CN100457271C - Drying method of supported catalyst and preparation method of hydrocracking catalyst - Google Patents

Abstract

The invention relates to a method for drying carrier catalyst and a method for preparing oil type hydrogen cracking catalyst. Wherein, it uses ultrasonic radiation in the drying process. Compared with present technique, the invention can reduce the non-uniform distribution of carrier components in the drying process, to improve the property. And the hydrogen cracking catalyst has improved activity and selectivity.

Description

The drying means of loaded catalyst and the preparation method of hydrocracking catalyst

Technical field

The present invention relates to the drying means of a kind of drying means of loaded catalyst, particularly load hydrogenation catalyst.The invention still further relates to a kind of preparation method of hydrocracking catalyst, particularly the preparation method of middle oil type hydrocracking catalyst.

Background technology

Loaded catalyst is widely used a kind of catalyst, and the general solution impregnating carrier that contains active component that adopts of loaded catalyst obtains through processes such as super-dry, roastings then.Hydrogenation catalyst generally is carrier with the refractory oxide, is active component with the metal with hydrogenation performance, and the preparation method of employing is mainly infusion process.As Hydrobon catalyst, hydrocracking catalyst, hydrotreating catalyst, catalyst for hydro-upgrading etc.The carrier of these hydrogenation catalysts mainly comprises aluminium oxide, silica, amorphous aluminum silicide, titanium oxide, zirconia, molecular sieve, active carbon, kaolin, clay etc., advances to select according to the performance requirement of catalyst.Active metal component is generally one or more in group vib and the VIII family.The preparation method is generally and will contains the solution impregnated catalyst carrier of active metal component, and dry then, roasting obtains final catalyst.

More and more heavier, the quality problem worse and worse of petroleum in the present world wide, hydrogen addition technology becomes the important manufacturing process of heavy hydrocarbon oil lighting and upgrading.The application of hydrogenation catalyst more and more widely, and is also more and more higher to the performance requirement of hydrogenation catalyst.

Hydrocracking catalyst is a kind of bifunctional catalyst, has hydrogenation performance and cracking performance, and non-noble metal hydrocracking catalyst generally selects for use VIB and VIII family metal to make the hydrogenation component, and acidic components can be selected crystal formation zeolite and/or amorphous aluminum silicide for use.Hydrocracking catalyst generally is divided into light oil type hydrogen cracking catalyst, middle oil type hydrocracking catalyst, flexibility hydrocracking catalyst etc. according to the difference of purpose product.Because the demand of distillate constantly increases between city's field alignment, therefore, middle oil type hydrocracking catalyst demand increases, the serviceability of centering oil type hydrocracking catalyst, and particularly middle grease separation is selected and is had higher requirement.The at present industrial middle oil type hydrocracking catalyst that generally uses all needs amorphous aluminum silicide and zeolite component to be used, to satisfy the dual needs to catalyst activity and middle distillates oil selectivity.

Zeolite facies have stronger acid centre to acid sial, can increase the lytic activity of catalyst, but its strong cracking ability can cause declining to a great extent of middle distillates oil selectivity, therefore need search out a kind of better equilibrium in active and this a pair of contradiction of middle distillates oil selectivity.Solve this a pair of contradiction of reactive activity and selectivity, must be according to of the requirement of middle oil type hydrocracking catalyst to acidic cleavage function and hydrogenating function balance coupling, the zeolite of development of new and amorphous silicon aluminum, and reach activity required in the course of reaction and optimum position optionally, thereby achieve the goal by adjust ratio that amorphous aluminum silicide and zeolite component suit and the distribution of metal component on carrier in carrier.

US4894142 discloses a kind of hydrocracking catalyst, purpose is to improve the middle distillates oil selectivity of catalyst, this catalyst is to contain amorphous aluminum silicide and a kind of low acidity Y zeolite, the related zeolite characteristics of this catalyst 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 zeolite that this patent relates to is a heat treatment of raw materials zeolite at high temperature, comprise the dry type heat treatment of 676-788 ℃ of following 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%, is not settled properly in active and this a pair of contradiction of middle distillates oil selectivity.

The US4517074 patent disclosure a kind of hydrocracking catalyst, produce the intermediate oil of 300-700 ℉ (149-371 ℃), charging is hydrodenitrogeneration and/or hydrodesulfurization charging preferably, this catalyst is except using zeolite component, its characteristics are to use a kind of Al ₂O ₃-SiO ₂Dispersion, its SiO ₂Content reaches 20%-65%, though the amorphous aluminum silicide in the dispersion has certain lytic activity, need be dispersed on the alumina substrate as macropore Υ-Al ₂O ₃Make carrier component, to obtain the pore volume and the specific surface of a large amount of hydrogenation metal component of carrying.Though this catalyst has higher middle distillates oil selectivity, general more than 80%, activity is lower, reach 60v% and transform, and reaction temperature is generally more than 400 ℃, this patent example by use a kind of in claim at Υ-Al ₂O ₃Be dispersed with the component of 75% high sial and cooperate zeolite such as the LZ-10 zeolite, reaction temperature also will reach 389 ℃.

In the preparation process of existing loaded catalyst, drying steps generally is to adopt common dry run, does not optimize drying condition, and the serviceability of catalyst is had certain influence.The CN1566280A patent disclosure Hydrobon Catalyst And Its Preparation Method of a kind of platiniferous and/or tungsten and nickel and/or brill, on this catalyst contains a kind of heat-resistant inorganic oxide carrier and loads on this carrier mutually and/or tungsten and nickel and/or brill, described catalyst is obtained by the dipping solution dipping heat-resistant inorganic oxide carrier and the drying of platiniferous and/or tungsten and nickel and/or brill compound, comprise a step in the dipping process wherein, the described dry microwave drying of adopting with the mixture of ultrasonic wave radiation impregnation solution and heat-resistant inorganic oxide carrier.Because adopted ultrasonic wave to handle and microwave drying, the catalyst of preparation has higher hydrodesulfurization activity.This procedure is comparatively complicated.

Summary of the invention

At the deficiencies in the prior art, the invention provides a kind of drying means of loaded catalyst, the active component of load is evenly dispersed on the carrier inner surface more.The present invention also provides a kind of preparation method of middle oil type hydrocracking catalyst, makes activity of such catalysts and selectivity reach the better fit effect.

The dry run of loaded catalyst of the present invention comprises following content: the catalyst carrier behind the dipping adopts conventional method to carry out drying, in dry run, use the ultrasonic wave radiation, the ultrasonic wave radiation is adopted and is interrupted radiative process, each radiated time is 0.5～120 minute, preferred 1～60 minute, radiation is 1-10 time altogether, and be 5-360 minute the blanking time when adopting repeatedly radiation, preferred interval 20～120 minutes.Radiant power be 1-5000 watt/liter by the ratio of radiant matter volume, preferred 10～1000 watts/liter.Frequency of ultrasonic is 10～180kHz, preferred 20～100kHz.

Drying condition is generally at 80～200 ℃, and dry 1～15 hour, can be dry under a temperature, also can in dry run, adjust baking temperature.The ultrasonic wave radiation is preferably in material moisture when being 90w%～30w%, finishes when material moisture is 10w%～50w%.

The preparation process of oil type hydrocracking catalyst comprises following content among the present invention: select to contain the catalyst carrier of Y zeolite, dipping solution impregnation catalyst agent carrier and drying and roasting with molybdenum and/or tungsten, nickel and/or brill compound get final catalyst.Wherein in dry run, use the ultrasonic wave radiation, the ultrasonic wave radiation is adopted and is interrupted radiative process, each radiated time is 0.5～120 minute, preferred 1～60 minute, radiation is 1-10 time altogether, preferred 1～4 time, be 5-360 minute the blanking time when adopting repeatedly radiation, preferred interval 20～120 minutes.Radiant power be 1-5000 watt/liter by the ratio of radiant matter volume, preferred 10～1000 watts/liter.Frequency of ultrasonic is 10～180kHz, preferred 20～100kHz.The ultrasonic wave radiation is preferably in material moisture when being 90w%～30w%, finishes when material moisture is 10w%～50w%.

Catalyst carrier can be selected the component of this area routine, can the selective oxidation silicone content be the amorphous silicon aluminium of 20w%～70w% as amorphous aluminum silicide, and the Y zeolite can adopt SiO ₂/ Al ₂O ₃Mol ratio is 7～30 Y zeolite.The content of amorphous aluminum silicide is generally 0～60w%, and the content of Y zeolite is generally 5w%～35w%.The content of reactive metal molybdenum and/or tungsten (in oxide) is generally 5w%～40w%, and the content of nickel and/or cobalt (in oxide) is generally 1w%～15w%.Catalyst can also contain carrier components such as aluminium oxide, and needed auxiliary component.

The drying condition of catalyst is generally at 80～200 ℃, and dry 1～15 hour, can be dry under a temperature, also can in dry run, adjust baking temperature.Also can adopt modes such as microwave drying.The roasting condition of catalyst is 350～550 ℃ of following roastings 1～8 hour.

Loaded catalyst of the present invention is owing to use ultrasonic radiation in dry run, greatly improved dry environment, make catalyst in dry run, metallic solution keeps even distribution always, can not make metal be tending towards concentrating on the catalyst outer surface because of capillarity, make the duct in the dry run especially maintain metallic solution than [inside, and then behind bone dry, the metal that can evenly distribute in the duct increases the effective active center.When being used for the preparation oil type hydrocracking catalyst, because the active metal component in the catalyst has good dispersity, the hydrogenation performance of catalyst is further improved, consequently help stopping the crackate that acid centre takes place and be hydrogenated to rock-steady structure, reduce further cracking, and then improve the selectivity of intermediate oil.

The specific embodiment

According to method provided by the invention, the ultrasonic generator that wherein said ultrasonic wave radiation is used can be to adopt prior art for preparing or commercially available any supersonic generator, as washing trough formula supersonic generator or probe type ultrasonic wave producer etc.

According to method provided by the invention, described molybdenum and/or tungsten, nickel and/or the cobalt compound of containing, can be by in the soluble compound that is selected from nickeliferous and/or cobalt metal one or more, as the solution of one or more preparations in their nitrate, acetate, soluble carbon hydrochlorate, chloride, soluble complexes; Can be by being selected from the soluble compound that contains molybdenum and/or tungsten metal one or more, as the solution of one or more preparations in molybdate, tungstates, the ethyl metatungstate, can be mixed solution by the solubility platform thing preparation of the soluble compound of nickeliferous and/or cobalt metal and molybdenum and/or tungsten metal; Can also be by the heteropoly acid of nickeliferous and/or cobalt metal and molybdenum and/or tungsten metal or the aqueous solution of salt preparation.According to method provided by the invention, to the solvent in the solution without limits, can be organic solvent, as alcohol, ether and acid, can be inorganic solvent, as water and their mixture.Preferably by the aqueous solution of nickel and/or cobalt metal soluble compound and/or molybdenum and/or the preparation of tungsten metal soluble compound.

In the hydrocracking catalyst provided by the invention, molybdenum and/or tungsten and nickel and/or cobalt content are the content of hydrogenation catalyst routine, in general, according to the oxide meter and with the catalyst is benchmark, the content of molybdenum and/or tungsten is 5-40 weight %, is preferably 12-35 weight %, and the content of nickel and/or brill is 1-15 weight, be preferably 5-13 weight, the method preparation that described catalyst is provided by the invention described above.

Catalyst preparation process of the present invention is simple, convenient, and easy operating is fit to industrial production.Catalyst of the present invention is used for hydrocracking process, to produce intermediate oil.Catalyst of the present invention is particularly suitable for treatment of heavy hydrocarbon material, the boiling range scope of heavy hydrocarbon material is at 250-600 ℃, generally at 300-550 ℃, have These characteristics feedstock oil such as gas oil, vacuum distillate, take off pitch prill oil, catalytic cracking recycle oil, shale oil, coal tar wet goods.Reaction condition generally under the hydrogen existence condition, reaction pressure 5-30MPa, hydrogen-oil ratio 100-5000, air speed 0.1-5.0h ^-1, reaction temperature 340-420 ℃.Catalyst of the present invention when handling common VGO, reaction condition generally under the hydrogen existence condition, the best 10-20MPa of reaction pressure, hydrogen-oil ratio 500-2000, air speed 0.5-1.5h ^-1, reaction temperature 370-410 ℃.

Further specify Preparation of catalysts method involved in the present invention and character and effect by the following examples.

Example 1

With industrial Y zeolite (SiO ₂/ Al ₂O ₃Mol ratio is 8, the content of Y zeolite in carrier is 40w%)-alumina support 50 gram places reaction vessel, take by weighing ammonium metatungstate 50 grams and be dissolved in water into 200 ml solns with nickel nitrate 23 grams, solution was joined the reaction vessel dipping 3 hours, dry down at 120 ℃ then, after dry 10 minutes, use the 25kHz ultrasonic wave it to be carried out radiation, radiation 20 minutes, radiant power is 500 watts/liter with the catalyst volume ratio, after radiation is finished, continue dry 120 minutes, and then carry out radiation once, radiated time is 40 minutes, condition continues drying again with for the first time, and be 6 hours total drying time.Dried catalyst is carried out high-temperature roasting again, and 500 ℃, roasting 4 hours obtains catalyst A, and its composition sees Table 1.

Example 2

Catalyst carrier contains Y zeolite (SiO ₂/ Al ₂O ₃Mol ratio is 11, and the content of Y zeolite in carrier is 40w%), amorphous aluminum silicide powder (silicon dioxide content 40w%, the content of amorphous silicon aluminium in carrier is 40w%, all the other are aluminium oxide).Weighing carrier 50 grams place reaction vessel, take by weighing ammonium metatungstate 50 grams and be dissolved in water into 200 ml solns with nickel nitrate 23 grams, solution was joined the reaction vessel dipping 3 hours, under 100 ℃, carry out drying then, after dry 30 minutes, use the 10kHz ultrasonic wave that it is carried out radiation, radiation 5 minutes, the volume ratio of radiant power and catalyst is 1200 watts/liter, after radiation is finished, continue dry 60 minutes, and then carry out radiation once, radiation 10 minutes, the volume ratio of radiant power and catalyst is 800 watts/liter, after radiation is finished, continued down dry 120 minutes at 130 ℃, and then carry out radiation once, the volume ratio of radiant power and catalyst is 500 watts/liter, radiation 5 minutes continues drying at 130 ℃ again, and making total drying time is 6 hours.Dried catalyst is carried out high-temperature roasting again, and 500 ℃, roasting 4 hours obtains catalyst B, and its composition sees Table 1.

Example 3

Catalyst carrier 50 grams of embodiment 2 place reaction vessel, take by weighing ammonium metatungstate 50 grams and be dissolved in water into 200 ml solns with nickel nitrate 23 grams, solution was joined the reaction vessel dipping 3 hours, put into baking oven then and under 90 ℃, carry out drying, after dry 60 minutes, use the 70kHz ultrasonic wave that it is carried out radiation, radiation 5 minutes, the volume ratio of radiant power and catalyst is 500 watts/liter, after radiation is finished, continued down dry 120 minutes at 95 ℃, and then carry out radiation once, radiation 90 minutes, the volume ratio of radiant power and catalyst is 15 watts/liter, after radiation is finished, continue dry 60 minutes at 120 ℃, and then carry out radiation once, radiation 20 minutes, the volume ratio of radiant power and dipping solution is 350 watts/liter, continues drying again, and making total drying time is 9 hours.Dried catalyst is carried out high-temperature roasting again, and 500 ℃, roasting 4 hours obtains catalyst C, and its composition sees Table 1.

Comparative example 1～2

Preparation is with example 1～2, but do not have the ultrasonic wave irradiation step.Be respectively D, E.

Table 1. catalyst physico-chemical property

The support/catalyst numbering	A	B	C	D	E
						WO 3，w％	24.04	23.37	24.06	24.08	23.40
NiO，w％	7.59	8.16	7.74	7.49	8.06
						Specific area, m 2/g	395	356	334	325	326
Pore volume, ml/g	0.72	0.65	0.60	0.65	0.60

The invention described above catalyst and reference catalyst thereof are estimated.Estimating with feedstock oil is triumph VGO, reaction pressure 14MPa, hydrogen to oil volume ratio 1500, air speed 1.5h ^-1Main character sees Table the activity that 2 height of estimating (65w%) reaction temperature when reaching identical conversion per pass by contrast are evaluated hydrocracking catalyst, and evaluate selection of catalysts according to the difference that product under the given conversion ratio distributes, the calculating of middle distillates oil selectivity obtains by " intermediate oil yield/＜370 ℃ product yield ".

Find out that from the catalyst physico-chemical property that table 1 is mentioned the catalyst pore volume and the specific surface of comparative example are all lower, can influence the dispersion and the hydrogenation activity thereof of metal undoubtedly.Shown also that from table 3 evaluation result catalyst of the present invention is at a kind of high aromatic hydrocarbons of processing, when height is done heavy raw oil, keep certain conversion ratio, middle distillates oil selectivity is higher, and reaction temperature is not higher than comparative example, illustrate that thus catalyst of the present invention on the basis that keeps greater activity, has good middle distillates oil selectivity.

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	A	B	C	D	E
						Reaction temperature, ℃	375	380	385	380	380
Middle distillates oil selectivity, %	80.1	82.2	78.3	74.1	74.1

Example 4

Carrier (trifolium-shaped bar) 50 grams of commercial alumina moulding are placed reaction vessel, take by weighing ammonium molybdate 112 grams and be dissolved in water into 200 ml solns with nickel nitrate 64 grams, solution was joined the reaction vessel dipping 3 hours, dry down at 120 ℃ then, after dry 10 minutes, use the 25kHz ultrasonic wave that it is carried out radiation, radiation 10 minutes, radiant power is 3000 watts/liter with the catalyst volume ratio, after radiation is finished, continue dry 120 minutes, and then carry out radiation once, radiant power is 1500 watts/liter with the catalyst volume ratio, radiated time is 30 minutes, condition continues drying again with for the first time, and be 6 hours total drying time.Dried catalyst is carried out high-temperature roasting again, and 500 ℃, roasting 4 hours obtains catalyst F, and its composition sees Table 4.

Comparative example 3

Preparation is with example 4, but do not have the ultrasonic wave irradiation step.Obtain catalyst G, its composition sees Table 4.

Table 4. catalyst physico-chemical property

The support/catalyst numbering	F	G
			MoO 3，w％	24.10	24.05
NiO，w％	3.65	3.60
			P，w％	1.81	1.80
Specific area, m 2/g	210	200
			Pore volume, ml/g	0.34	0.32

The invention described above catalyst and reference catalyst thereof are estimated.Estimating with feedstock oil is triumph VGO, reaction pressure 14MPa, hydrogen to oil volume ratio 1000, air speed 1.0h ^-1Main character sees Table 2.Evaluation obtains by contrast reaction temperature and refined oil nitrogen content.

Find out that from table 4 body and catalyst physico-chemical property the catalyst pore volume and the specific surface of comparative example are all lower, can influence the dispersion and the hydrogenation activity thereof of metal undoubtedly.Shown also that from table 5 evaluation result catalyst of the present invention handling a kind of high aromatic hydrocarbons, when height is done heavy raw oil, having higher denitrification activity.

Table 5 evaluating catalyst result

The catalyst numbering	F	G
			Reaction temperature, ℃	370	376
N，μg/g	4	18

Claims (10)

1, a kind of drying means of loaded catalyst, comprise following content: the catalyst carrier behind the dipping adopts conventional method to carry out drying, in dry run, use the ultrasonic wave radiation, the ultrasonic wave radiation is adopted and is interrupted radiative process, each radiated time is 0.5～120 minute, altogether radiation is 1-10 time, and be 5-360 minute the blanking time when adopting repeatedly radiation, radiant power be 1-5000 watt/liter by the ratio of radiant matter volume.

2, in accordance with the method for claim 1, it is characterized in that described each radiated time is 1～60 minute, adopting repeatedly the emissive intervals time is 20～120 minutes, radiant power with by 10～1000 watts/liter of the ratios of radiant matter volume.

3, in accordance with the method for claim 1, it is characterized in that described frequency of ultrasonic is 10～180kHz.

4, in accordance with the method for claim 1, it is characterized in that described frequency of ultrasonic is 20～100kHz.

5, in accordance with the method for claim 1, it is characterized in that described drying condition is at 80～200 ℃, dry 1～15 hour.

6, a kind of preparation method of middle oil type hydrocracking catalyst, comprise following content: the catalyst carrier of selecting to contain the Y zeolite, with molybdenum and/or tungsten compound, and dipping solution impregnation catalyst agent carrier and the drying and the roasting of nickel and/or cobalt compound, final catalyst got; It is characterized in that wherein in dry run, using the ultrasonic wave radiation, the ultrasonic wave radiation is adopted and is interrupted radiative process, each radiated time is 0.5～120 minute, radiation is 1-10 time altogether, be 5-360 minute the blanking time when adopting repeatedly radiation, radiant power be 1-2000 watt/liter by the ratio of radiant matter volume.

7, in accordance with the method for claim 6, it is characterized in that described each radiated time is 1～60 minute, adopting repeatedly the emissive intervals time is 20～120 minutes, radiant power with by 10～1000 watts/liter of the ratios of radiant matter volume.

8, in accordance with the method for claim 6, it is characterized in that described frequency of ultrasonic is 10～180kHz.

9, in accordance with the method for claim 6, it is characterized in that described frequency of ultrasonic is 20～100kHz.

10, in accordance with the method for claim 6, it is characterized in that, is benchmark with the weight of catalyst carrier, and the content of amorphous aluminum silicide is 0～60w%, and the content of Y zeolite is 5w%～35w%; Weight with catalyst is benchmark, and the content of reactive metal molybdenum and/or tungsten is counted 5w%～40w% with oxide, and the content of nickel and/or cobalt is counted 1w%～15w% with oxide; The drying condition of catalyst is at 80～200 ℃, and dry 1～15 hour, the roasting condition of catalyst was 350～550 ℃ of following roastings 1～8 hour.