CN101144033B - Hydrocracking catalyst and preparation thereof - Google Patents
Hydrocracking catalyst and preparation thereof Download PDFInfo
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- CN101144033B CN101144033B CN2006101129867A CN200610112986A CN101144033B CN 101144033 B CN101144033 B CN 101144033B CN 2006101129867 A CN2006101129867 A CN 2006101129867A CN 200610112986 A CN200610112986 A CN 200610112986A CN 101144033 B CN101144033 B CN 101144033B
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Abstract
The invention relates to a hydrocracking catalyst and a method for preparing the same, wherein the catalyst contains effective dose of cracking active component, effective dose of hydrogenating active metal component and medium, in which the medium is compounded by a big pore volume aluminum oxide with more than 0.6-1.2ml/g of pore volume, a moderate pore volume aluminum oxide with 0.48-0.6ml/g of pore volume and a small pore volume aluminum oxide with 0.2-less than 0.48ml/g of pore volume. The medium contains 10-60 percent by weight of small pore volume aluminum oxide, 5-60 percent by weightof moderate pore volume aluminum oxide and 15-60 percent by weight of big pore volume aluminum oxide. The catalyst is prepared by mixing, forming and roasting effective dose of cracking active component and the medium to prepare the carrier, and introducing the carrier into effective dose of hydrogenating active metal components. Compared with the catalyst provided by the prior art, the catalyst of the invention has increased activity and better strength.
Description
Technical field
The invention relates to a kind of hydrocracking catalyst and preparation thereof.
Background technology
Hydrocracking catalyst is a kind of dual-function catalyst, and it has lytic activity and hydrogenation activity simultaneously, promptly contains acidic components and hydrogenation activity component simultaneously; The cracking component generally is selected from acid sial, comprising: silica-alumina, zeolite molecular sieve and composition thereof, hydrogenation activity component generally are selected from metal, metal oxide and/or the metallic sulfide of group vib and VIII family in the periodic table of elements.Along with heavy, the poor qualityization of petroleum resources, hydrocracking raw material is variation day by day.Process the more needs of medium solid and inferior raw material in order to adapt to hydrocracking, generally can improve the performance of the processing heavy feedstocks of catalyzer by the pore volume that improves catalyzer.And the common method that improves the catalyzer pore volume can realize by the method for introducing the large pore volume component in carrier of hydrocracking catalyst.
CN1054150C discloses a kind of catalyst for hydrocracking diesel oil, and carrier that this catalyzer is made up of aluminum oxide, amorphous aluminum silicide and molecular sieve and the hydrogenation active metals that loads on this carrier are formed WO in the catalyzer
3Content be that the content of 10-30 heavy %, NiO are that the content of the heavy % of 2-15, molecular sieve is that the content of the heavy % of 5-45, aluminum oxide is that the content of the heavy % of 30-70, amorphous aluminum silicide is the heavy % of 5-25, described molecular sieve is a Y zeolite, its infrared total acid content is 0.5-1 mmole/gram, and lattice constant is 2.436-2.444 nanometers.Described aluminum oxide is pore volume 0.8-1.1 milliliter/gram; Surface-area 230-400 rice
2The little porous aluminum oxide of/gram.
CN1055961C discloses a kind of hydrocracking catalyst that is specially adapted to produce intermediate oil, contain amorphous silicon al composition and aperture alumina adhesive, the content of amorphous aluminum silicide is 30-60w%, at least a group vib element and at least a VIII family element, hydrogenation metal oxide compound total content is 20-35w%, surplus is the aperture alumina adhesive, it is characterized in that catalyst specific surface 150-300m
2/ g, pore volume 0.25-0.50ml/g, the 4-15nm pore distribution is at 60-90%, infrared acidity 0.30-0.50mmol/g.
CN1400284A catalyst for hydrogenation treatment of diesel oil, this catalyzer contains a kind of carrier and the molybdenum and/or tungsten and nickel and/or the cobalt that load on this carrier, it is characterized in that, described carrier is made up of aluminum oxide and zeolite, the weight ratio of aluminum oxide and zeolite is 90:10-50:50, described aluminum oxide is the aluminum oxide that is composited according to the weight ratio of 75:25-50:50 by little porous aluminum oxide and macroporous aluminium oxide, wherein, to be diameter account for the aluminum oxide of total pore volume more than 95% less than the pore volume in 80 dust holes to little porous aluminum oxide, and macroporous aluminium oxide is that the pore volume in diameter 60-600 dust holes accounts for the aluminum oxide of total pore volume more than 70%.
The hydrocracking catalyst that contains large pore volume matrix that prior art provides is more suitable for the hydrocracking of heavy hydrocarbon oil, and its defective is that the hydrocarbon oil hydrogenation activity of conversion of catalyzer is low on the one hand, is the intensity difference of catalyzer on the one hand; Although have higher intensity and contain aperture appearance matrix components catalyzer, catalyst activity is low.
Summary of the invention
The technical problem to be solved in the present invention is at containing the low defective of hydrocracking catalyst hydrocarbon oil hydrogenation activity of conversion that large pore volume matrix components and/or aperture hold matrix components in the prior art, and higher hydrocracking catalyst of a kind of new hydrocarbon oil hydrogenation activity of conversion and preparation method thereof is provided.
The invention provides a kind of hydrocracking catalyst, contain the cracking activity component of significant quantity, the hydrogenation active metals component and the matrix of significant quantity, wherein said matrix is by a kind of pore volume〉the large pore volume aluminum oxide of 0.6～1.2ml/g, a kind of pore volume be the middle pore volume aluminum oxide of 0.48～0.6ml/g and a kind of pore volume 0.2～＜aperture of 0.48ml/g holds aluminum oxide and is composited, with described matrix is benchmark and by weight percentage, the medium and small porous aluminum oxide content of described matrix is 10～60%, mesoporous aluminas content is 5～60%, and macroporous aluminium oxide content is 15～60%.
The invention provides a kind of hydrocracking catalyst preparation method, comprise the cracking activity component of significant quantity is mixed with the precursor of matrix and/or described matrix, moulding and roasting prepare carrier, in described carrier, introduce the hydrogenation active metals component of significant quantity afterwards, the precursor of wherein said matrix and/or described matrix is a kind of pore volume〉large pore volume aluminum oxide and/or this large pore volume aluminum oxide precursor of 0.6～1.2ml/g, a kind of pore volume be 0.48～0.6ml/g middle pore volume aluminum oxide and/or should in pore volume aluminum oxide precursor and a kind of pore volume 0.2～＜aperture of 0.48ml/g holds the mixture that aluminum oxide and/or this aperture hold the aluminum oxide precursor, with described matrix is benchmark and by weight percentage, wherein the aperture alumina content is 10～60%, mesoporous aluminas content is 5～60%, and macroporous aluminium oxide content is 15～60%.
Compare with the catalyzer that prior art provides, the invention provides activity of such catalysts and obviously improve.In addition, the invention provides catalyzer and maintain intensity preferably.
For example compared with the support of the catalyst RS-2 that only contains macropore and little porous aluminum oxide by support of the catalyst CS1 provided by the invention, its intensity level improves 8N/mm, and the pore volume value improves 0.104ml/g.The CS1 preparing carriers is become catalyzer C-1, and its specific activity is active high by 5.5% by the catalyzer RC-1 of RS-2 preparing carriers.
Embodiment
According to catalyzer provided by the invention, described aluminum oxide is selected from the aluminum oxide among any γ, η, θ, δ and the χ that can satisfy requirement of the present invention, also can be to contain one or more to be selected from titanium, magnesium, boron, zirconium, thorium, niobium, rare earth and to dose aluminum oxide among γ, η, θ, δ and the χ of component, be preferably γ-aluminum oxide and contain one or more and be selected from γ-aluminum oxide that titanium, magnesium, boron, zirconium, thorium, niobium, rare earth are dosed component.They can be commercially available commodity, also can be by any one existing method preparation.With the catalyzer is benchmark, and the content of described catalyzer mesostroma is preferably 15～80 weight %, more preferably 20～70 weight %.
The pore volume of described matrix adopts oil and petroleum products experimental technique standard GB/T5819-19958 method to measure.
Described cracking activity component is selected from the silica-alumina of the cracking activity component of Chang Zuowei hydrocracking catalyst, in the molecular sieve one or more.Wherein, the molecular sieve that is usually used in the hydrogenation cracking activity component, as being zeolite with macroporous structure, as zeolite with faujusite, Beta zeolite, omega zeolite structure, it can be zeolite with central hole structure, as have mordenite, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-48 zeolite, an isostructural zeolite of ZSM-57 zeolite, can be zeolite also, as have Erionite zeolite, the zeolite structured zeolite of ZSM-34 with small structure.Further preferably have the faujusite structure zeolite, have the zeolite structured zeolite of Beta, have in the zeolite of mordenite structure one or more.Described zeolite with faujusite structure is preferably y-type zeolite, further preferred wherein be HY zeolite, rare-earth type Y zeolite REY, rare-earth type HY zeolite REHY, overstable gamma zeolite USY, rare-earth type overstable gamma zeolite REUSY, phosphorated Y and super steady a kind of in HY type zeolite, the dealuminium Y type beta stone of reaching.With the catalyzer is benchmark, and the cracking activity components contents is preferably 5～60 weight % in the described catalyzer, more preferably 5～50 weight %.
Described hydrogenation active metals component is selected from least a group VIII and at least a group vib metal component.In oxide compound and with the catalyzer is benchmark, the content that is selected from the group vib metal component in the described catalyzer is preferably 5～50 weight %, 10～40 weight % more preferably, the content that is selected from the group VIII metal component is preferably 1～15 weight %, more preferably 2～9 weight %.
In the catalyzer provided by the invention, can also contain the material that any material that does not influence the catalytic performance of catalyzer provided by the invention maybe can improve the catalytic performance of catalyzer provided by the invention.As introducing in the components such as fluorine, phosphorus, boron one or more, be benchmark in element and with the catalyzer, the introducing amount of above-mentioned auxiliary agent is no more than 10 weight %, preferably is no more than 5 weight %.
Can also contain one or more in the catalyzer provided by the invention and be selected from and contain oxygen or nitrogenous organism, preferred oxygen-containing organic compound is selected from one or more in organic alcohol, the organic acid; Preferred organic compounds containing nitrogen is selected from one or more in organic amine, the organic ammonium salt.For example, oxygenatedchemicals can be ethylene glycol, glycerol, polyoxyethylene glycol (molecular weight is 200-1500), Diethylene Glycol, butyleneglycol, acetate, toxilic acid, oxalic acid, nitrilotriacetic acid, 1, in 2-CDTA, citric acid, tartrate, the oxysuccinic acid one or more, organic compounds containing nitrogen can be quadrol, EDTA and ammonium salt thereof.The mol ratio of organism and group VIII metal component is 0.01-10, is preferably 0.05-8.
According to method provided by the invention, described moulding adopts ordinary method to carry out, as methods such as compressing tablet, spin, extrusions.When extrusion moulding, can add an amount of extrusion aid and/or tackiness agent, extrusion moulding then.The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, do not give unnecessary details at this.This area customary way and condition are adopted in described roasting, can be 350-650 ℃ as maturing temperature; Be preferably 400-600 ℃, roasting time is 2-6 hours, is preferably 3-5 hours.
According to method provided by the invention, the method for described introducing hydrogenation active metals component can be to contact with described carrier after the hydrogenation active metals compound is mixed with solution containing, as the method by dipping.Described dipping method is an ordinary method, by adjusting and control, prepare that to specify the method for hydrogenation metal and organic additive content catalyzer be conventionally known to one of skill in the art to concentration, consumption or the carrier consumption of the solution that contains the hydrogenation active metals compound.Preferably include the step of drying, roasting or not roasting after the described dipping.The condition of described drying and roasting is the habitual condition of preparation catalyzer, as drying temperature is 80-350 ℃, be preferably 100-300 ℃, be 1-24 hour time of drying, be preferably 2-12 hour, maturing temperature is 350-550 ℃ and is preferably 400-500 ℃ that roasting time is 1-10 hour, is preferably 2-8 hour.
Described hydrogenation active metals component is selected from least a group VIII and at least a group vib metal component.Describedly containing in the soluble compound that the hydrogenation active metals compound is selected from these metals one or more, for example, can be in the water-soluble salt of these metals one or more.
When also containing one or more the adjuvant component that is selected from fluorine, phosphorus and the boron in the described catalyzer, its introducing method can be that the compound that will contain described auxiliary agent directly mixes with described matrix with described molecular sieve, the method for moulding and roasting is introduced; Can be the compound that will contain described auxiliary agent contacts with described carrier after the hydrogenation active metals compound is mixed with mixing solutions with containing; Can also be to contact and roasting with described carrier behind the independent obtain solution of the compound that contains auxiliary agent.When auxiliary agent and hydrogenation active metals group are introduced described carrier respectively, preferably at first auxiliary compound solution contacts with described carrier and roasting with containing, contact with the solution that contains the hydrogenation active metals compound more afterwards, for example by methods such as ion-exchange, dipping, co-precipitation, preferred pickling process, wherein said maturing temperature is 350-550 ℃, is preferably 400-500 ℃, roasting time is 2-8 hour, is preferably 3-6 hour.
When described catalyzer contains organism, described organic introducing method, can be with described organism with contain the compound of other component, as contain in the hydrogenation active metals compound one or more and be mixed with the described carrier of dipping and dry behind the mixing solutions; Can also be with the described carrier of dipping behind the independent obtain solution of organism and dry.When being introduced separately into organism, preferably at first introduce other components, as at first introducing the hydrogenation active metals component, introduce organism afterwards again.Described organic introducing amount makes that the mol ratio of organism and group VIII metal component is 0.01-10 in the catalyzer, is preferably 0.05-8.The described dry conventional process that adopts is carried out, and drying temperature wherein is preferably 100-300 ℃, is preferably 1-12 hour time of drying, and further preferred drying temperature is 100-280 ℃, and be 2-8 hour time of drying.
According to the ordinary method in this area, catalyzer provided by the invention is before using, usually can be in the presence of hydrogen, under 140-370 ℃ temperature, carry out prevulcanized with sulphur, hydrogen sulfide or sulfur-bearing raw material, this prevulcanized can be carried out also can original position vulcanizing in device outside device, is translated into sulfide type.
Catalyzer provided by the invention is applicable to hydrocarbon raw material carried out hydrocracking, has hydrocarbon fraction than lower boiling and lower molecular weight with production.Described hydrocarbon raw material can be various heavy mineral oils or synthetic oil or their mixed fraction oil, as straight run gas oil (straight run gas oil), vacuum gas oil (vacuum gas oil), metal removal oil (demetallized oils), long residuum (atmosphericresidue), diasphaltene vacuum residuum (deasphalted vacuum residue), coker distillate (coker distillates), catalytic cracking distilled oil (cat craker distillates), shale oil (shale oil), asphalt sand oil (tar sand oil), liquefied coal coil (coalliquid) etc.The hydrocracking that catalyzer provided by the invention is specially adapted to heavy and inferior distillate oil is 149-371 ℃ to produce boiling range, and especially boiling range is the hydrocracking process of 180-370 ℃ of intermediate oils.
When catalyzer provided by the invention is used for distillate hydrocracking, can under the hydrocracking process condition of routine, use, as temperature of reaction 200-650 ℃, preferred 300-510 ℃, reaction pressure 3-24 MPa, preferred 4-15 MPa, liquid hourly space velocity 0.1-10 hour
-1Preferred 0.2-5 hour
-1, hydrogen to oil volume ratio 100-5000, preferred 200-1000.
To the present invention be described by example below.
Agents useful for same in the example except that specifying, is chemically pure reagent.
Comparative Examples 1
This Comparative Examples is described the preparation of reference catalyst carrier
(the Chang Ling catalyst plant is produced to get the 250g Y zeolite, lattice constant 24.58, sodium oxide content 0.1%, trade(brand)name LAY, butt 75%) (Shandong Aluminum Plant produces with 568 gram alumina hydrate powders, trade(brand)name SD powder, pore volume 0.38ml/g, butt 66%), 260 gram alumina hydrate powders (produce by the Chang Ling catalyst plant, trade(brand)name CL powder, pore volume 0.91ml/g, butt 72%) mixes, be extruded into circumscribed circle diameter afterwards and be 1.6 millimeters trilobal bar, wet bar was in 120 ℃ of oven dry 4 hours, 550 ℃ of roasting temperatures 3 hours, carrier RS-1, support of the catalyst is formed and the carrier crushing strength, pore volume sees Table 1.
Comparative Examples 2
This Comparative Examples is described the preparation of reference catalyst carrier
Get 250g Y zeolite (with Comparative Examples 1) and contain the aqueous solution of analytical pure nitric acid 20ml with 426 gram SD powder (with Comparative Examples 1), 391 gram CL powder (with Comparative Examples 1), 30 gram sesbania powder, 750ml, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, 120 ℃ of oven dry, 550 ℃ of roasting temperatures 3 hours, get carrier RS-2, support of the catalyst composition and carrier crushing strength, pore volume see Table 1.
Example 1
The preparation of this case description support of the catalyst of the present invention
Get 250g Y zeolite (with Comparative Examples 1) with 227 gram SD powder (with Comparative Examples 1), 313 gram CL powder (with Comparative Examples 1), (Sasol company produces 268 gram SB, trade(brand)name SB, pore volume 0.53ml/g, butt 70%) powder, 30 gram sesbania powder, 750ml contain the aqueous solution of analytical pure nitric acid 20ml, are extruded into circumscribed circle diameter and are 1.6 millimeters trilobal bar, 120 ℃ of oven dry, 550 ℃ of roasting temperatures 3 hours, support C S-l, support of the catalyst forms and carrier crushing strength, pore volume see Table 1.
Example 2
The preparation of this case description support of the catalyst of the present invention
Get 250g Y zeolite (with Comparative Examples 1) with 35 gram SD powder (with Comparative Examples 1), 64 gram CL powder (with Comparative Examples 1), 229 gram SB powder (with example 1), 30 gram sesbania powder, 750ml contain the aqueous solution of analytical pure nitric acid 20ml, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, 120 ℃ of oven dry, 550 ℃ of roasting temperatures 3 hours, get support C S-2, support of the catalyst composition and carrier crushing strength, pore volume see Table 1.
Example 3
The preparation of this case description support of the catalyst of the present invention
(Sasol produces the aluminum silicon powder of silicon oxide-containing 40% to get the 250g aluminum silicon powder, trade name Sira-40, butt 80%) with 1091 gram SD powder (with Comparative Examples 1), 1250 gram CL powder (with Comparative Examples 1), 257 gram SB powder (with example 1), 1800ml contains the aqueous solution of analytical pure nitric acid 55ml, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, 120 ℃ of oven dry, 450 ℃ of roasting temperatures 6 hours, get support C S-3, support of the catalyst composition and carrier crushing strength, pore volume see Table 1.
Table 1
The result that table 1 provides can illustrate, obviously improved by the crushing strength of carrier provided by the invention.
Example 4
This example illustrates catalyzer provided by the invention and preparation thereof.
Get 100g CS-l carrier with containing ammonium metawolframate (Sichuan Zigong Hard Alloy Foundry, tungsten oxide content is 82 weight %) 44 the gram, nickelous nitrate (Beijing Yili Fine Chemicals Co., Ltd.'s product, nickel oxide content is 25.4 weight %) the 25 80ml aqueous solution dippings that restrain, in 120 ℃ of dryings 4 hours, 480 ℃ of roastings 4 hours, obtain catalyzer C-1, its composition sees Table 2.
Example 5
This example illustrates catalyzer provided by the invention and preparation thereof.
Preparation catalyzer used carrier, ammonium metawolframate, nickelous nitrate and consumption are with example 4, and different is when the dipping hydrogenation active metals, adds the 5g citric acid in dipping solution, and catalyzer obtains catalyzer C-2 in 150 ℃ of processing 16 hours.Wherein the mol ratio of citric acid and group VIII metal component is 0.26, and in 4 hours samples of 480 ℃ of roastings, the composition of catalyzer C-2 sees Table 2.
Example 6
This example illustrates catalyzer provided by the invention and preparation thereof.
Get 100g CS-2 carrier with containing ammonium metawolframate (Sichuan Zigong Hard Alloy Foundry, tungsten oxide content is 82 weight %) 22 the gram, nickelous nitrate (Beijing Yili Fine Chemicals Co., Ltd.'s product, nickel oxide content is 25.4 weight %) the 10 80ml aqueous solution dippings that restrain, in 120 ℃ of dryings 4 hours, 480 ℃ of roastings 4 hours, intermediate C-3a, again with the 70ml aqueous solution dipping that contains quadrol 12.3g, 60 ℃ of vacuum-dryings get catalyzer C-3.Wherein the mol ratio of quadrol and group VIII metal component is 6.0, and in 480 ℃ of roastings 3 hours, this catalyzer composition saw Table 2.
Example 7
This example illustrates catalyzer provided by the invention and preparation thereof.
Get the C-3a of 100g example 6 gained, the 70ml aqueous solution dipping of Xiao Suangu (Beijing Yili Fine Chemicals Co., Ltd.'s product, cobalt oxide content are 24.5 weight %) 30 gram was in 120 ℃ of dryings 4 hours, 500 ℃ of roastings got catalyzer C-4 in 1 hour, and the catalyzer composition sees Table 2.
Example 8
This example illustrates catalyzer provided by the invention and preparation thereof.
Get the C-3a of 100g example 6 gained, the aqueous solution dipping that contains ammonia 10g again with the 70ml that contain Ammonium Heptamolybdate (Tianjin four directions chemical industry company limited, molybdenum oxide content is 89 weight %) 22 grams was in 120 ℃ of dryings 4 hours, 400 ℃ of roastings got catalyzer C-4 in 6 hours, and the catalyzer composition sees Table 2.
Comparative Examples 3～4
This Comparative Examples reference catalyst and preparation thereof
Other are identical with example 4 except that carrier is respectively RS-1, RS-2, and its composition sees Table 2
Table 2
Example 9～10
The hydrocracking performance of this example explanation catalyzer of the present invention.
Raw materials used oil is vacuum gas oil, and its physico-chemical property sees Table 3.
The evaluation method of catalyzer: the particle that catalyzer C-l, C-2 is broken into diameter 2-3 millimeter respectively, catalyzer 16g packs in 30 milliliters of fixed-bed reactor, under nitrogen atmosphere, use earlier before the reaction and contain the kerosene of 2 heavy % dithiocarbonic anhydride 300 ℃ of following prevulcanizeds 25 hours, switch the reaction raw materials reaction then, temperature of reaction is 380 ℃, the hydrogen dividing potential drop is 6.4 MPas, liquid hourly space velocity (LHSV) 0.75 hour
-1, hydrogen-oil ratio (volume) 800.
The weight percentage less than 350 ℃ of components accounts for the transformation efficiency than value defined catalyzer of stock oil less than the weight percentage of 350 ℃ of components in the oil to generate, and the results are shown in Table 4.
Comparative Examples 5～6
Adopt example 9 identical method evaluate catalysts RC-1 and RC-2, evaluation result sees Table 4.
Table 3
| Stock oil | |
| Density (20 ℃), g/cm 3 | 0.8932 |
| S, weight % | 2.12 |
| N，mg/1 | 683 |
| Simulation distil (ASTMD-1160) | |
| IBP/50/70/90 | 305/393/402/422 |
Table 4
| Example | Catalyzer | Transformation efficiency % |
| Comparative Examples 5 | RC-1 | 61.3 |
| Comparative Examples 6 | RC-2 | 65.8 |
| Example 9 | C-1 | 71.3 |
| Example 10 | C-2 | 74.3 |
The result who is provided by table 4 can illustrate, compares with reference catalyst to the invention provides activity of such catalysts and obviously improve.
Claims (10)
1. hydrocracking catalyst, the cracking activity component that contains significant quantity, the hydrogenation active metals component and the matrix of significant quantity, wherein said matrix by a kind of pore volume greater than 0.6 to large pore volume aluminum oxide smaller or equal to 1.2ml/g, a kind of pore volume be the middle pore volume aluminum oxide of 0.48～0.6ml/g and a kind of pore volume 0.2～＜aperture of 0.48ml/g holds the aluminum oxide that aluminum oxide is composited, with described matrix is benchmark and by weight percentage, the medium and small pore volume alumina content of wherein said matrix is 10～60%, middle pore volume alumina content is 5～60%, and the large pore volume alumina content is 15～60%.
2. according to the described catalyzer of claim 1, it is characterized in that described cracking activity component is selected from silica-alumina, have the zeolite molecular sieve of faujusite structure, have the zeolite structured zeolite molecular sieve of Beta or have in the zeolite molecular sieve of mordenite structure one or more.
3. according to the described catalyzer of claim 2, it is characterized in that described faujusite is selected from one or more in HY zeolite, rare-earth type Y zeolite REY, rare-earth type HY zeolite REHY, overstable gamma zeolite USY, rare-earth type overstable gamma zeolite REUSY, the dealuminium Y type beta stone.
4. according to the described catalyzer of claim 1, it is characterized in that described catalyzer contains to be selected from and contains in oxygen or the nitrogenous organism one or more, the mol ratio of organism and group VIII metal component is 0.01-10.
5. catalyzer according to claim 4 is characterized in that described oxygen-bearing organic matter is selected from one or more in organic alcohol, the organic acid, and itrogenous organic substance is an organic amine, and the mol ratio of organism and group VIII metal component is 0.05-8.
6. the described Preparation of catalysts method of claim 1, comprise the cracking activity component of significant quantity is mixed with the precursor of matrix and/or described matrix, moulding and roasting prepare carrier, in described carrier, introduce the hydrogenation active metals component of significant quantity afterwards, the precursor of wherein said matrix and/or described matrix be a kind of pore volume greater than 0.6 to large pore volume aluminum oxide and/or this large pore volume aluminum oxide precursor smaller or equal to 1.2ml/g, a kind of pore volume be 0.48～0.6ml/g middle pore volume aluminum oxide and/or should in pore volume aluminum oxide precursor and a kind of pore volume 0.2～＜aperture of 0.48ml/g holds the mixture that aluminum oxide and/or this aperture hold the aluminum oxide precursor, with described matrix is benchmark and by weight percentage, the medium and small pore volume alumina content of described matrix is 10～60%, middle pore volume alumina content is 5～60%, and the large pore volume alumina content is 15～60%.
7. in accordance with the method for claim 6, it is characterized in that described cracking activity component is selected from silica-alumina, have the zeolite molecular sieve of faujusite structure, have the zeolite structured zeolite molecular sieve of Beta or have in the zeolite molecular sieve of mordenite structure one or more.
8. in accordance with the method for claim 7, it is characterized in that described faujusite is selected from one or more in HY zeolite, rare-earth type Y zeolite REY, rare-earth type HY zeolite REHY, overstable gamma zeolite USY, rare-earth type overstable gamma zeolite REUSY, the dealuminium Y type beta stone.
9. method according to claim 6, it is characterized in that, described method also comprises introduces organic step, described organism is selected from and contains in oxygen and the nitrogenous organism one or more, and it is 0.01-10 that organic introducing amount makes the organism in the catalyzer and the mol ratio of group VIII metal component.
10. method according to claim 9, it is characterized in that, described oxygen-bearing organic matter is selected from one or more in organic alcohol, the organic acid, itrogenous organic substance is an organic amine, and it is 0.05-8 that described organic introducing amount makes the organism in the final catalyzer and the mol ratio of group VIII metal component.
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| CN101757929B (en) * | 2008-12-24 | 2012-01-25 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN103100411B (en) * | 2011-11-11 | 2014-10-15 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst containing molecular sieve and amorphous silica-alumina |
| CN103100443B (en) * | 2011-11-11 | 2014-10-15 | 中国石油化工股份有限公司 | Preparation method of catalyst carrier material containing molecular sieve and amorphous silica-alumina |
| CN103100406B (en) * | 2011-11-11 | 2014-09-17 | 中国石油化工股份有限公司 | Method for preparing hydrogenation catalyst |
| CN104043478B (en) * | 2013-03-15 | 2016-11-16 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and preparation thereof and application |
| CN103949280B (en) * | 2014-05-14 | 2016-04-13 | 武汉凯迪工程技术研究总院有限公司 | Be suitable for the Catalysts and its preparation method that living beings Fischer-Tropsch synthesis oil produces aviation kerosine |
| CN105983414B (en) * | 2015-01-28 | 2019-01-18 | 中国石油天然气股份有限公司 | The preparation method of active matrix, catalyst containing active matrix and preparation method thereof |
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| CN1221020A (en) * | 1997-12-23 | 1999-06-30 | 中国石油化工总公司 | Method of hydrogenation conversion for masrolar D |
| US6309537B1 (en) * | 1998-12-10 | 2001-10-30 | Institut Francais Du Petrole | Hydrotreating hydrocarbon feeds in an ebullating bed reactor |
| CN1400284A (en) * | 2001-07-31 | 2003-03-05 | 中国石油化工股份有限公司 | Catalyst for hydrogenation treatment of diesel oil and its preparation method |
| CN1470608A (en) * | 2003-07-01 | 2004-01-28 | 中国石油天然气集团公司 | Molecular sieve containing catalyst for deep hdyrogenation of middle distillate and its preparing method |
-
2006
- 2006-09-14 CN CN2006101129867A patent/CN101144033B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1221020A (en) * | 1997-12-23 | 1999-06-30 | 中国石油化工总公司 | Method of hydrogenation conversion for masrolar D |
| US6309537B1 (en) * | 1998-12-10 | 2001-10-30 | Institut Francais Du Petrole | Hydrotreating hydrocarbon feeds in an ebullating bed reactor |
| CN1400284A (en) * | 2001-07-31 | 2003-03-05 | 中国石油化工股份有限公司 | Catalyst for hydrogenation treatment of diesel oil and its preparation method |
| CN1470608A (en) * | 2003-07-01 | 2004-01-28 | 中国石油天然气集团公司 | Molecular sieve containing catalyst for deep hdyrogenation of middle distillate and its preparing method |
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