CN103785445B - Preparation method of middle distillate-type hydrocracking catalyst - Google Patents
Preparation method of middle distillate-type hydrocracking catalyst Download PDFInfo
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- CN103785445B CN103785445B CN201210427732.XA CN201210427732A CN103785445B CN 103785445 B CN103785445 B CN 103785445B CN 201210427732 A CN201210427732 A CN 201210427732A CN 103785445 B CN103785445 B CN 103785445B
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Abstract
The present invention discloses a preparation method of a middle distillate-type hydrocracking catalyst. The method of the present invention includes the following steps: (1) preparing a catalyst carrier containing a molecular sieve and an inorganic refractory oxide; (2) preparing a solution containing a hydrazine derivative, dipping the catalyst carrier obtained in the step (1), and then drying the carrier; (3) preparing a dipping solution containing a VIB group metal compound and a VIII group metal compound; (4) dipping the materials obtained in the step (2) in the dipping solution prepared in the step (3), and then drying; (5) performing a heat treatment at 200-450 DEG C in the air atmosphere to the materials obtained in the step (4) for 1-6 h; and (6) activating the materials obtained in the step (5) after the heat treatment by using hydrogen, so as to obtain the hydrocracking catalyst used for the hydrocracking reaction after the activation. The hydrocracking catalyst provided by the invention is used for the treatment of heavy hydrocarbon materials, does not require prevulcanization, has low inactivation rate, and can facilitate the highest-yield production of middle distillates.
Description
Technical field
The present invention relates to a kind of preparation method of hydrocracking catalyst, this catalyst has excellent hydrocracking performance, and active high, middle distillates oil selectivity is high.
Background technology
Hydrocracking catalyst is a kind of bifunctional catalyst, there is Hydrogenation and cracking performance, non-noble metal hydrocracking catalyst generally selects VI B and VIII race's metal to make hydrogenation component, and cracking performance provides primarily of acidic components, and acidic components can select crystal formation zeolite and/or amorphous aluminum silicide etc.Simple amorphous aluminum silicide, although selective higher, active low, operational flexibility is restricted, in most of hydrocracking catalyst all with crystal formation zeolite for acidic components, or crystal formation zeolite and amorphous aluminum silicide are acidic components jointly.
The middle oil type hydrocracking catalyst major part that commercial plant uses at present is the catalyst containing zeolite, and the zeolite component adopted mainly y-type zeolite, β zeolite and two kinds of zeolites are used in combination, and catalyst all will carry out presulfurization before reactions, metal component is made to be converted into sulphided state, to improve the serviceability of catalyst.But use the health of the higher vulcanizing agent of sulfur content not only contaminated environment, harm operating personnel, and sulfidation is numerous and diverse, needs to drop into a lot of manpower and materials.
US4820402 discloses a kind of hydrocracking catalyst, has used β zeolite, and this patent is thought, in order to improve middle distillates oil selectivity and reduce hydrogen consumption, the silica/alumina molecular proportion at least 50:1 of the zeolite component in catalyst, general 100:1, even 200:1.The middle distillates oil selectivity order that variety classes zeolite is used for catalyst is: ZSM-20> β >Y type, process Arabic VGO, when control 60v% transforms, middle distillates oil selectivity 45-65v%, wherein acidic components are β zeolite, during conversion ratio 60v%, the catalyst middle distillates oil selectivity that this patent relates to is no more than 70v%.
US4894142 discloses a kind of hydrocracking catalyst, object is the middle distillates oil selectivity improving catalyst, be characterized in by using the dry type heat treatment method passing into inert gas being included in 676-788 DEG C of hydrothermal treatment consists or best 704 DEG C, obtain a kind of low acidity Y zeolite, but because this zeolitic acid is spent low, high for reaction temperature during catalytic component process feedstock oil, general more than 400 DEG C, inhibit hydrogenation reaction, the thermal cracking performance trend of zeolite strengthens, the middle distillates oil selectivity of catalyst is improved not obvious, middle distillates oil selectivity is no more than 70%.
US5447623 discloses hydrocracking catalyst and the technique thereof of a kind of compound β zeolite and Y zeolite, but this catalyst is mainly used in light oil type hydrogen cracking catalyst, embodiment 50-185 DEG C of naphtha yield improves obviously, and the use of β zeolite relatively only uses the catalyst activity of Y zeolite also high.Although this catalyst also may be used for middle oil type hydrocracking catalyst, due to the characteristic of used β zeolite, in middle oil type catalyst, the content range of β zeolite is generally limited between 2.5w%-10w%, and generally must be dispersed in γ-Al with the use of one
2o
3and so on the sial on macroporous aluminium oxide matrix, the middle oil type catalyst that this patent relates to is for ensureing middle distillates oil selectivity, and activity of having to force down, makes reaction temperature higher, general more than 390 DEG C, thus result in poor adaptability to raw material.
The hydrogenation component of above-mentioned hydrocracking catalyst is the metal component of oxidation state, needs to carry out normal vulcanizing treatment before using, and the serviceability of catalyst needs to improve further.In hydrocracking catalyst, although hydrogenation activity and cracking activity main body are provided by two kinds of components, but in the catalyst, the effect of two kinds of components is not well-separated, but the interactional coordinated effect that influences each other, hydrocracking reaction is the reaction that raw material has been worked in coordination with on two kinds of activated centres.How regulating in hydrocracking catalyst, the correlation of hydrogenation active component and cracking active component, is the important content improving the comprehensive serviceability of hydrocracking catalyst.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of middle oil type hydrocracking catalyst, hydrocracking catalyst of the present invention is for the treatment of heavy hydrocarbon material, and without the need to carrying out presulfurization, deactivation rate is slow, maximum can produce intermediate oil.
In the present invention, oil type hydrocracking catalyst preparation method comprises following process:
(1) preparation contains the catalyst carrier of molecular sieve and inorganic refractory oxide;
(2) preparation is containing hydrazine derivative solution, and the catalyst carrier of impregnation steps (1), then dry;
(3) preparation contains the dipping solution of VI B race metallic compound and VIII race's metallic compound;
(4) material that the dipping solution impregnation steps (2) that step (3) is prepared obtains, then dry;
(5) material that step (4) obtains is heat-treated in air atmosphere; Heat treatment for process 1-6 hour at 200-450 DEG C;
(6) material after step (5) heat treatment carries out Hydrogen activation, obtains the hydrocracking catalyst for hydrocracking reaction after activation.
In hydrocracking catalyst preparation method of the present invention, in preparation method, the consumption of various materials stock is determined by having following composition: with catalyst carrier weighing scale, the content of molecular sieve is generally 2% ~ 45%, is preferably 4% ~ 15%; With the weighing scale of catalyst, metal component of group VIB (weighing scale of W and/or Mo) content is generally 10%-40%, is better 15%-35%, best 18%-28%, metal component of group VIII (weighing scale with Ni and/or Co) content is generally 1%-10%, is better 2%-9%, preferably 4%-8%.Inorganic refractory oxide is surplus.The initial feed of various component can be the material source of this area routine.
In hydrocracking catalyst preparation method of the present invention, molecular sieve is generally one or more in Y molecular sieve, beta-molecular sieve, ZSM-5 molecular sieve, SAPO-11 molecular sieve, modenite, ZSM-22 molecular sieve, ZSM-23 molecular screen and mesopore molecular sieve, is preferably Y molecular sieve and/or beta-molecular sieve.Required molecular sieve can carry out the modification be suitable for, as hydrothermal treatment consists modification, acid treatment modification etc.One or more in inorganic refractory oxide is generally aluminium oxide, silica, silica-alumina (i.e. amorphous aluminum silicide), silica-alumina are scattered in aluminium oxide (being namely dispersed in the amorphous aluminum silicide in aluminium oxide) wherein, silica is covered with paint, lacquer, colour wash, etc. aluminium oxide, magnesia, zirconia, boron oxide and titanium dioxide, are preferably amorphous aluminum silicide and/or alumina component.
In hydrocracking catalyst preparation method of the present invention, the preparation of catalyst carrier can adopt the method for this area routine, obtains catalyst carrier as required material finally formed the steps such as the mixing of required ratio, shaping, dry, roasting in catalyst.Drying is generally dry 4-12 hour at 80-150 DEG C, and roasting is roasting 2-6 hour at 400-600 DEG C.
In hydrocracking catalyst preparation method of the present invention, hydrazine derivative can use any hydrazine derivative, preferably uses dialkyl group hydrazine, particularly dimethyl hydrazine NH
2n (CH
3)
2.The mass concentration of hydrazine derivative is 20%-70%.Drying process after dipping hydrazine derivative is dry 4-12 hour at 80-100 DEG C.
In hydrocracking catalyst preparation method of the present invention, VI B race metallic compound and VIII race's metallic compound can select the common soluble compound being formulated as the aqueous solution in this area.
In hydrocracking catalyst preparation method of the present invention, flood for saturated dipping or excess solution impregnation, dipping can once carry out, and also can repeatedly flood.Drying process after dipping is dry 4-12 hour at 80-150 DEG C.
In hydrocracking catalyst preparation method of the present invention, Hydrogen activation process and condition are: under a hydrogen atmosphere, are that 2-10 DEG C/min rises to 200-500 DEG C from room temperature with heating rate, and at intensification outlet temperature constant temperature 2-4 hour.Hydrogen purity is wherein greater than 95%(volume), hydrogen gas space velocity is 50-1000h
-1, pressure can be normal pressure to 1MPa, be preferably normal pressure.
Hydrocracking catalyst prepared by the inventive method, for vacuum distillate be raw material inceasing output of jet fuel and diesel oil hydrocracking process in, reaction pressure preferably at 6-20MPa, hydrogen to oil volume ratio 500:1-2000:1, raw material volume air speed 0.5-2.0hr
-1, reaction temperature 350-410 DEG C.Feedstock oil, before carrying out hydrocracking, carries out hydrofinishing, and organic nitrogen content is wherein reduced to below 50ug/g, is preferably below 20ug/g.
Hydrazine derivative is first impregnated in catalyst carrier by method for preparing catalyst of the present invention, sufficient modification and pore structure modulation are carried out to the acidic components (comprising molecular sieve and amorphous aluminum silicide) in carrier, there is certain adjustment in the distribution over a molecular sieve of the active metal component of follow-up dipping or load situation, reduce strong acid center quantity, support acidity is balanced, effectively can reduce catalyst coking in operation process, reduce the deactivation rate of catalyst, the extending catalyst life-span.
In hydrocracking catalyst preparation process of the present invention, introduce the hydrazine derivative matched with active metal component, and common for hydrocracking catalyst sulfidation is cancelled, adopt hydrogen reducing mode to carry out activation process to metal-containing compound with containing the catalyst of hydrazine derivative.The hydrocracking catalyst active metal component adopting the method to prepare has desirable Hydrogenation on the one hand, and the acid centre of active metal component to molecular sieve creates certain effect on the other hand.Show by analysis, the B acid site of active metal and molecular sieve interacts, significantly improve the acid strength distribution on zeolite, strong acid is reduced, middle intensity acid increases, acid site number increases to some extent, and L acid site number reduces relatively, can reduce fine melt function like this, increase the activity that moderate strength acid amount is conducive to improving catalyst, reduce reaction temperature, and improve the selective of intermediate oil (kerosene and diesel oil).Hydrocracking catalyst of the present invention can significantly improve the nitrogen resistance of catalyst simultaneously, and when using identical acidic components, the resistance to nitrogen ability of catalyst of the present invention significantly improves.
Detailed description of the invention
Hydrocracking catalyst prepared by the inventive method is applicable to hydrocracking process, be particularly suitable for treatment of heavy hydrocarbon material, the boiling range of heavy hydrocarbon material is generally within the scope of 250-600 DEG C, and preferably within the scope of 300-550 DEG C, wherein the cut of more than 70w% is more than 350 DEG C.There is the feedstock oil of These characteristics as gas oil, vacuum distillate, de-pitch prill oil, catalytic cracking recycle oil, shale oil, coal tar wet goods.Reaction condition generally under hydrogen existence condition, reaction pressure 5-20MPa, hydrogen to oil volume ratio 100:1-5000:1, raw material volume air speed 0.1-5.0hr
-1, reaction temperature 350-450 DEG C.Hydrocracking process generally comprises the hydrofinishing of leading portion, for removing most S, N in feedstock oil, and the saturated severity reducing the operation of hydrocracking section of polycyclic aromatic hydrocarbon, but this catalyst can reduce the severity of refining stage operation, embodies good effect when high nitrogen-containing.
Following embodiment describes the present invention, but does not limit its scope.Under hydrogen atmosphere, reduction activation is carry out under normal pressure.
Comparative example 1
By 25.3 grams of Y sieves (butt 95wt%), 71.4 grams of amorphous aluminum silicide (SiO
2content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 70wt%), 122.9 grams of macroporous aluminium oxides (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier T-1, character is in table 1.
The maceration extract room temperature immersion of carrier tungstenic and nickel (ammonium metatungstate and nickel nitrate, lower with) 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 hours, obtain catalyst B J-1, catalyst property was in table 2.Catalyst uses the common vulcanizing treatment of row of advancing, and sulfidation is with hydrogen sulfide containing hydrogen 230 DEG C of constant temperature 8 hours, 280 DEG C of constant temperature 8 hours, 320 DEG C of constant temperature 8 hours.
Embodiment 1
Prepare the dimethyl hydrazine NH that weight concentration is 30%
2n (CH
3)
2solution, by the above-mentioned dried carrier T-1 solution impregnation prepared 2 hours, 100 DEG C of dryings 4 hours, then use the maceration extract room temperature immersion 2 hours of tungstenic and nickel, 100 DEG C of dryings 4 hours, heat treatment 6 hours at 150 DEG C in air atmosphere, then reduction activation in a hydrogen atmosphere, reduction activation program is for rise to 450 DEG C with 5 DEG C/min from room temperature, be 2 DEG C/min with heating rate, rise to 500 DEG C from 450 DEG C, and 500 DEG C of constant temperature 2 hours, be prepared into catalyst C-1 of the present invention.
Comparative example 2
By 14.7 grams of beta-molecular sieves (butt 95wt%), 151.4 grams of amorphous aluminum silicide (SiO
2content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 70wt%), 57.1 grams of macroporous aluminium oxides (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier T-2, character is in table 1.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 hours, obtain catalyst B J-2, catalyst property was in table 2.Catalyst uses the common vulcanizing treatment of row of advancing, and sulfidation is with hydrogen sulfide containing hydrogen 230 DEG C of constant temperature 8 hours, 280 DEG C of constant temperature 8 hours, 320 DEG C of constant temperature 8 hours.
Embodiment 2
Prepare the dimethyl hydrazine NH that weight concentration is 40%
2n (CH
3)
2solution, by the carrier T-2 of comparative example 2 solution impregnation prepared 2 hours, 100 DEG C of dryings 5 hours, use the maceration extract room temperature immersion 2 hours of tungstenic and nickel again, 100 DEG C of dryings 6 hours, heat treatment 1 hour at 400 DEG C in air atmosphere, then in a hydrogen atmosphere, carry out Hydrogen activation, first rise to 350 DEG C with 10 DEG C/min from room temperature, be 1 DEG C/min with heating rate, rise to 500 DEG C from 350 DEG C, and 500 DEG C of constant temperature 4 hours, prepare catalyst C-2.
Comparative example 3
By 8.4 grams of Y molecular sieves (butt 95wt%), 85.7 grams of amorphous aluminum silicide (SiO
2content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 70wt%), 131.42 grams of macroporous aluminium oxides (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier T-3, character is in table 1.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst B J-3, catalyst property is in table 2.Catalyst uses the common vulcanizing treatment of row of advancing, and sulfidation is with hydrogen sulfide containing hydrogen 230 DEG C of constant temperature 8 hours, 280 DEG C of constant temperature 8 hours, 320 DEG C of constant temperature 8 hours.
Embodiment 3
Prepare the dimethyl hydrazine NH that concentration is 60%
2n (CH
3)
2solution, by the carrier T-3 of comparative example 3 solution impregnation prepared 2 hours, 110 DEG C of dryings 5 hours, then use the maceration extract room temperature immersion 2 hours of tungstenic and nickel, 110 DEG C of dryings 6 hours, heat treatment 2 hours at 350 DEG C in air atmosphere, then carries out activation process in a hydrogen atmosphere, first rises to 450 DEG C with 8 DEG C/min from room temperature, be 1 DEG C/min with heating rate, rise to 650 DEG C from 450 DEG C, and 650 DEG C of constant temperature 4 hours, prepare catalyst C-3.
Embodiment 4
This embodiment describes the Activity evaluation of catalyst and the comparative example catalyst prepared by the present invention.Fixed bed hydrogenation experimental rig is evaluated.
Appreciation condition is: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity 1.0h during material liquid
-1, use vacuum distillate (VGO) as feedstock oil, feedstock oil character lists in table 3.Evaluated under above-mentioned process conditions by the catalyst prepared in above-mentioned each example, the evaluation result obtained lists in table 4.
As can be seen from Table 4, catalyst of the present invention activity when refined oil nitrogen content significantly improves is higher, and product property is better.As can be seen from Table 4, catalyst of the present invention activity when refined oil nitrogen content significantly improves is higher, and deactivation rate is slow, and product property is better.
the physico-chemical property of table 1 catalyst carrier
| Numbering | T-1 | T-2 | T-3 |
| Molecular sieve, wt% | 12.0 | 7.0 | 4.0 |
| Amorphous aluminum silicide, wt% | 25.0 | 53.0 | 30.0 |
| Macroporous aluminium oxide, wt% | 43.0 | 20.0 | 46.0 |
| Adhesive, wt% | 20.0 | 20.0 | 20.0 |
table 2 catalyst composition and character
| Numbering | BJ-1 | C-1 | BJ-2 | C-2 | BJ-3 | C-3 |
| W，wt% | 15.1 | 15.6 | 18.0 | 18.5 | 20.4 | 20.8 |
| Ni，wt% | 3.4 | 3.6 | 5.73 | 5.81 | 6.2 | 6.4 |
| Pore volume, ml/g | 0.56 | 0.54 | 0.53 | 0.54 | 0.55 | 0.56 |
| Specific area, m 2/g | 324 | 334 | 279 | 289 | 281 | 305 |
table 3 feedstock oil main character
| Feedstock oil | Vacuum distillate |
| Density (20 DEG C), kg/m 3 | 920.6 |
| Boiling range, DEG C | |
| IBP/10% | 328/413 |
| 30%/50% | 450/471 |
| 70%/90% | 493/522 |
| 95%/EBP | 534/545 |
| Nitrogen, μ g/g | 1575 |
| Carbon, wt% | 85.25 |
| Hydrogen, wt% | 11.96 |
| Carbon residue, wt% | 0.35 |
table 4 COMPARATIVE CATALYST's evaluation result of the present invention
| Catalyst | BJ-1 | BJ-2 | BJ-3 | C-1 | C-2 | C-3 |
| Refined oil nitrogen content, μ g/g | 3 | 5 | 8 | 25 | 30 | 35 |
| Reaction temperature, DEG C | 383 | 390 | 393 | 365 | 374 | 378 |
| Product yield and character | ||||||
| Heavy naphtha | ||||||
| Yield, wt% | 9 | 8.9 | 10.7 | 9.7 | 8.8 | 10.1 |
| Virtue is dived, wt% | 61.9 | 62.8 | 60.8 | 62.5 | 62.5 | 60.6 |
| Jet fuel | ||||||
| Yield, wt% | 25.3 | 23.8 | 24.6 | 26.5 | 24.8 | 25 |
| Smoke point, mm | 24 | 23 | 22 | 24 | 24 | 23 |
| Aromatic hydrocarbons, volume % | 8.9 | 10 | 12.4 | 8.2 | 8.6 | 10.7 |
| Diesel oil | ||||||
| Yield, wt% | 36.5 | 35.9 | 33.6 | 35.9 | 37.9 | 33 |
| Cetane number | 58.2 | 56.4 | 55.5 | 62.8 | 60.5 | 60.9 |
| Tail oil | ||||||
| Yield, wt% | 24.2 | 28.5 | 28.6 | 24.3 | 25.1 | 28.9 |
| BMCI value | 9.8 | 10 | 11 | 9.4 | 9.9 | 11.4 |
| Chemical hydrogen consumption, wt% | 2.21 | 2.18 | 2.26 | 2.21 | 2.34 | 2.23 |
| Middle distillates oil selectivity, wt% | 81.5 | 83.5 | 81.5 | 82.4 | 83.7 | 81.6 |
| Deactivation rate, DEG C d -1 | 0.05 | 0.03 | 0.02 | <0.01 | <0.01 | <0.01 |
Claims (9)
1. an oil type hydrocracking catalyst preparation method in, is characterized in that: comprise following process:
(1) preparation contains the catalyst carrier of molecular sieve and inorganic refractory oxide;
(2) preparation is containing hydrazine derivative solution, and the catalyst carrier of impregnation steps (1), then dry, hydrazine derivative is dialkyl group hydrazine, and the mass concentration of hydrazine derivative is 20%-70%, and drying is dry 4-12 hour at 80-100 DEG C;
(3) preparation contains the dipping solution of VI B race metallic compound and VIII race's metallic compound;
(4) material that the dipping solution impregnation steps (2) that step (3) is prepared obtains, then dry;
(5) material that step (4) obtains is heat-treated in air atmosphere; Heat treatment for process 1-6 hour at 200-450 DEG C;
(6) material after step (5) heat treatment carries out Hydrogen activation, obtains the hydrocracking catalyst for hydrocracking reaction after activation.
2. method according to claim 1, is characterized in that: the consumption of various materials stock is determined by having following composition: with catalyst carrier weighing scale, the content of molecular sieve is 2% ~ 45%; With catalyst weight, metal component of group VIB content is 10%-40%, and metal component of group VIII content is 1%-10%.
3. method according to claim 1, is characterized in that: molecular sieve is one or more in Y molecular sieve, beta-molecular sieve, ZSM-5 molecular sieve, SAPO-11 molecular sieve, modenite, ZSM-22 molecular sieve, ZSM-23 molecular screen.
4. method according to claim 1, is characterized in that: inorganic refractory oxide is one or more in aluminium oxide, silica, silica-alumina, magnesia, zirconia, boron oxide and titanium dioxide.
5. method according to claim 1, is characterized in that: hydrazine derivative is dimethyl hydrazine NH
2n (CH
3)
2.
6. method according to claim 1, is characterized in that: Hydrogen activation process and condition are: under a hydrogen atmosphere, is that 2-10 DEG C/min rises to 200-500 DEG C from room temperature with heating rate, and at intensification outlet temperature constant temperature 2-4 hour.
7. the method according to claim 1 or 6, is characterized in that: hydrogen volume purity is greater than 95%, and hydrogen gas space velocity is 50-1000h
-1, pressure is that normal pressure is to 1MPa.
8. the application of catalyst in the hydrocracking process taking vacuum distillate as raw material inceasing output of jet fuel and diesel oil that in claim 1 to 7 prepared by arbitrary described method, it is characterized in that: reaction pressure 6-20MPa, hydrogen to oil volume ratio 500:1-2000:1, raw material volume air speed 0.5-2.0hr
-1, reaction temperature 350-410 DEG C.
9. application according to claim 8, is characterized in that: feedstock oil, before carrying out hydrocracking, carries out hydrofinishing, and organic nitrogen content is wherein reduced to below 50ug/g.
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| CN1353168A (en) * | 2000-11-03 | 2002-06-12 | 中国石油天然气股份有限公司 | Hydrorefining catalyst and its preparing process |
| CN101088615A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Process of treating hydrogenation catalyst before application |
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| CN101088615A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Process of treating hydrogenation catalyst before application |
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