CN103769199B - The preparation method of sulfurized hydrogenation Cracking catalyst - Google Patents
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Abstract
The invention discloses a kind of preparation method of sulfurized hydrogenation Cracking catalyst.The method comprises: selective hydrocracking catalyst support component; carrier component at least comprises a kind of acidic cracking components; add water carrier component powder making beating; obtain slurries d; then ammonium molybdate and/or ammonium tungstate salting liquid a, ammonium sulfide solution b, nickel salt and/or cobalt salt solution c are passed into after reacting in slurries d; after filtration, wash, under the protection of inert gas after drying; add adhesive kneading; through shaping; drying and roasting under the protection of inert gas, obtain sulfurized hydrogenation Cracking catalyst.The inventive method makes active metal be uniformly dispersed, and easily generates more active higher II type Ni(Co) Mo(W) the active phase of S, make the state of cure (vulcanization) of catalyst high, the utilization ratio of active metal is high, thus improves the Hydrogenation of catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of sulfurized hydrogenation Cracking catalyst.
Background technology
In recent years, along with the minimizing day by day of petroleum reserves, international oil price climbs up and up, and the trend of crude oil heaviness, in poor quality is more and more serious, and the demand of market to high-quality middle cut oil product constantly increases.Therefore, volume increase intermediate oil, improves diesel and gasoline ratio, improves this imbalance between supply and demand and seem particularly important, and the key solving this contradiction is the selective high hydrocracking catalyst of exploitation midbarrel oil type.Current industrialized hydrocracking catalyst, its metal active constituent major part is all exist in the form of an oxide, and need activity over catalysts convert metal oxides to be sulfide during actual use, therefore, catalyst needs through over cure before use or claims presulfurization.
Conventional catalyst vulcanization process adopts " in device " sulfuration or title " original position " sulfuration, namely first the catalyst of oxidation state is loaded in hydrogenation reactor, then in the process constantly heated up, pass into hydrogen in reactor and vulcanizing agent carries out presulfurization, this method brings following problem: (1) will set up special presulfurization equipment on hydrogenation plant; (2) water that the vulcanizing agent added in sulfidation and reaction generate and hydrogen sulfide very easily cause the corrosion of high-pressure reactor and relevant devices, cause device damage and potential safety hazard; (3) sulfidation is longer, incurs loss through delay on-stream time.(4) vulcanizing agent used is inflammable, poisonous, to environment in sulfidation; (5) cost of in-situ presulfurization is higher.
For this reason, there is pre-curing technology outside simple, efficient, pollution-free and that cost is low scene (or claiming " device is outer " presulfurization), presulfurization by catalyst is transferred to the catalyst that the catalyst special vulcanization reaction device carrying out or makes has been sulphided state, thus make can use in catalyst loading hydrogenation reactor, need not sulfuration again, this technology has become the development trend of hydrocracking catalyst technology of preparing in recent years.
At present, hydrocracking catalyst " device the is outer " pre-curing technology of open report mainly contains two kinds of technology paths:
(1) the first technology path be first vulcanizing agent is adopted distillation, the method for melting or dipping is incorporated in the space of the hydrocracking catalyst of oxidation state, then catalyst member presulfurization is made through hyperthermic treatment in the presence of an inert gas, finally catalyst is loaded in hydrogenation reactor, in the presulfurization completing catalyst in temperature-rise period in the presence of hydrogen gas that goes into operation;
(2) the second technology path is in special prevulcanisation-devices, completes the presulfurization of catalyst, then make non-hypergolic presulfurization catalyst through oxygen-containing gas Passivation Treatment under the existence of hydrogen and hydrogen sulfide or labile organic sulfurizing agent.
CN85107953 discloses a kind of method processing hydrogenation catalyst, wherein mainly comprise first dissolve with petroleum solvent and dilution elementary sulfur, multiple organic polysulfide is at 50 ~ 150 DEG C of impregnation process hydrocracking catalysts, then process at lower than 275 DEG C in the atmosphere of no hydrogen, reactive metal oxides is carried out sulfuration, finally activates at higher than the temperature of 275 DEG C in the presence of hydrogen gas.CN91101805.7 discloses a kind of method of being mixed by sulphur in the hole of hydrocarbon processing catalysts, and its feature is: the vulcanizing agent process catalyst first adopting solvent dilution, then in the presence of water vapor, and vulcanizing treatment at higher than the temperature of 250 DEG C.Vulcanizing agent used is made up of elementary sulfur and the organosulfur compound that easily decomposites hydrogen sulfide in presence of hydrogen, and solvent used is the solvent naphtha containing olefine fraction or vegetable oil.US 6,365,542 discloses the method for the outer sulfuration of a kind of hydrocracking catalyst device, be characterized in first with the oil containing elementary sulfur, alkene at 100 ~ 120 DEG C of process catalyst, then at the temperature of 100 ~ 300 DEG C through inert gas treatment.US 6,417, the 134 a kind of ex situ presulfiding methods disclosing hydrotreating catalyst, be characterized in elementary sulfur, organic sulfur compound, organic polysulfide, the oil containing alkene, the impregnation process catalyst at the temperature of 300 DEG C of the component containing ethylene linkage of first using solvent dilution, then at the temperature of 250 ~ 600 DEG C, use hydrogen treat, finally use oxygen-containing gas passivation.Said method is all carry out presulfurization process to ready-made oxidized catalyst, has the following disadvantages like this in preparation process: the oxide M oO of hydrocracking catalyst active metal Mo, W, Co, Ni
3, WO
3, there is strong interaction in CoO, NiO and carrier surface, cause active metal component sulfuration difficulty and not exclusively, the hydrogenation activity of catalyst reduced, and serious environmental pollution can be caused in sulfidation.
CN200410039449.5 discloses a kind of preparation method of sulfide type catalyst, it is by molybdenum dithiophosphate (tungsten) hydrochlorate of solubility and Co(Ni by the mode of incipient impregnation) atom substep or a step load on the carrier of catalyst, and through heating in inert gas, thus obtained load has the sulfide type catalyst of metal sulfide.Because Thiomolybdate and thiqtung state etc. are water insoluble, obtain solution needs to add organic solvent, and complicated process of preparation is unsuitable for large-scale industrial production.In addition, the method is in high-temperature process, and due to the volatilization of organic solvent, strengthen the interaction of hydrogenation component and carrier, have impact on the sulfuration of catalyst, sulphidity is relatively low, and the activity and selectivity of catalyst declines.
" petroleum refining and chemical industry " (2011,42 (6): 50-56) have studied the impact of sintering temperature on the reactivity worth of sulfur-bearing precursor hydrocracking catalyst.By the mode of kneading by ammonium thiomolybdate and nickel nitrate load on the carrier of catalyst, and through heating in inert gas, obtain the sulfide type catalyst of sulfur-bearing metal sulfide.The method technique is simple, state of cure (vulcanization) is high, makes the sulfurized hydrogenation Cracking catalyst obtained have higher activity and selectivity, but the catalyst metals dispersing uniformity prepared due to kneading method is poor, using rate of metal is low, have impact on activity and the product property of catalyst.
Summary of the invention
For overcoming above-mentioned the deficiencies in the prior art part, the invention provides the preparation method of the sulfurized hydrogenation Cracking catalyst that a kind of metal dispersion is even, state of cure (vulcanization) is high, activity is high and product is of fine quality.
The preparation method of sulfurized hydrogenation Cracking catalyst of the present invention, comprising:
(l) preparation dimolybdate salt and/or ammonium tungstate salting liquid a, formulating vulcanization ammonium salt solution b, preparation nickel salt and/or cobalt salt solution c;
(2) selective hydrocracking catalyst support component, carrier component at least comprises a kind of acidic cracking components, and add water carrier component powder making beating, obtains slurries d;
(3) solution a, solution b and solution c are passed into slurries d, control reaction temperature at 50 ~ 80 DEG C, the time of passing into is 0.5 ~ 2 hour;
(4) material of step (3) gained carried out filter, wash, dry under the protection of inert gas, obtain catalyst intermediate;
(5) catalyst intermediate is added adhesive kneading, through extruded moulding, dry under the protection of inert gas, roasting, makes sulfurized hydrogenation Cracking catalyst.
In step (1), in ammonium molybdate and/or ammonium tungstate solution, every 100 ml contain 5 ~ 30gMo and/or W, are preferably 5 ~ 10gMo and/or W.The concentration of ammonium sulfide solution is 5wt% ~ 30wt%, is preferably 10wt% ~ 15wt%.In nickel salt and/or cobalt salt slurries, every 100 ml contain 5 ~ 20gNi and/or Co, are preferably 5 ~ 10gNi and/or Co.Described nickel salt and/or cobalt salt be selected from nitrate, carbonate, subcarbonate, acetate, chloride one or more.
In step (2), described carrier of hydrocracking catalyst component at least comprises a kind of acidic cracking components, acidic cracking components comprises molecular sieve or amorphous acidic components, and molecular sieve generally comprises one or more in Y zeolite, beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesopore molecular sieve etc.Amorphous acidic components are generally one or more in amorphous aluminum silicide, amorphous silicon magnesium etc.Required molecular sieve can require according to serviceability the modification carrying out being suitable for.In hydrocracking catalyst, carrier component can also comprise acid more weak inorganic refractory oxide, is generally aluminium oxide or contains auxiliary agent aluminium oxide.With the weight of final catalyst for benchmark, the general content of acidic cracking components is 10wt% ~ 60wt%, Mo and/or W in the content of element for 10wt% ~ 30wt%, Co and/or Ni in the content of element for 2wt% ~ 10wt%, simultaneously can also salic 0 ~ 50 wt %.
In step (2), the volume ratio of carrier component powder and water is 1:5 ~ 1:30, is preferably 1:10 ~ 1:20.Described carrier component powder is hydroxide and/or the oxide powder that can generate carrier component.Such as amorphous acidic components adopt contained amorphous silica-alumina dry glue powder and/or amorphous silicon magnesium dry glue powder, and aluminium oxide adopts aluminum oxide dry glue powder, and molecular sieve adopts molecular sieve powder etc.The active metal component of hydrocracking catalyst of the present invention is W and/or Mo and Ni and/or Co, can contain auxiliary agent simultaneously.The selection of carrier of hydrocracking catalyst component, active metal component and auxiliary agent and consumption can according to this area general knowledge according to application need specifically determine.
In step (3), the molal quantity of control Mo and/or W is 1:10 ~ 1:2 with the ratio of the molal quantity of ammonium sulfide.
In step (4), described inert gas is preferably nitrogen, and described drying condition is as follows: when 90 ~ 140 DEG C drying 4 ~ 10.
In step (5), binding agent is generally the little porous aluminum oxide through peptization.Shapingly can to determine, as extrusion etc. according to the shape of final catalyst.Described drying condition was as follows: 100 ~ 130 DEG C of dryings 4 ~ 14 hours, roasting condition was as follows: 450 ~ 600 DEG C of roastings 3 ~ 10 hours.
In the preparation method of sulfurized hydrogenation Cracking catalyst of the present invention, the imbibition ability of carrier powder is very strong, after making beating process, carrier powder is through fully water suction, be present in slurries d with graininess, as ammonium molybdate and/or ammonium tungstate solution a, when ammonium sulfide solution b and solution c passes into slurries d, ammonium molybdate or ammonium tungstate and ammonium sulfide react the water-fast particle generated tiny and uniform Thiomolybdate or thiqtung state, because carrier component powder does not substantially have capillary absorption ability after making beating, so Thiomolybdate and/or thiqtung state are deposited on the surface of carrier powder equably, in subsequent processes, MoS that the is tiny and lower valency be evenly distributed is decomposed to form at carrier surface
2and WS
2plates, form more corner angle, be conducive to molybdenum and/cobalt is adsorbed onto edges and corners, active higher II type Ni(Co is formed with Mo or W) Mo(W) the active phase of S, make the state of cure (vulcanization) of catalyst high, improve the utilization ratio of active metal, thus improve the Hydrogenation of catalyst.And in the inventive method, the active metallic content of catalyst can adjust flexibly, avoid Thiomolybdate and/or low the brought difficulty of thiqtung state solubility.In addition, the inventive method is less on the pore volume of carrier component, aperture and specific area impact, and therefore, pore volume, the specific area of gained hydrocracking catalyst are larger.
Hydrocracking catalyst prepared by the inventive method, the Thiomolybdate generated due to reaction and/or thiqtung state decomposes are molybdenum sulfide and/or tungsten sulfide, nickel salt and/or cobalt salt are converted into the sulfide of nickel and/or cobalt after follow-up heating, therefore, the hydrocracking catalyst of gained itself is sulphided state, in use without the need to sulfuration again.Result of study proves, load have the catalyst of the lower valency sulfide of Mo, W, Co, Ni in room temperature and drier air be safe, not self-heating with diergolic, therefore, according to this invention method prepared by catalyst, as long as through inert gas treatment, and adopt room temperature airtight and lucifuge packaging, can ensure that catalyst stores, the security of transport and filling process.
The sulfurized hydrogenation Cracking catalyst of the inventive method gained is applicable to need sulphided state hydrocracking catalyst catalytic process.
The sulfurized hydrogenation Cracking catalyst that the inventive method obtains is used for hydrocracking process, be suitable for treatment of heavy hydrocarbon material, comprise in vacuum gas oil (VGO), coker gas oil, deasphalted oil, thermal cracking gas oil, catalytic gas oil, the various hydrocarbon-type oil of catalytic cracking circulation wet goods one or more, raw material is generally the hydro carbons containing boiling point 300 ~ 600 DEG C, and nitrogen content can at 50 ~ 2500 μ g/g.
Detailed description of the invention
Below in conjunction with embodiment in detail technical characterstic of the present invention is described in detail.In the present invention, wt% is mass fraction, and v% is volume fraction.
Embodiment 1
Catalyst catA involved in the present invention.
Preparation Ammoniun Heptamolybdate Solution 250 ml(a), containing 10g molybdenum 100ml in solution, preparation 10wt% ammonium sulfide solution 500ml(b), preparation nickel nitrate solution 40ml(c), containing 5g nickel/100ml in slurries, take 120g contained amorphous silica-alumina dry glue powder, 30gY molecular sieve powder (SiO
2/ Al
2o
3mol ratio is 40, lattice constant is 2.432nm, infrared acidity 0.19mmol/g, specific area 866m
2/ g, pore volume 0.52ml/g); join in 1500g water and be beaten into slurries (d); (a) and (b) and (c) are slowly added in slurries (d); stir; hierarchy of control temperature 65 DEG C; react filtration after 1 hour, washing, by the 100 DEG C of dryings drying in 6 hours under the protection of inert gas of gained material, obtain catalyst intermediate.After catalyst intermediate being put into roller Homogeneous phase mixing, then add the adhesive that 180g is made up of nitric acid and SB alumina peptization, kneading, rolls, and making can the paste of extrusion, extruded moulding.Under the protection of nitrogen, 120 DEG C of dryings 6 hours, 500 DEG C of roastings 4 hours, obtained catalyst catA.
Embodiment 2
Catalyst catB involved in the present invention.
Preparation ammonium tetramolybdate solution 400 ml(a), containing 5g molybdenum 100/ml in solution, preparation 15wt% ammonium sulfide solution 300ml(b), preparation nickel nitrate solution 30ml(c), containing 8 nickel/100ml in slurries, take 110g contained amorphous silica-alumina dry glue powder, 28g beta-molecular sieve powder (SiO
2/ A1
2o
3=28(molecular proportion), lattice constant is 1.198nm, and relative crystallinity is 95%, infrared acidity 0.174mmol/g, specific area 894m
2/ g, pore volume 0.54lml/g); join in 1500g water and be beaten into slurries (d); (a) and (b) and (c) are slowly added in slurries (d); stir; hierarchy of control temperature 65 DEG C; react filtration after 1 hour, washing, by the 110 DEG C of dryings drying in 5 hours under the protection of inert gas of gained material, obtain catalyst intermediate.After catalyst intermediate being put into roller Homogeneous phase mixing, then add the adhesive that 180g is made up of nitric acid and SB alumina peptization, kneading, rolls, and making can the paste of extrusion, extruded moulding.Under the protection of nitrogen, 120 DEG C of dryings 6 hours, 500 DEG C of roastings 4 hours, obtained catalyst catB.
Embodiment 3
Catalyst catC involved in the present invention.
Preparation ammonium metatungstate solution 250 ml(a), containing 10g tungsten 100ml in solution, preparation 10wt% ammonium sulfide solution 500ml(b), preparation nickel nitrate solution 40ml(c), containing 5g nickel/100ml in slurries, take 120g contained amorphous silica-alumina dry glue powder, 30gY molecular sieve powder (SiO
2/ Al
2o
3mol ratio is 40, lattice constant is 2.432nm, infrared acidity 0.19mmol/g, specific area 866m
2/ g, pore volume 0.52ml/g); join in 1500g water and be beaten into slurries (d); (a) and (b) and (c) are slowly added in slurries (d); stir; hierarchy of control temperature 60 C; react filtration after 1 hour, washing, by the 100 DEG C of dryings drying in 6 hours under the protection of inert gas of gained material, obtain catalyst intermediate.After catalyst intermediate being put into roller Homogeneous phase mixing, then add the adhesive that 180g is made up of nitric acid and SB alumina peptization, kneading, rolls, and making can the paste of extrusion, extruded moulding.Under the protection of nitrogen, 120 DEG C of dryings 6 hours, 500 DEG C of roastings 4 hours, obtained catalyst catC.
Comparative example 1
Prepared by reference catalyst D.Take 106g amorphous aluminum silicide, 33gY molecular sieve (character is with embodiment 1), after putting into roller Homogeneous phase mixing, then add the adhesive that 180g is made up of nitric acid and SB alumina peptization, kneading, rolls, and making can the paste of extrusion, extruded moulding.110 DEG C of dryings 6 hours, are then placed in Muffle furnace, be roasting 4 hours in the air of 500 DEG C, obtain reference agent carrier D in temperature.
Take four thio ammonium molybdate 56.9g, add 30ml monoethanolamine and 20ml distilled water, stir lower dissolving, obtain sanguine settled solution A.Take nickel oxide powder 6.5g, add 20ml monoethanolamine and 5.0g tartaric acid, dissolve under adding thermal agitation, obtain blue-green settled solution B.Solution A and solution B are mixed to get solution C.At room temperature place with this solution impregnation 100g reference agent carrier D and dry for 24 hours.Catalyst after drying is placed in tube furnace, and at 350 DEG C, logical nitrogen treatment 4 hours, obtains reference catalyst catD.
Comparative example 2
With 200ml Mo-Ni co-impregnated solution (MoO
336g/100ml and 10g/100ml is respectively with the concentration of NiO) excessive dipping 100g reference agent carrier D 2 hours, 100 DEG C of dryings 6 hours, 500 DEG C of roastings 4 hours, obtained reference catalyst catE.
Reference catalyst catEization adopts the kerosene containing carbon disulfide to be sulfurized oil.Presulfurization condition is as follows: hydrogen dividing potential drop 14.7MPa, curing temperature 370 DEG C, vulcanizing agent content 2wt%, volume space velocity 1.0h
-1, hydrogen to oil volume ratio 1000.
Comparative example 3
In " petroleum refining and chemical industry " (2011,42 (6): 50-56), the preparation method of catalyst prepares reference catalyst F.Take 116g amorphous aluminum silicide, 32gY molecular sieve (character is with embodiment 1), 55.0g ammonium thiomolybdate, 42g nickel nitrate, after putting into roller Homogeneous phase mixing, then add the adhesive that 180g is made up of nitric acid and SB alumina peptization, kneading, roll, making can the paste of extrusion, extruded moulding.Under the protection of nitrogen, 110 DEG C of dryings 6 hours, are then placed in Muffle furnace roasting 4 hours at 500 DEG C, obtained catalyst catF.
The physico-chemical property of table 1 embodiment and comparative example gained catalyst
| Catalyst is numbered | catA | catB | catC | catD | catE | catF |
| Catalyst forms, in element, and wt% | ||||||
| Mo | 15.9 | 14.9 | － | 17.4 | 16.8 | 16.7 |
| W | － | 16.3 | － | － | － | |
| Ni | 4.3 | 3.8 | 3.6 | 4.5 | 4.7 | 4.1 |
| Catalyst property | ||||||
| Specific area, m 2/g | 271 | 380 | 268 | 194 | 197 | 241 |
| Pore volume, ml/g | 0.49 | 0.51 | 0.48 | 0.33 | 0.34 | 0.42 |
The invention described above catalyst catA, catB, catC and comparative example catalyst catD, catE, catF are carried out 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 Activating Test the results are shown in Table 3.
Table 2 evaluation uses feedstock oil character
| Feedstock oil | Iran VGO |
| Density (20 DEG C)/gcm -3 | 0.9025 |
| Boiling range/DEG C | |
| IBP/10%/50% | 308/369/430 |
| 90%/95%/EBP | 50/3526/560 |
| Carbon residue, wt% | 0.2 |
| S，wt% | 1.5 |
| N，wt% | 0.11 |
| BMCI value | 41.5 |
Table 3 catalyst activity evaluation result
| Catalyst is numbered | catA | catB | catC | catD | catE | catF |
| Reaction temperature, DEG C | 368 | 369 | 369 | 382 | 380 | 375 |
| Product slates | ||||||
| < 370 DEG C of conversion ratios, wt% | 64.0 | 64.3 | 64.2 | 64.6 | 65.1 | 63.8 |
| Middle distillates oil selectivity, wt%(132 ~ 370 DEG C) | 85.7 | 85.8 | 85.4 | 81.9 | 83.1 | 84.2 |
| Major product character | ||||||
| Heavy naphtha (82 ~ 132 DEG C) | ||||||
| Virtue is dived, wt% | 60.1 | 59.9 | 61.4 | 59.6 | 59.5 | 59.8 |
| Jet fuel (132 ~ 282 DEG C) | ||||||
| Freezing point, DEG C | <-60 | <-60 | <-60 | <-60 | <-60 | <-60 |
| Aromatic hydrocarbons, wt% | 3.7 | 3.7 | 3.6 | 3.9 | 4.0 | 4.1 |
| Smoke point, mm | 28 | 27 | 28 | 27 | 28 | 27 |
| Diesel oil (282 ~ 350 DEG C) | ||||||
| Cetane number | 64 | 64 | 62 | 59 | 61 | 59 |
| Condensation point, DEG C | -10 | -16 | -11 | -9 | -8 | -8 |
| Tail oil (> 370 DEG C) | ||||||
| BMCI | 8.7 | 9.3 | 8.9 | 10.6 | 10.7 | 10.5 |
Claims (13)
1. a preparation method for sulfurized hydrogenation Cracking catalyst, comprising:
(l) preparation dimolybdate salt and/or ammonium tungstate salting liquid a, formulating vulcanization ammonium salt solution b, preparation nickel salt and/or cobalt salt solution c;
(2) selective hydrocracking catalyst support component, carrier component at least comprises a kind of acidic cracking components, and add water carrier component powder making beating, obtains slurries d;
(3) solution a, solution b and solution c are passed into slurries d, control reaction temperature at 50 ~ 80 DEG C, the time of passing into is 0.5 ~ 2 hour;
(4) material of step (3) gained carried out filter, wash, dry under the protection of inert gas, obtain catalyst intermediate;
(5) catalyst intermediate is added adhesive kneading, through extruded moulding, dry under the protection of inert gas, roasting, makes sulfurized hydrogenation Cracking catalyst.
2. in accordance with the method for claim 1, it is characterized in that in step (1), in ammonium molybdate and/or ammonium tungstate solution, every 100 ml contain 10 ~ 30gMo and/or W; The concentration of ammonium sulfide solution is 5wt% ~ 30wt%; In nickel salt and/or cobalt salt slurries, every 100 ml contain 5 ~ 20gNi and/or Co.
3. in accordance with the method for claim 1, it is characterized in that in step (1), in ammonium molybdate and/or ammonium tungstate solution, every 100 ml contain 5 ~ 10gMo and/or W; The concentration of ammonium sulfide solution is 10wt% ~ 15wt%; In nickel salt and/or cobalt salt slurries, every 100 ml contain 5 ~ 10gNi and/or Co.
4., according to the preparation method of catalyst according to claim 1, it is characterized in that in step (2), acidic cracking components comprise in molecular sieve and amorphous acidic components one or more.
5., according to the preparation method of catalyst according to claim 4, it is characterized in that one or more that described molecular sieve comprises in Y zeolite, beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesopore molecular sieve; Amorphous acidic components are one or more in amorphous aluminum silicide, amorphous silicon magnesium.
6. according to the preparation method of catalyst according to claim 1, it is characterized in that: contain aluminium oxide in hydrocracking catalyst in carrier component or contain auxiliary agent aluminium oxide.
7. according to the preparation method of catalyst according to claim 1, it is characterized in that: with the weight of final catalyst for benchmark, acidic cracking components content is 10wt% ~ 60wt%, Mo and/or W in the content of element for 10wt% ~ 30wt%, Co and/or Ni is in the content of element for 2wt% ~ 10wt%, and the content of aluminium oxide is 0 ~ 50 wt %.
8. according to the preparation method of catalyst according to claim 1, it is characterized in that: in step (2), the volume ratio of carrier component powder and water is 1:5 ~ 1:30.
9. according to the preparation method of catalyst according to claim 1, it is characterized in that: in step (2), the volume ratio of carrier component powder and water is 1:10 ~ 1:20.
10. in accordance with the method for claim 1, it is characterized in that in step (3), the molal quantity of control Mo and/or W is 1:10 ~ 1:2 with the ratio of the molal quantity of ammonium sulfide.
11., according to the preparation method of catalyst according to claim 1, is characterized in that: described nickel salt and/or cobalt salt be selected from nitrate, carbonate, subcarbonate, acetate, chloride one or more.
12., according to the preparation method of catalyst according to claim 1, is characterized in that: in step (4), described drying condition is as follows: when 90 ~ 140 DEG C drying 4 ~ 10.
13., according to the preparation method of catalyst according to claim 1, is characterized in that: in step (5), described drying condition is as follows: 100 ~ 130 DEG C of dryings 4 ~ 14 hours, roasting condition was as follows: 450 ~ 600 DEG C of roastings 3 ~ 10 hours.
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| EP2264129A2 (en) * | 2009-04-27 | 2010-12-22 | Petroleo Brasileiro S.A. | Process for hydrotreating biomass oil diluted in a refinery stream of petroleum hydrocarbons |
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| CN1394684A (en) * | 2002-04-10 | 2003-02-05 | 中国科学院大连化学物理研究所 | Preparation method of transition metal carbide catalyst and its catalytic performance |
| CN101722055A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | Method for preparing sulfide type catalyst |
| EP2264129A2 (en) * | 2009-04-27 | 2010-12-22 | Petroleo Brasileiro S.A. | Process for hydrotreating biomass oil diluted in a refinery stream of petroleum hydrocarbons |
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