0.2-0.6mmol/g, preferably 0.25-0.5mmol/g.

Compare with the super-hydrophobic Y zeolite of prior art for preparing, the super-hydrophobic Y zeolite of the inventive method preparation has higher degree of crystallinity, specific surface, ratio, lattice constant, silica alumina ratio and the secondary pore of suitable non-framework aluminum and total aluminium.High-ratio surface and more secondary pore have not only promoted the performance of hydrogenation activity, also help the raising to the open loop activity of polycyclic aromatic hydrocarbon, and can reduce carbon deposit.Thereby with reference catalyst relatively, handle a kind of vacuum gas oil (VGO) equally, all show better activity and middle distillates oil selectivity.

Zeolite involved in the present invention is used for catalyst that hydrocracking process of the present invention relates to use can not only satisfy when producing intermediate oil hydrocracking catalyst to the needs of lytic activity, simultaneously less acid site and more weak acid centre have reduced the chance of second pyrolysis and excessive fragmentation generation, the catalyst that makes hydrocracking process of the present invention relate to use not only has higher lytic activity, also has good middle distillates oil selectivity simultaneously.During hydrocracking heavy oil, being that the catalyst of acidic components is compared with super-hydrophobic Y zeolite with prior art for preparing, is that the catalyst of acidic components has middle distillates oil selectivity height, active good characteristics with the super-hydrophobic Y zeolite of the inventive method preparation.When using the feedstock oil that one-stage serial PROCESS FOR TREATMENT various types of properties differs greatly, when keeping being not less than the conversion ratio of 60w%, middle distillates oil selectivity is not less than 80%, and reaction temperature is not higher than 390 ℃; Even if under the single hop list agent process conditions of high nitrogen charging, reaction temperature generally is not higher than 405 ℃ yet.

Catalyst of the present invention is used for hydrocracking process, be particularly suitable for treatment of heavy hydrocarbon material, the boiling range scope of heavy hydrocarbon material is at 250-600 ℃, generally at 300-550 ℃, catalyst of the present invention is when handling common VGO, and reaction condition generally is under the hydrogen existence condition, the best 10-20MPa of reaction pressure, hydrogen to oil volume ratio 500-2000, air speed 0.5-2.0h ^-1, reaction temperature 370-420 ℃.Catalyst of the present invention is mainly used in hydrocracking process production intermediate oil, and it is active high that the zeolite of the present invention of related use has catalyst of the present invention, the characteristics that middle distillates oil selectivity is good.The high open loop activity that zeolite of the present invention had of related use makes catalyst of the present invention be particularly suitable for processing the high aromatic hydrocarbons height of many rings and does inferior heavy pledge material.

Example 1

(1) 1M ³Add 130kg industry NH in the swap tank of liner enamel ₄NO ₃(chemical plant, Dalian product, purity＞99.5%) adds 800 liters of industrial water purification, is made into 2M NH ₄NO ₃Solution is heated to 70 ℃, adds 120KgNaY zeolite (Wenzhou catalyst plant product, butt 50w%), stirs exchange 3 hours down at 70 ℃, repeats this exchange step 12 times, filters, and is washed to neutrality, obtains Na ₂O content is 0.18% Y zeolite, oven dry.(2) zeolite of above-mentioned washing oven dry is put into revolving burner, be rapidly heated to 650 ℃, at 0.4MPa pressure, roasting is 6 hours under 100% steam, obtains super-hydrophobic Y zeolite A of the present invention.Its physico-chemical property sees Table 1.

Example 2

(1) gets 5.0kg NaY zeolite (with the example 1) NH that to be added to 50 liters of concentration be 2M ₄NO ₃In the solution, stir down at 100 ℃, ion-exchange 2 hours exchanges secondary altogether, and filter then, wash to neutrality, and oven dry, obtain product I.(2) product I is placed the high-pressure rotary stove, at 550 ℃, roasting is 2 hours under the 100% steam 0.1MPa pressure, obtains product II.(3) NH that product II is put into 50 liters of concentration is 2M ₄NO ₃In the solution, stir ion-exchange 2 hours down, exchange altogether 3 times, filter then, wash to neutrality at 100 ℃, and oven dry, product III obtained.(4) with product III as in the revolving burner, at 550 ℃, roasting is 4 hours under the 100% steam 0.2MPa pressure, obtains zeolite B of the present invention.Its physico-chemical property sees Table 1.

Example 3

(1) NH that 2.0kg NaY zeolite (with example 2) is added to 160 liters of concentration is 3M ₄NO ₃In the solution, stir ion-exchange 0.5 hour down at 150 ℃, coion exchange 12 times obtains Na ₂O content is 0.17% Y zeolite, and oven dry obtains product I.(2) product I is put into revolving burner, at 700 ℃, 0.01MPa pressure, roasting is 4 hours under 100% steam, obtains product II.(3) get product II400g, putting into concentration is 4 liters of hydrochloric acid solutions of 0.4M, handles 2 hours, filters, washs to neutral, and oven dry obtains super-hydrophobic Y zeolite C of the present invention.Its physico-chemical property sees Table 1.

Example 4:

The super-hydrophobic Y zeolite A100 that example 1 is obtained restrains; Putting into concentration is 1 liter of acetylacetone,2,4-pentanedione solution of 0.4M, handles 2 hours, filters, and with 3 liters of deionized water washings, oven dry obtains super-hydrophobic Y zeolite D.Its physico-chemical property sees Table 1.

Example 5 (reference)

(1) NH that 3.0kg NaY zeolite (with example 1) is joined 18 liters of concentration is 2M ₄NO ₃In the solution, 90 ℃ of following ion-exchanges 1 hour, coion exchange 8 times, filtration, washing, drying obtain Na ₂O content is 0.27% Y zeolite.(2) the Y zeolite behind the washing and drying is placed revolving burner, at 750 ℃, 0.8MPa pressure, hydrothermal treatment consists is 6 hours under 100% steam, obtains super-hydrophobic Y zeolite E.Its physico-chemical property sees Table 1.

Example 6 (reference)

(1) NH that 1.0kg NaY zeolite (with example 1) is joined 8 liters of concentration is 1.5M ₄NO ₃In the solution, stir down at 100 ℃, ion-exchange 2 hours exchanges 2 times altogether, filters then, washs to neutrality, and oven dry obtains product I.(2) with product I at 550 ℃, 0.1MPa pressure under 100% steam, at rotation kiln roasting 2 hours, obtains product II.(3) with product II (1) ion-exchange 1 time set by step, obtain Na ₂O content is the Y zeolite product III of 0.37W%.(4) at 800 ℃, 0.1MPa pressure, under 100% steam, hydrothermal treatment consists product III4h obtains super-hydrophobic Y zeolite F in the high-pressure rotary stove.Its physico-chemical property sees Table 1.

Example 7 (reference)

The hydrochloric acid solution that it is 1.5M that the super-hydrophobic Y zeolite D600g that example 4 is obtained puts into 6 liters of concentration was handled 2 hours, filtered, washing is to neutral, obtains Y zeolite G after the oven dry.Its physico-chemical property sees Table 1.

Example 8 (reference)

Synthetic SiO ₂/ Al ₂O ₃Than the LZ-210 zeolite (preparation method who is narrated with U.S. Pat 4503023) that is 9: 1, press the method for U.S. Pat 4597956 narrations again, method with a kind of aluminum sulfate crystallizing and washing is handled washes out applied fluoride in this secondary synthesis step.With this LZ-210 zeolite that obtains as the raw material zeolite, again in 100% water vapour 750 ℃ of hydrothermal treatment consists 16 hours, obtain super-hydrophobic Y zeolite H.Its physico-chemical property sees Table 1.

The physico-chemical property of table 1 super-hydrophobic Y zeolite A-G

Example	1	2	3	4	5	6	7	8
									The zeolite numbering	A	B	C	D	E	F	G	H
Non-framework aluminum/total aluminium * 100%	45	40	35	10	75	65	15	83
									Secondary pore (＞2.0nm) %	50	52	56	54	53	55	58	30
Infrared acidity (mmol/g)	0.22	0.33	0.55	0.30	0.12	0.15	0.19	0.17
									Na 2O w％	0.15	0.14	0.10	0.11	0.26	0.35	0.23	1.25
Specific surface (BET method) m 2/g	630	660	780	840	520	470	750	710
									SiO 2/Al 2O 3(mol ratio)	5.2	6.0	13.0	23.9	5.3	5.4	32.0	9.4
Lattice constant, nm	2.430	2.432	2.428	2.430	2.429	2.428	2.429	2.430
									Ion exchange capacity	0.051	0.045	0.057	0.053	0.041	0.035	0.060	0.032
N-butanol absorption residual value	0.22	0.25	0.15	0.17	0.25	0.22	0.51	0.43
									Water adsorption amount, 25 ℃ of P/P 0＝0.1w％	4.3	2.1	4.0	4.5	3.0	2.7	10.2	1.0

It below is the comparing result that zeolite involved in the present invention and reference zeolite are used for midbarrel oil type hydrocracking catalyst.Feedstock oil character sees Table 2.Middle distillates oil selectivity calculates by " (boat yield of coal+diesel yield)/＜370 ℃ of product yields ".Table 3 data show that catalyst A selectivity of the present invention is significantly higher than reference catalyst X under the suitable situation of activity; Catalyst A activity of the present invention is significantly higher than reference catalyst E under the suitable situation of middle distillates oil selectivity.Illustrate that super-hydrophobic Y zeolite involved in the present invention is used for hydrocracking catalyst processing heavy oil and has excellent middle oil selectivity and activity.The reaction pressure of following examples is 15MPa, and feedstock oil enters the cracking zone cracking through giving after refining, and hydrogen to oil volume ratio is 1500, and air speed is 1.5h ^-1

Example 9

Get zeolite A31.1g of the present invention, add 80g amorphous aluminum silicide (SiO ₂Content 40w%, specific area 310m ²/ g, pore volume is 0.75ml/g) and the mixed paste of pinching into of 250g alumina adhesive, extruded moulding, 110 ℃ of dryings 12 hours, after 500 ℃ of activation made carrier in 4 hours, again with W-Ni altogether the maceration extract dipping make catalyst finally contain nickel oxide 7w%, tungsten oxide 22w%, 110 ℃ of dryings 12 hours, and 500 ℃ of activation obtained catalyst A after 3 hours.

Example 10

Except the zeolite A in the example 9 is changed into the zeolite E, preparation process and catalyst are formed identical with example 9.The catalyst that obtains is compiled and is E.

Example 11

Except the zeolite A in the example 9 being changed into outside a kind of high acidity USY type zeolite (infrared acidity 1.1mmol/g, Fushun Petrochemical Company catalyst plant), preparation process and catalyst are formed identical with example 9.The catalyst that obtains is compiled and is X.Table 2. raw material oil properties

Density, d 4 20	0.9066
		Boiling range, ℃
IBP	346
		10％	388
50％	433
		90％	489
EP	526
		Mass spectral analysis, w%
Alkane	18.3
		Cycloalkane	43.1
Aromatic hydrocarbons	34.8
		Colloid	3.8
Carbon residue, w%	0.01
		S，w％	0.59
N，μg/g	1419
		The BMCI value	43.2

Table 3. evaluating catalyst result

The catalyst numbering	Catalyst A	Catalyst E	Catalyst X
				Reaction temperature, ℃	380	400	380
Conversion ratio, w%	60	60	60
				Middle distillates oil selectivity, %	83.2	82.1	74.1

Following example be just form by catalyst of the present invention with Y zeolite involved in the present invention and scope in the catalyst that obtains, find out that from the result of table 4 they have all shown good active and middle distillates oil selectivity.

Example 11

Get zeolite C20.7g, the commodity amorphous silicon al composition 86.3g (SiO that a kind of Fushun Petrochemical Company catalyst plant is produced ₂Content 40w%, specific area 290m ²/ g, pore volume is 0.7ml/g), the back that is mixed is dissolved in the mixed paste of pinching into of adhesive that rare nitric acid peptization 28g aperture boehmite of 85ml distilled water is made with 5.7ml40% nitric acid, behind the post orifice plate extruded moulding of φ 1.7mm garden, 110 ℃ of dryings, got carrier in 3 hours through 500 ℃ of activation again, be total to the maceration extract dipping with W-Ni again, 110 ℃ of dryings, got catalyst CAT1 of the present invention in 3 hours through 500 ℃ of activation.Catalyst is compiled to CAT1, consists of WO ₃23.5w%, NiO 7.2w%, hydrophobic Y zeolite 10w%.Catalyst specific surface 260m ²/ g, pore volume 0.320ml/g.

Example 12

Get zeolite C41.6g of the present invention, a kind of acid sial component 106.3g (SiO that is dispersed on the macroporous aluminium oxide matrix ₂Content 25w% is a kind of macroporous aluminium oxide 56.3g to be mixed the back drying with a kind of acid sial component 50.0g making beating make specific area 350m ²/ g, pore volume is 0.9ml/g), the back that is mixed is dissolved in the mixed paste of pinching into of adhesive that rare nitric acid peptization 28g aperture boehmite of 85ml distilled water is made with 5.7ml40% nitric acid, after crossing φ 1.7mm garden post orifice plate extruded moulding, 110 ℃ of dryings, activate 3 hours through 500 ℃ again and get carrier, be total to the maceration extract dipping, got CAT2 of the present invention in 3 hours through 500 ℃ of activation again with W-Ni.Catalyst is compiled to CAT2, consists of MoO ₃23.4w%, NiO6.7w%, hydrophobic Y zeolite 20w%.Catalyst specific surface 268m ²/ g, pore volume 0.329ml/g.

Example 13

Get zeolite C62.4g involved in the present invention, commodity macroporous aluminium oxide 116.4g (the specific area 450m that a kind of Fushun Petrochemical Company catalyst plant is produced ²/ g, pore volume is 1.2ml/g), the back that is mixed is dissolved in the mixed paste of pinching into of adhesive that rare nitric acid peptization 28g aperture boehmite of 85ml distilled water is made with 5.7ml40% nitric acid, after crossing φ 1.7mm garden post orifice plate extruded moulding, at 110 ℃ of dry carriers that get, be total to the maceration extract dipping with W-Ni, got catalyst CAT3 of the present invention in 3 hours through 500 ℃ of activation again.Catalyst is compiled to CAT3, consists of WO ₃24.5w%, NiO6.8w%, hydrophobic Y zeolite 30w%.Catalyst specific surface 278m ²/ g, pore volume 0.318ml/g.

Comparative example:

Be a kind of existing commercial senior middle school catalyst for distillate hydro-cracking (the Fushun Petrochemical Company catalyst plant is produced, the industrial trade mark 3824) catalyst.The key component of catalyst is that the trade mark is y-type zeolite and the macroporous aluminium oxide of USY, and metal group becomes WO ₃20.6w%, NiO6.1w%.Catalyst specific surface 287m ²/ g, pore volume 0.346ml/g, numbering CAT4.Table 4 evaluation result catalyst CAT1 CAT2 CAT3 CAT4 reaction temperature (℃) 385 376 372 380 conversion ratios, w% 60 60 60 60 middle distillates oil selectivities, %83.9 82.1 80.2 74.5

Embodiment 14

This example uses the catalyst CAT2 of the present invention of embodiment 12, and according to the process conditions of US5190903, reaction pressure is 13.8MPa, and hydrogen to oil volume ratio is 1500, and air speed is 1.0h ^-1Feedstock oil is directly contacted with catalyst of the present invention, handle the close heavy VGO of a kind of character (api gravity 22.9, boiling range 340-540 ℃, sulfur content is 1.5w%, nitrogen content 1200 μ g/g),＜371 ℃ of product yields are during up to 85w%, and only 395 ℃ of reaction temperatures are collected 149-371 ℃ of (300-700) intermediate oil, middle distillates oil selectivity 74.5% illustrates that catalyst of the present invention has good activity and middle distillates oil selectivity.

Claims (13)

1, a kind of hydrocracking catalyst that is used to produce intermediate oil, active metal component is selected from group vib metal and VIII family metal, in catalyst, contain 10-40w% by metal oxide group vib metal, in catalyst, contain 1-10w% by metal oxide VIII family, and inorganic metal refractory oxide carrier component, it is characterized in that also containing a kind of low acidity modification super-hydrophobic Y zeolite, content is 5-40w%, said Y zeolite SiO ₂/ Al ₂O ₃Mol ratio is 5.0-25, and lattice constant is 2.420-2.440nm, and the secondary pore of＞2.0nm accounts for more than 40%, specific surface 600-850m ²/ g, infrared acidity 0.20-0.60mmol/g, Na ₂O content＜0.2w%, non-framework aluminum account for the 10-50w% of the total aluminium of zeolite, at 25 ℃, and P/P ₀Be 0.1 o'clock, water adsorption amount is less than 5w%, and n-butanol adsorption experiment residual value is less than 0.4, ion exchange capacity＜0.07.

2, by the catalyst of claim 1, the specific area that it is characterized in that described catalyst is 150-300m ²/ g, pore volume are 0.25-0.45ml/g, and infrared acidity is 0.25-0.55mmol/g.

3, by the catalyst of claim 1, it is characterized in that described super-hydrophobic Y zeolite SiO ₂/ Al ₂O ₃Mol ratio 6.0-17, lattice constant 2.425-2.435nm,＞2.0nm secondary micropore accounts for more than 50%, specific surface 700-800m ²/ g, infrared acidity 0.25-0.50mmol/g.

4, by the catalyst of claim 1, it is characterized in that described refractory metal oxide is selected from aluminium oxide and/or sial and titanium oxide, zirconic a kind of.

5, press the catalyst of claim 1, it is characterized in that described group vib metal is selected from Mo and/or W, its content accounts for the 15-30w% that catalyst is formed by oxide, and described VIII family metal is selected from Co and/or Ni, and its content accounts for the 4-8w% that catalyst is formed by oxide.

6, a kind of claim 1 Preparation of catalysts method adopts conventional shaping of catalyst and reactive metal carrying method, it is characterized in that the preparation method of related super-hydrophobic Y zeolite is as follows:

A, preparation Na ₂The Y zeolite of O content＜0.2w%;

B, the zeolite that step a is obtained place the high-temperature roasting stove, at self steam or feed under the water vapor conditions, in 550-700 ℃, under the 0.01-1.0MPa press water steam roasting 0.5-10 hour, make SiO ₂/ Al ₂O ₃Mol ratio is the super-hydrophobic Y zeolite of 5.2-6.0.

7, by the method for claim 6, it is characterized in that the resulting super-hydrophobic Y zeolite of step b is carried out optionally dealuminzation, obtain SiO ₂/ Al ₂O ₃Mol ratio is the super-hydrophobic Y zeolite of 6.5-25.

8, by the method for claim 6, it is characterized in that described Na ₂The Y zeolite of O content＜0.2w% prepares with the following step:

A, usefulness solubility ammonium salt and the ion-exchange of NaY zeolite, temperature is 70-150 ℃, time 0.5-3.0 hour, repeated exchanged twice obtained Na ₂The Y zeolite product I of O content＜3.0w%;

B, the zeolite I that step a is obtained place the high-temperature roasting stove, at self steam or feed under the water vapor conditions, at 450-600 ℃, under the 0.01-0.20MPa press water steam, roasting 0.5-3.0 hour, obtain product II;

C, product II is carried out ion-exchange 2-3 time again by a step, make Na ₂The Y zeolite of O content＜0.2w%.

9, by the method for claim 8, it is characterized in that the solubility ammonium salt among the described step a is selected from ammonium chloride, ammonium nitrate, ammonium sulfate, in the aqueous solution with the NaY zeolite at 70-150 ℃ of ion-exchange 0.5-3.0 hour, repeated exchanged is repeatedly prepared Na ₂The Y zeolite of O content＜0.2w%.

10, by the method for claim 6, it is characterized in that step b is: the zeolite that step a is obtained places the high-temperature roasting stove, at self steam or feed under the water vapor conditions, in 570-650 ℃, under the 0.1-0.6MPa press water steam roasting 2-6 hour, makes SiO ₂/ Al ₂O ₃Mol ratio is the super-hydrophobic Y zeolite of 5.2-6.0.

11, by the method for claim 7, it is characterized in that described selectivity dealuminzation is to be undertaken by being selected from a kind of of acid solution, organic complexing agent.

12, by the method for claim 11, it is characterized in that described acid solution is selected from hydrochloric acid, nitric acid, acetic acid, oxalic acid, described organic complexing agent is selected from acetylacetone,2,4-pentanedione, ethylenediamine tetra-acetic acid.

13, by the method for claim 8 or 9, it is characterized in that adopting the concentration of exchange slurries mesolite in the described ion-exchange step is 0.05-1.0g/ml, the soluble ammonium concentration of salt solution is 1-4M, and the exchange temperature is 80-120 ℃, and be 1-2 hour swap time.