CN102039151B - Hydrocracking catalyst and preparation method thereof - Google Patents
Hydrocracking catalyst and preparation method thereof Download PDFInfo
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- CN102039151B CN102039151B CN 200910204243 CN200910204243A CN102039151B CN 102039151 B CN102039151 B CN 102039151B CN 200910204243 CN200910204243 CN 200910204243 CN 200910204243 A CN200910204243 A CN 200910204243A CN 102039151 B CN102039151 B CN 102039151B
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Abstract
The invention discloses a hydrocracking catalyst and a preparation method thereof. The catalyst is prepared by a carbonization method and is amorphous silica aluminum subject to hydro-thermal treatment. The amorphous silica aluminum prepared by the method has the characteristics of large specific surface, large pore volume, centralized pore distribution and appropriate acidity; an enough channel is provided for reactants, the reactants and products are convenient to enter/exit, the active ingredients of the carrier are greatly increased, and the distribution uniformity of the acid centre in the pore channel is improved; and moreover, as a larger space and a specific surface are provided for loading metal, the hydrogenated metal has higher dispersibility, the metal utilization rate is improved, and the catalyst provided by the invention has appropriate cracking activity as well as high hydrogenation activity and medium oil selectivity. The catalyst provided by the invention is particularly suitable for finishing the single-stage hydrocracking process once.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, treatment of heavy hydrocarbon class raw material especially, that produces intermediate oil contains hydrocracking catalyst of amorphous aluminum silicide and preparation method thereof.
Background technology
As one of main means of heavy oil lighting, it is strong that hydrocracking technology has an adaptability to raw material, good product quality, and the intermediate oil yield is high, tail oil added value advantages of higher, the status in modern age petroleum refining industry has become more and more important.
Hydrocracking catalyst is a kind of bifunctional catalyst, and it contains acidic components and hydrogenation component simultaneously.Group vib and group VIII metal that hydrogenation activity generally is selected from the periodic table of elements provide; And acid source comprises carriers such as zeolite and inorganic oxide, and the carrier of hydrocracking catalyst also need provide specific surface and pore volume to carry hydrogenation metal and reaction compartment simultaneously.The activity of hydrocracking catalyst and middle distillates oil selectivity are normally conflicting; Under square one; Active raising will be accompanied by optionally sacrifices, and the acidity through sial and zeolite content and support acidity component thereof in the adjustment catalyst realizes the hydrogenation of catalyst and the coupling of cracking function usually.
GB2166971 discloses a kind of preparation method of amorphous aluminum silicide; Both after pH 12～12.5 times mixes alkali metal aluminate and silicate; Make with reacting aluminum sulfate, silicone content can reach about 35% again, but its shortcoming is that pore volume and specific surface are not high; As the sial of supported catalyst, can not higher metal dispersity be provided for active component.In addition, this patent preparation characteristic is to adopt pump rapid mixing mode to become glue, and high to equipment requirements, the production difficulty is big, has certain limitation.
CNl210755A discloses a kind of amorphous aluminum silicide and preparation method thereof, its silica content 10～50wt%, specific surface 350～600m
2/ g, pore volume 0.8～1.5ml/g, infrared acidity 0.25～0.55mmol/g, its preparation process is NH
3H
2O and aluminic acid form aluminium oxide analysing silicon hydrochlorate afterwards earlier, and this contains ammonia, nitrogen waste water, contaminated environment with generation.In addition, the amorphous aluminum silicide strong acid that this method obtains is more, can cause catalyst to get excessive fragmentation, is unfavorable for that catalyst gets selectivity and must improve.
US6902664 discloses and a kind ofly has been used to produce intermediate oil and gets hydrocracking catalyst; Catalyst contains a kind of amorphous aluminum silicide of high homogeneous phase; In the pH value is about 2.5 with the silicate alkali metal aluminate and after mixing, and adds ammoniacal liquor again, end when pH value reaches 6.5～7.5.This amorphous aluminum silicide specific surface 360～420m
2/ g, pore volume 0.50～0.55ml/g, the specific surface and the pore volume of this amorphous aluminum silicide are little, and pore size distribution is not concentrated, and awaits further to improve.
Along with developing rapidly of petrochemical industry, the requirement of amorphous aluminum silicide is constantly increased, the prior art for preparing amorphous aluminum silicide uses NH mostly
3H
2O is as precipitating reagent, and this contains the waste water of ammonia, nitrogen with generation, and environment is polluted, and the petroleum refining industry in 2l century should follow the strategy of sustainable development, the principle of paying attention to economic benefit, protection environment simultaneously and economizing on resources.Therefore, adopt the good amorphous aluminum silicide of preparation method's nature of production of non-environmental-pollution will become more important.
CNl 033285A has introduced a kind of low-voltage hydrogenation denitrification catalyst of fraction oil of petroleum, and wherein used carrier is the amorphous aluminum silicide that adopts Carbonization Preparation.Raw material is sodium metaaluminate and carbon dioxide, adds minor amount of silicon, SiO
2Content only accounts for 2% in carrier.The specific surface and the pore volume of this amorphous aluminum silicide are lower, can not higher metal dispersity be provided for active component, and acidity is also lower, are not suitable for as carrier of cracking.
CN 1597093A has introduced a kind of amorphous aluminum silicide that adopts Carbonization Preparation, batch production operation, SiO
2Content is 8%～50%, but pore volume, specific area are low relatively, and pore size distribution do not concentrate, and awaits further to improve.
US4758338 and US4721696 provide the preparation method of the silicon modified aluminas that is used for hydrotreating catalyst.The pH swing method is adopted in the preparation of its alumina support;, 2～10 swings of pH value add sodium metasilicate with the pH swing method after making alumina sol more than 5 times; Thereby make the silicon modified aluminas; This product surface is long-pending little, and the aperture is big, and the hole of
accounts for 50～60%; And silicone content is not high, and is main as the heavy oil hydrodesulfurization catalyst carrier that does not need the acidic cleavage function.
CN 1597093A discloses a kind of amorphous aluminum silicide that adopts Carbonization Preparation, and silicon oxide-containing 8wt%～50wt%, specific surface are 300～550m
2/ g, pore volume are 0.7～1.5ml/g, and infrared acidity is 0.32～0.50mmol/g, and its shortcoming is that strong acid is more, and L acid is less relatively, and this all can cause catalyst to get excessive fragmentation, are unfavorable for that catalyst gets selectivity and must improve.
Summary of the invention
In order to overcome the deficiency of prior art, the invention provides high hydrocracking catalyst of a kind of intermediate oil selectivity and preparation method thereof.This hydrocracking catalyst is acid suitable, and pore structure is reasonable, the suitable treatment heavier hydrocarbon feeds.
Hydrocracking catalyst of the present invention; Weight with catalyst is benchmark; Its composition comprises: the content of amorphous aluminum silicide is 20%～60%, the content of Y zeolite be content 0～15%, group vib metal (in oxide) be 10%～30% with the content of group VIII metal (in oxide) be 4%～10%; The character of wherein used amorphous aluminum silicide is following: silicon oxide-containing 8wt%～50wt%, specific area is 300～600m
2/ g, preferably 350～600m
2/ g, pore volume are 0.70～1.60ml/g, preferably 0.75～1.30ml/g; The shared pore volume of bore dia 6～10nm accounts for 80%～95% of total pore volume; Infrared total acid content is 0.30～0.45mmol/g, and middle strong acid amount/infrared total acid content is 0.56～0.81, and it is 1.4～2.3 that L acid measures the acid amount.
The used group vib metal of the present invention is selected from Mo and/or W, and its content is preferably 10wt%～25wt% in oxide; The group VIII metal is selected from Co and/or Ni, and its content is preferably 3wt%～7wt% in oxide.Wherein VIB/ (VIB+VIII) metallic atom ratio is 0.30～0.70, is preferably 0.45～0.50.
The specific area of catalyst of the present invention is 180～250m
2/ g, pore volume are at 0.28～0.50ml/g, and the pore volume of bore dia 4～10nm accounts for 70%～95% of total pore volume, are preferably 80%～95%, and infrared acidity is at 0.19～0.40mmol/g.
The preparation process of hydrocracking catalyst of the present invention comprises: after amorphous aluminum silicide and Y zeolite are mixed; Add adhesive mix pinch, roll agglomerating after, obtain carrier, load hydrogenation active metals again through extruded moulding; Wherein amorphous aluminum silicide adopts Carbonization Preparation, comprises the steps:
A, prepare sodium aluminate solution and sodium silicate solution respectively;
B, with adding part or all of sodium silicate solution in the sodium aluminate solution, feed CO then
2Gas, the control reaction temperature is 10～40 ℃, is preferably 15～35 ℃, the pH value that is controlled to glued bundle is 8～11; Wherein as the CO that feeds
2Gas flow accounts for 40%～100% of total feeding amount, is preferably at 50%～80% o'clock, adds the excess silicon acid sodium solution;
C, under the control temperature and pH value of step b, said mixture ventilates and to stablize 10～30 minutes;
D, the solidliquid mixture of step c gained is filtered Cake Wash;
E, with the making beating of the filter cake of steps d gained, carry out hydrothermal treatment consists then, through filter, drying, obtain amorphous aluminum silicide of the present invention; Described hydrothermal treatment consists condition is following: at 120～150 ℃, 0.5～4.0MPa water vapor pressure was handled 2～5 hours down.
Among the step a, the concentration of sodium aluminate solution is 15～55g Al
2O
3/ l is preferably 15～35g Al
2O
3/ l, the concentration of sodium silicate solution is 50～200g SiO
2/ l is preferably 50～150g SiO
2/ l.
Add part or all of sodium silicate solution among the step b, be the 5wt%～i00wt% of the whole sodium silicate solutions that added.Said CO
2The concentration of gas is 30v%～60v%.Become the stirring of ventilating in the glue process at step b.
The detailed process of step b be below several kinds of situation: (1) adds whole sodium metasilicate in sodium aluminate after, feed CO
2Gas; (2) in sodium aluminate, behind the adding part sodium metasilicate, feed whole CO
2Gas adds the excess silicon acid sodium solution then in mixture; (3) in sodium aluminate, behind the adding part sodium metasilicate, feed portion C O
2Gas leads to CO more on one side
2Gas adds the excess silicon acid sodium solution on one side.
The dope filtration of steps d gained also is washed till neutrality with 50～90 ℃ of deionized waters.
Is 8: 1～10: 1 with step e gained filter cake by the solid-liquid volume ratio, adds the water making beating.
The described drying condition of step e was following: 110～130 ℃ of dryings 6～8 hours.
The used amorphous aluminum silicide of the present invention is a feedstock production with sodium aluminate, sodium metasilicate and carbon dioxide.This method is particularly suitable for adopting the producer of sintering process explained hereafter aluminium oxide, with product sodium aluminate solution and by-product CO between wherein
2Gas is the raw material production amorphous aluminum silicide, the Na that is produced
2CO
3Mother liquor can be circulated to sintering process so that part Na to be provided
2CO
3, form closed cycle, and do not produce contaminated wastewater.
Y zeolite of the present invention can adopt the used molecular sieve of conventional hydrocracking catalyst, and preferred character is following: SiO
2/ Al
2O
3Mol ratio is 35～60, lattice constant is 2.430～2.434nm, infrared acidity 0.15～0.32mmol/g, specific surface 840～920m
2/ g, pore volume 0.50～0.78ml/g.
The carrying method of catalyst activity metal of the present invention can adopt routine techniques preparations such as kneading method, infusion process, preferably adopts first extruded moulding, again the mode of impregnating metal component.After Preparation of catalysts of the present invention adopts Y zeolite and amorphous aluminum silicide dry glue powder to mix, add an amount of adhesive that is prepared by aluminium oxide and nitric acid peptization, mixedly pinch or be rolled into paste, extruded moulding is generally the cylinder bar of 3～8 millimeters of diameters.100～130 ℃ of dryings of carrier warp 4～14 hours were 500～600 ℃ of roastings 3～10 hours.After the activation, adopt saturated or excessive maceration extract dipping to contain the maceration extract of hydrogenation metal, carried out 100～130 ℃ of dryings again 4～14 hours, process catalyst 450～550 ℃ of following roastings 3～10 hours.
Amorphous aluminum silicide of the present invention has passed through hydrothermal treatment consists; Thereby make amorphous aluminum silicide have bigger specific area and pore volume; Pore size distribution is more concentrated, and the pore volume of aperture 6～10nm accounts for 80%～95% of total pore volume, and variation has also taken place acidity simultaneously; Middle strong acid/infrared total acid and L/B acid ratio are higher, help improving the intermediate oil selectivity of hydrocracking catalyst.
Hydrocracking catalyst of the present invention is used for hydrocracking process, is suitable for treatment of heavy hydrocarbon material, is applicable to that the heavy charge scope of this law is very wide; They comprise vacuum gas oil (VGO), coker gas oil, deasphalted oil; Thermal cracking gas oil, catalytic gas oil, the various hydrocarbon-type oils of catalytic cracking circulation wet goods; Also can mix use, raw material is generally the hydro carbons that contains 300～600 ℃ of boiling points, and nitrogen content can be at 50～2500 μ g/g.
Hydrocracking catalyst of the present invention is specially adapted in the single hop single pass method for hydrogen cracking, and operating condition is following: 350～500 ℃ of reaction temperatures are more preferably 380～420 ℃; Hydrogen dividing potential drop 6～20MPa; Be more preferably 9～15MPa, hydrogen to oil volume ratio 500～2000: 1, be more preferably 800～1500: 1; Volume space velocity 0.5～1.8h-1 is more preferably 0.8～1.5h during liquid
-1
Compared with prior art, hydrocracking catalyst of the present invention has adopted Large ratio surface, large pore volume, and pore distribution concentration and amorphous aluminum silicide that have appropriate acid is as carrier component; Be not merely reactant enough passages are provided, help the turnover of reactant and product, the active ingredient of carrier is improved greatly; Improved the uniformity that acid centre distributes in the duct; Bigger space and specific surface bearing metal is provided in addition, made hydrogenation metal have higher dispersiveness, improved the utilization rate of metal; Make catalyst of the present invention not only have suitable lytic activity, have more high hydrogenation activity and middle distillates oil selectivity.Therefore, catalyst of the present invention is used for hydrocracking process and produces intermediate oil, has the characteristics of greater activity and high middle distillates oil selectivity.
The specific embodiment
Among the present invention, specific area and porous are to adopt the low temperature liquid nitrogen determination of adsorption method.Infrared total acid content among the present invention, the sour amount of B, L acid amount and middle strong acid amount are to adopt Nicolet 560 type determination of infrared spectroscopy, and wherein middle strong acid amount is meant the acid amount that 250～450 ℃ of humidity provinces record.Among the present invention, wt% representes mass percent, and v% representes percentage by volume.
Below in conjunction with embodiment the present invention is further described.
Instance 1～3 prepares process for the related amorphous aluminum silicide of catalyst of the present invention, and instance 4～7 is a catalyst preparation process.
Embodiment 1
It is 200g Al that solid sodium aluminate is mixed with concentration
2O
3The dense sodium aluminate solution of/l, being diluted to concentration again is 20g Al
2O
3/ L sodium aluminate working solution is got and is contained SiO
2The sodium silicate solution of 28wt%, being diluted to concentration again is 100g SiO
2/ l sodium metasilicate working solution.Get 10L sodium aluminate working solution and place in the glue jar, add 0.3L sodium metasilicate working solution then, 24 ℃ of control reaction temperatures, feeding concentration is the CO of 55v%
2Gas, the CO of feeding 80%
2Behind the gas, Yi Bian feed CO
2Gas adds 0.6L sodium metasilicate working solution on one side, and the pH value that is controlled to glued bundle is 10.0, ventilates then and stablizes 10 minutes, and dope filtration also is washed till neutrality with 75 ℃ of deionizations.Is to add water making beating at 8: 1 with the filter cake of gained by the solid-liquid volume ratio, and at 120 ℃, the 1MPa water vapor pressure was handled 2 hours down, and after 8 hours, crushing screening gets amorphous aluminum silicide product G L-1 120 ℃ of dryings.
This amorphous aluminum silicide silicon oxide-containing 30wt%, specific surface is 435m
2/ g, pore volume are 0.87ml/g, and the pore volume of bore dia 6～10nm accounts for 89% of total pore volume.Infrared acidity is 0.43mmol/g, and wherein middle the strong acid amount/infrared total acid content is 0.67, and L acid amount/B acid amount is 1.82.
Embodiment 2
Sodium aluminate working solution concentration 25g Al
2O
3/ L, sodium metasilicate working solution concentration 100SiO
2/ l gets 10L sodium aluminate working solution and places in the glue jar, adds 0.5L sodium metasilicate working solution then, 20 ℃ of control reaction temperatures, and feeding concentration is the CO of 35v%
2Gas feeds CO
250% o'clock of gas comprises feeding amount always adds 0.6L sodium metasilicate working solution while ventilate, and the pH value that is controlled to glued bundle is 9.5; Ventilate then and stablized 15 minutes, dope filtration also is washed till neutrality with 75 ℃ of deionizations, and filter cake is to add water at 8: 1 to pull an oar by the solid-liquid volume ratio; At 120 ℃; 1.0MPa water vapor pressure was handled 2 hours down, after 8 hours, crushing screening gets amorphous aluminum silicide product G L-2 120 ℃ of dryings.
This amorphous aluminum silicide silicon oxide-containing 30wt%, specific surface is 470m
2/ g, pore volume are 0.99ml/g, and the pore volume of bore dia 6～10nm accounts for 91% of total pore volume.Infrared acidity is 0.45mmol/g, and wherein middle the strong acid amount/infrared total acid content is 0.73, and L acid amount/B acid amount is 1.91.
Instance 3
Sodium aluminate working solution concentration 25g Al
2O
3/ L, sodium metasilicate working solution concentration 50SiO
2/ l gets 10L sodium aluminate working solution and places in the glue jar, adds 0.8L sodium metasilicate working solution then, 21 ℃ of control reaction temperatures, and feeding concentration is the CO of 40v%
2Gas stops when the pH value reaches 9.0, ventilates then and stablizes 20 minutes; Be washed till neutrality, filter cake is to add the water making beating at 8: 1 by the solid-liquid volume ratio, at 140 ℃; The 3MPa water vapor pressure was handled 2 hours down, and after 8 hours, crushing screening gets amorphous aluminum silicide product G L-3 120 ℃ of dryings.
This amorphous aluminum silicide silicon oxide-containing 20wt%, specific surface is 480m
2/ g, pore volume are 1.07ml/g,, the pore volume of bore dia 6～10nm accounts for 92% of total pore volume.Infrared acidity is 0.37mmol/g, and wherein middle the strong acid amount/infrared total acid content is 0.65, and L acid amount/B acid amount is 1.58.
Embodiment 4
Carrier A involved in the present invention and catalyst catA.Get 100g amorphous aluminum silicide GL-1,9.5gY zeolite (SiO
2/ Al
2O
3Be 40, lattice constant is 2.432nm, infrared acidity 0.19mmol/g, specific surface 866m
2/ g, pore volume 0.52ml/g) with the adhesive that 150g is processed by nitric acid and SB aluminium oxide peptization, mixed pinching rolled, but processes the paste of extrusion, extruded moulding.120 ℃ of dryings 6 hours, 550 ℃ of roastings 4 hours make carrier A.Again with the 200ml excessive dipping of Mo-Ni co-impregnated solution 80g carrier A 2 hours, 100 ℃ of dryings 6 hours, 500 ℃ of roastings 4 hours make catalyst catA.
Embodiment 5
Carrier B involved in the present invention and catalyst catB.Get the adhesive that 100GL-1 amorphous aluminum silicide, 9.5g embodiment 4 used Y zeolites and 150g are processed by nitric acid and SB aluminium oxide peptization, mix and pinch, roll, but process the paste of extrusion, extruded moulding.110 ℃ of dryings 6 hours, 550 ℃ of roastings 4 hours make carrier B.Again with the 200ml excessive dipping of W-Ni co-impregnated solution 80g carrier B 2 hours, 110 ℃ of dryings 6 hours, 500 ℃ of roastings 4 hours make catalyst catB.
Embodiment 6
Preparation condition is with instance 5.Replace amorphous aluminum silicide GL-1 by GL-2, make support C and catalyst catC.
Embodiment 7
Preparation condition is with instance 5.Replace amorphous aluminum silicide GL-1 by GL-3, make carrier D and catalyst catD.
Comparative example 1
It is 200g Al that solid sodium aluminate is mixed with concentration
2O
3The dense sodium aluminate solution of/l, being diluted to concentration again is 20g Al
2O
3/ L sodium aluminate working solution is got and is contained SiO
2The sodium silicate solution of 28wt%, being diluted to concentration again is 100g SiO
2/ l sodium metasilicate working solution.Get 10L sodium aluminate working solution and place in the glue jar, add 0.3L sodium metasilicate working solution then, 24 ℃ of control reaction temperatures, feeding concentration is the CO of 55v%
2Gas, the CO of feeding 80%
2Behind the gas, Yi Bian feed CO
2Gas adds 0.6L sodium metasilicate working solution on one side, and the pH value that is controlled to glued bundle is 10.0, ventilates then and stablizes 10 minutes, and dope filtration also is washed till neutrality with 75 ℃ of deionized waters.Get amorphous aluminum silicide product DGL-1 at 8 hours crushing screenings of 120 ℃ of dryings.
This amorphous aluminum silicide silicon oxide-containing 30wt%, specific surface is 430m
2/ g, pore volume are 0.84ml/g, and the pore volume of bore dia 6～10nm accounts for 72% of total pore volume.Infrared acidity is 0.44mmol/g, and wherein middle the strong acid amount/infrared total acid content is 0.40, and L acid amount/B acid amount is 0.95.
Comparative example 2
Reference carrier E and reference catalyst catE.Take by weighing the adhesive that 100g reference amorphous aluminum silicide DGL-1,9.2g instance 4 used Y zeolites and 150g are processed by nitric acid and SB aluminium oxide peptization, mix and pinch, roll, but process the paste of extrusion, extruded moulding.120 ℃ of dryings 6 hours, 550 ℃ of roastings 4 hours make carrier reference E.Again with the 200ml excessive dipping of W-Ni co-impregnated solution 80g carrier E 2 hours, 110 ℃ of dryings 6 hours, 500 ℃ of roastings 4 hours make reference catalyst catE.Table 1 is the character of embodiment gained catalyst.
Table 1 embodiment gained catalyst physico-chemical property
Can find out from table 1; It is higher relatively than comparative example gained catalyst that the inventive method prepares the pore volume and the specific surface of catalyst, and the decentralization that this helps improving metal has increased the effective rate of utilization of metal; And 4～10nm pore size distribution is more concentrated; The middle strong acid of catalyst/infrared total acid and L/B acid increase substantially, and the excessive fragmentation that these have all avoided raw molecule effectively is beneficial to the raising of catalyst middle distillates oil selectivity.The invention described above catalyst catA, catB, catC, catD and comparative example catalyst catE are carried out active evaluation test.Test is carried out on the 200ml small hydrogenation device, adopts single hop single pass flow process, and raw materials used oiliness matter is seen table 2.Operating condition is following: hydrogen dividing potential drop 14.7MPa, hydrogen to oil volume ratio 1200: 1, volume space velocity 0.92h during liquid
-1The catalyst activity result of the test is seen table 3.
Table 2 feedstock oil character
| The feedstock oil title | Iran VGO |
| Density (20 ℃), g/cm 3 | 0.9164 |
| Boiling range, ℃ | 528～531 |
| Viscosity (50 ℃), mm 2/s | 33.69 |
| Viscosity (100 ℃), mm 2/s | 6.944 |
| Condensation point, ℃ | 34 |
| Acid number, mgKOH/g | 0.49 |
| Carbon residue, % | 0.32 |
| S，μg/g | 16000 |
| N，μg/g | 1475 |
| C，％ | 85.25 |
| H，％ | 11.96 |
| The BMCI value | 48.2 |
| Refractive power/n D 70 | 1.4899 |
Table 3 catalyst activity evaluation result
Evaluation result by table 3 catalyst can find out, the prepared catalyst of the present invention has good middle distillates oil selectivity on the basis of greater activity.
Claims (20)
1. hydrocracking catalyst; Weight with catalyst is benchmark; Its composition comprises: the content of amorphous aluminum silicide is 20%～60%, the content of Y zeolite be content 0～15%, the group vib metal oxide be 10%～30% and the content of group VIII metal oxide be 4%～10%; The character of wherein used amorphous aluminum silicide is following: silicon oxide-containing 8%～50%, specific area are 300～600m
2/ g, pore volume are 0.70～1.60mL/g, and the shared pore volume of bore dia 6～10hm accounts for 80%～95% of total pore volume, and infrared total acid content is 0.30～0.45mmol/g, and middle strong acid amount/infrared total acid content is 0.56～0.81, and L acid amount/B acid amount is 1.4～2.3.
2. according to the described hydrocracking catalyst of claim 1, the specific area that it is characterized in that described amorphous aluminum silicide is 350～600m
2/ g, pore volume are 0.75～1.30mL/g.
3. according to the described hydrocracking catalyst of claim 1, it is characterized in that used group vib metal is selected from Mo and/or W, its content is counted 10wt%～25wt% with oxide; The group VIII metal is selected from Co and/or Ni, and its content is counted 3wt%～7wt% with oxide.
4. according to claim 1 or 3 described hydrocracking catalysts, it is characterized in that in the described catalyst, the atomic ratio of group vib metal and group VIII metal is following: VIB/ (VIB+VIII) metallic atom ratio is 0.30～0.70.
5. according to the described hydrocracking catalyst of claim 1, the specific area that it is characterized in that said catalyst is 180～250m
2/ g, pore volume are at 0.28～0.50mL/g, and the pore volume of bore dia 4～10nm accounts for 70%～95% of total pore volume, and infrared acidity is at 0.19～0.40mmol/g.
6. according to the described hydrocracking catalyst of claim 1, it is characterized in that the character of said Y zeolite is following: SiO
2/ Al
2O
3Mol ratio is 35～60, lattice constant is 2.430～2.434nm, infrared acidity 0.15～0.32mmol/g, specific area 840～920m
2/ g, pore volume 0.50～0.78mL/g.
7. the preparation method of the arbitrary said hydrocracking catalyst of claim 1～6; Comprise: after amorphous aluminum silicide and Y zeolite are mixed, add adhesive mix pinch, roll agglomerating after, through extruded moulding; Dry and roasting obtains carrier, load hydrogenation active metals again; Wherein amorphous aluminum silicide adopts Carbonization Preparation, comprises the steps:
A, prepare sodium aluminate solution and sodium silicate solution respectively;
B, with adding part or all of sodium silicate solution in the sodium aluminate solution, feed CO then
2Gas, the control reaction temperature is 10～40 ℃, the pH value that is controlled to glued bundle is 8～11; Wherein as the CO that feeds
2Gas flow accounts for 40% of total feeding amount～100% o'clock, adds the excess silicon acid sodium solution;
C, under the control temperature and pH value of step b, the mixture of step b gained ventilates and to stablize 10～30 minutes;
D, the solidliquid mixture of step c gained is filtered Cake Wash;
E, with the making beating of the filter cake of steps d gained, carry out hydrothermal treatment consists then, through filter, drying, obtain amorphous aluminum silicide; Described hydrothermal treatment consists condition is following: at 120～150 ℃, 0.5～4.0MPa water vapor pressure was handled 2～5 hours down.
8. according to the described method of claim 7, it is characterized in that among the described step b, as the CO that feeds
2Gas flow accounts for 50% of total feeding amount～80% o'clock, adds the excess silicon acid sodium solution.
9. according to the described preparation method of claim 7, it is characterized in that among the described step a that the concentration of sodium aluminate solution is 15～55g Al
2O
3/ L, the concentration of sodium silicate solution is 50～200g SiO
2/ L.
10. according to the described preparation method of claim 7, it is characterized in that adding part or all of sodium silicate solution among the step b, be the 5wt%～100wt% of the whole sodium silicate solutions that added.
11., it is characterized in that said CO according to the described preparation method of claim 7
2The concentration of gas is 30v%～60v%.
12., it is characterized in that the detailed process of step b adopts one of following method: (1) adds whole sodium metasilicate in sodium aluminate after, feed CO according to the described preparation method of claim 7
2Gas; (2) in sodium aluminate, behind the adding part sodium metasilicate, feed whole CO
2Gas adds the excess silicon acid sodium solution then in mixture; (3) in sodium aluminate, behind the adding part sodium metasilicate, feed portion C O
2Gas leads to CO more on one side
2Gas adds the excess silicon acid sodium solution on one side.
13., it is characterized in that the described washing of steps d is that filter cake is washed till neutrality with 50～90 ℃ of deionized waters according to the described preparation method of claim 7.
14. according to the described preparation method of claim 7, it is characterized in that the described making beating of step e is is 8: 1～10: 1 by the solid-liquid volume ratio, in filter cake, add the water making beating.
15., it is characterized in that the described drying condition of step e is following: 110～130 ℃ of dryings 6～8 hours according to the described preparation method of claim 7.
16., it is characterized in that the condition of said carrier drying and roasting is following according to the described preparation method of claim 7: 100～130 ℃ of dryings of warp 4～14 hours, 500～600 ℃ of roastings 3～10 hours.
17. according to the described preparation method of claim 7; The carrying method that it is characterized in that said reactive metal adopts infusion process; Behind the dipping reactive metal, condition dry and roasting is following: 100～130 ℃ of dryings 4～14 hours, and 450～550 ℃ of following roastings 3～10 hours.
18. a method for hydrogen cracking is characterized in that adopting the arbitrary described hydrocracking catalyst of claim 1～6.
19., it is characterized in that described method for hydrogen cracking is the single hop single pass according to the described method of claim 18.
20., it is characterized in that the operating condition of described method for hydrogen cracking is following according to the described method of claim 19: 350～500 ℃ of reaction temperatures, hydrogen dividing potential drop 6～20MPa, hydrogen to oil volume ratio 500～2000: 1, volume space velocity 0.5～1.8h during liquid
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014047752A1 (en) * | 2012-09-28 | 2014-04-03 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst for unsaturated compound |
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| CN103191773B (en) * | 2012-01-06 | 2015-05-13 | 中国石油化工股份有限公司 | Method for preparing hydrocracking catalyst |
| CN103191775B (en) * | 2012-01-06 | 2014-08-20 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst |
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| CN107029779B (en) * | 2015-07-28 | 2019-03-22 | 中国石油化工股份有限公司 | A kind of multi-stage porous hydrocracking catalyst and its application containing Y type molecular sieve |
| CN106391102B (en) * | 2015-07-28 | 2018-11-30 | 中国石油化工股份有限公司 | A kind of multi-stage porous hydrocracking catalyst of the molecular sieve of type containing Beta and its application |
| CN107661756B (en) * | 2016-07-29 | 2021-03-09 | 神华集团有限责任公司 | Hydrocracking catalyst for co-production of lubricating oil base oil, preparation method and application thereof, and Fischer-Tropsch wax hydrocracking method |
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| CN113019425B (en) * | 2019-12-25 | 2022-09-09 | 中国石油化工股份有限公司 | Hydrotreating catalyst carrier, hydrotreating catalyst and preparation method thereof |
| CN111502621B (en) * | 2020-05-25 | 2022-04-01 | 山东立鑫石油机械制造有限公司 | Thick oil double-injection thin-extraction device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597093A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Method of preparing amorphous silica-alumina using carbonization |
| CN101239314A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing amorphous aluminum silicide and preparation thereof |
| CN101239328A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Amorphous silica-alumina and its preparing method |
-
2009
- 2009-10-21 CN CN 200910204243 patent/CN102039151B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597093A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Method of preparing amorphous silica-alumina using carbonization |
| CN101239314A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing amorphous aluminum silicide and preparation thereof |
| CN101239328A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Amorphous silica-alumina and its preparing method |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2005-219955A 2005.08.18 |
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