CN1966620B - Catalytic dewaxing catalyst - Google Patents
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Abstract
The invention relates to a kind of deparaffinage catalyst which contains molecular sieve, base material and active hydrogenating metal. The mentioned molecular sieve refers to betazeolite and at least one kind of molecular sieve which have pore structures; the base material refers to aluminium oxide and aluminium oxide-silicon oxide; the hydrogenating active metal refers to at least one VIB group metal and one VIII group metal. The content scope of betazeolite (on the base of catalyst) is from higher than 30wt% to 70wt%, of which the content of molecular sieves which contain pore structure is 2-30wt%; the content of the aluminium oxide is 2-30wt%; the content of aluminium oxide-silicon oxide is 5-50%; the content (by the weight of the oxide) of the VIB group metal is 5-30wt%; the contentof the VIII group metal is 1-6wt%. The catalyst in the invention has better diesel oil catalyzing deparaffinage activity and selectivity.
Description
Technical field
The present invention relates to a kind of catalytic dewaxing catalyst.
Background technology
Produce the product that has the good flow performance under the low temperature by waxy feeds, as rocket engine fuel, low-coagulation diesel oil, lubricated wet goods, dewaxing is necessary.Wherein said wax is meant long-chain n-praaffin or has the generate longer-chain hydrocarbons compound of a small amount of short-side chain, comprises the long chain alkane, chain alkyl aromatic hydrocarbons and the chain alkyl naphthenic hydrocarbon that have a small amount of short-side chain.
Traditional process for dewaxing adopts solvent dewaxing process, and the main drawback of this technology is that running cost is very high, and energy consumption is big, and condensation point reduction amplitude is limited.Another kind of process for dewaxing is catalytic dewaxing, this method is under hydro condition, utilizes unique duct of molecular sieve catalyst and suitable acidity, depresses in certain temperature and hydrogen branch, make wax component optionally cracking or isomery in the stock oil, thereby reduce its condensation point.
US4,767,522 disclose a kind of catalytic dewaxing process, the dewaxing catalyst that this method adopts contains the mesopore aluminosilicate zeolite of a kind of restriction index 2-12, the beta-molecular sieve of 5-60 weight % and a kind of hydrogenation component, described mesopore zeolite molecular screening be from ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and TMA offretite, hydrogenation component are precious metal.
US4,568,655 disclose a kind of catalyzer that contains beta-zeolite molecular sieve, this catalyzer is a carrier with the beta-zeolite molecular sieve that contains 5-30 weight % and the inorganic oxide of 95-70 weight %, at least a VIB of being selected from of load and at least a hydrogenation/dehydrogenation metal component that is selected from VIII, the aperture that described catalyzer accounts for about 75% hole of total pore volume is not more than 100 dusts, and the aperture in about 20% hole is greater than 300 dusts.Described catalyzer also contains and is selected from ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-34, ZSM-35, ZSM-38, ZSM-48, TMA offretite, clinoptilolite and erionite.Described inorganic oxide is selected from aluminum oxide, silicon oxide, aluminium oxide-silicon oxide, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-Thorotrast, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, silica-alumina-titanium oxide, silica-alumina-zirconium white, silica-alumina-magnesium oxide, silicon oxide-magnesium oxide-zirconium white and clay.
In the prior art, for as US4,767,522 these classes are the dewaxing catalyst of hydrogenation active metals with the precious metal, because it is poisoned by heteroatomic compounds such as institute's sulfur-bearings in the raw material easily, to heteroatomic compound content requirement harshness in the charging, its application is restricted.For as US4,568, though being the hydrogenation active metals catalyzer with the base metal, 655 these classes have the dewaxing function concurrently, dewaxing effect is poor.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of new catalytic dewaxing catalyst is provided.
Catalyzer provided by the invention is by molecular sieve, matrix and hydrogenation active metals component are formed, wherein, described molecular sieve is beta-zeolite molecular sieve and at least a molecular sieve with central hole structure, described matrix is aluminum oxide and silica-alumina, described hydrogenation active metals component is selected from the metal component of at least a group vib and at least a group VIII, with the catalyzer is benchmark, the content of beta-zeolite molecular sieve is〉30 weight % to 70 weight %, content with molecular sieve of central hole structure is 2-30 weight %, the content of aluminum oxide is 2-30 weight %, the content of silica-alumina is 5-50 weight %, in oxide compound, the content of group vib metal component is 5-30 weight %, the content of group VIII metal component is 1-6 weight %.
Compare with existing dewaxing catalyst, the catalytic dewaxing activity and the selectivity of catalyzer provided by the invention obviously improve.
For example, (content of beta-zeolite molecular sieve is 55.7 weight %, and the content of ZSM-5 molecular sieve is 13.9 weight %, and the content of aluminum oxide is 7.0 weight % to adopt a kind of catalytic dewaxing catalyst C2 provided by the invention, the content of silica-alumina is 10.4 weight %, WO
3Content is 10.4 weight %, and NiO content is 2.6 weight %), be 370 ℃ to a kind of catalytic cracking diesel oil in temperature of reaction, reaction pressure is 6.0 MPas, total liquid hourly space velocity is 1.0 hours
-1, hydrogen to oil volume ratio is to dewax under 500 the condition, and it is 94.5 heavy % that liquid is received, and is 86.6 heavy % greater than 170 ℃ of olefiant yields of life, and condensation point is-26 ℃; Correspondingly, (content of beta-zeolite molecular sieve is 15.7 weight %, and the content of ZSM-5 molecular sieve is 53.9 weight %, and the content of aluminum oxide is 17.4 weight %, WO to adopt reference catalyst CB2
3Content is 10.4 weight %, and NiO content is 2.6 weight %) time, it only is 91.0 heavy % that liquid is received, and is 86.0 heavy % greater than 170 ℃ of olefiant yields of life, condensation point is-23 ℃; (content of beta-zeolite molecular sieve is 28.6 weight %, and the content of ZSM-5 molecular sieve is 2.0 weight %, and the content of aluminum oxide is 29.8 weight %, and the content of silica-alumina is 26.6 weight %, WO to adopt another reference catalyst CB3
3Content is 10.4 weight %, and NiO content is 2.6 weight %) time, it is 95.0 heavy % that liquid is received, and is 88.5 heavy % greater than 170 ℃ of olefiant yields of life, condensation point only is-18 ℃.
Embodiment
According to catalyzer provided by the invention, with the catalyzer is benchmark, the content of beta-zeolite molecular sieve is preferably 31-60 weight %, content with molecular sieve of central hole structure is preferably 4-20 weight %, the content of aluminum oxide is preferably 5-20 weight %, the content of silica-alumina is preferably 10-40 weight %, and in oxide compound, the content that the content of group vib metal component is preferably 10-25 weight %, group VIII metal component is preferably 1-5 weight %.
According to catalyzer provided by the invention, wherein said beta-zeolite molecular sieve can be commercially available commodity, also can adopt any one prior art for preparing.The mol ratio of preferred silicon oxide and aluminum oxide is at least 25 beta-zeolite molecular sieve, the mol ratio of more preferred silicon oxide and aluminum oxide is the beta-zeolite molecular sieve of 30-200, for the visible EP164 of the description of this beta-zeolite molecular sieve, 939, U.S.Patent.No.4,923,690, U.S.Patent.No.5,164,169, patents such as CN1108213A, CN1108214A, CN1086792A are not given unnecessary details here.
Described molecular sieve with central hole structure can be the aluminosilicate zeolite type molecular sieve with central hole structure, for example, is selected from ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, one or more in ZSM-48 and the TMA offretite; Also can be non-zeolitic molecular sieves, for example, be selected from SAPO-11, SAPO-31, the SAPO-41 molecular sieve one or more with central hole structure.Has the visible U.S.Pat.No.3 of description of the molecular sieve of central hole structure for these, 702,886, U.S.Pat.No.3,709,979, U.S.Pat.No.3,832,449, U.S.Pat.No.4,076,842, U.S.Pat.No.4,016,245, U.S.Pat.No.4,046,859, U.S.Pat.No.4,397,827, U.S.Pat.No.4,440,871, U.S.Pat.No.4, patents such as 689,138 are not given unnecessary details here.
Described aluminum oxide is selected from one or more among γ, η, θ, δ and the χ, is preferably γ-aluminum oxide.They can be commercially available commodity or adopt any one prior art for preparing.
Described silica-alumina carrier can be commercially available commodity or adopt any one prior art for preparing.Preferred silica-alumina is the silica-alumina of γ-aluminum oxide phase structure with feature.For example, a kind of silica-alumina of the γ-aluminum oxide phase structure with feature can be obtained after high roasting by Siral series hydrated silica-aluminum oxide that German Condea company produces.With silicon oxide-aluminum oxide is benchmark, and the content of silicon oxide is 1-60 weight %, is preferably 1-45 weight %.
Described group VIII metal component chosen from Fe, cobalt, nickel are preferably nickel, and VI family metal component is selected from molybdenum, tungsten, is preferably tungsten.
The invention provides catalyzer and adopt this area customary way preparation, the Preparation of catalysts method comprises the precursor of described molecular sieve, aluminum oxide and/or aluminum oxide and precursor mixing, moulding and the roasting of silica-alumina and/or silica-alumina in a preferred embodiment, afterwards under being enough to hydrogenation active metals component deposition condition thereon, it is contacted with the solution that contains the hydrogenation active metals compound, for example by methods such as ion-exchange, dipping, co-precipitation, preferred pickling process.The precursor of wherein said aluminum oxide can be selected from one or more in various hydrated aluminum oxides, the aluminium colloidal sol, also can be in various hydrated aluminum oxides, the aluminium colloidal sol one or more of being selected from of titaniferous, silicon, magnesium, boron, zirconium, thorium, niobium, rare earth, be preferably the hydrated aluminum oxide that contains pseudo-boehmite.The precursor of described silica-alumina can be selected from one or more in various hydrated silica-aluminum oxide, is preferably the hydrated silica-aluminum oxide with structure of similar to thin diaspore.
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 400～650 ℃ as the temperature of roasting, are preferably 450～600 ℃, and roasting time is 1～15 hour, is preferably 3～10 hours.
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 can be used for the catalytic dewaxing of various waxy feeds oil, as boiling point at the waxy feeds oil more than 170 ℃, the particularly catalytic dewaxing of content of wax catalytic cracking diesel oil, hydrocracking tail oil, to produce the product oil of low condensation point.
The following examples will the present invention is further illustrated.
Example 1
This example illustrates catalyzer provided by the invention and preparation thereof.
With 78.8 gram (dry basis) beta-molecular sieve (Chang Ling refinery catalyst plant products, the mol ratio of silicon oxide and aluminum oxide is 31.0), 10.0 gram ZSM-5 molecular sieve (Chang Ling refinery catalyst plant product, the mol ratio of silicon oxide and aluminum oxide is 50), 81.2 gram (dry basis) silicon oxide-aluminum oxide powder (Condea company product, silica content 40 heavy %), 30.0 gram (dry basis) aluminum oxide powder (Chang Ling refinery catalyst plant product) mixes, and to be extruded into circumscribed circle diameter on banded extruder be 1.4 millimeters trilobal bar, wet bar is 120 ° of dryings after 4 hours, in 560 ℃ of roastings 4 hours, obtain support of the catalyst Z1.The composition of carrier Z1 is listed in (calculated value) in the table 1.
Get 100 gram carrier Z1, with nickelous nitrate [Ni (NO
3)
26H
2O] and ammonium metawolframate [(NH
4)
2W
4O
1318H
2O] nickeliferous (in oxide compound) 2.0 gram of preparation, 80 milliliters of dippings of the aqueous solution of tungsten (in oxide compound) 25.0 grams, in 3 hours, 480 ℃ roastings of 120 ℃ of oven dry 4 hours, obtain catalyzer C1 afterwards.The composition of catalyzer C1 is listed in (calculated value) in the table 2.
Example 2
This example illustrates catalyzer provided by the invention and preparation thereof.
With 80 gram (dry basis) beta-molecular sieve (Chang Ling refinery catalyst plant products, the mol ratio of silicon oxide and aluminum oxide is 50.2), 20 gram ZSM-5 molecular sieve (Chang Ling refinery catalyst plant products, the mol ratio of silicon oxide and aluminum oxide is 50), 15 gram (dry basis) silicon oxide-aluminum oxide powder (Condea company products, silica content 60 heavy %), 10 gram (dry basis) aluminum oxide powders (Chang Ling refinery catalyst plant product) and 90 ml deionized water that contain 3 milliliters of concentrated nitric acids mix, mix and pinch, be extruded into circumscribed circle diameter then and be 1.4 millimeters trilobal bar, wet bar is 120 ° of dryings after 4 hours, in 560 ℃ of roastings 4 hours, obtain support of the catalyst Z2.The composition of carrier Z2 is listed in (calculated value) in the table 1.
Get 100 gram carrier Z2, with nickelous nitrate [Ni (NO
3)
26H
2O] and ammonium metawolframate [(NH
4)
2W
4O
1318H
2O] nickeliferous (in oxide compound) 3.0 gram of preparation, 80 milliliters of dippings of the aqueous solution of tungsten (in oxide compound) 12.0 grams, in 3 hours, 480 ℃ roastings of 120 ℃ of oven dry 4 hours, obtain catalyzer C2 afterwards.The composition of catalyzer C2 is listed in (calculated value) in the table 2.
Example 3
This example illustrates catalyzer provided by the invention and preparation thereof.
With 90 gram (dry basis) beta-molecular sieve (Chang Ling refinery catalyst plant products, the mol ratio of silicon oxide and aluminum oxide is 31.0), 10 gram SAPO-11 molecular sieves (Chang Ling refinery catalyst plant product), 60 gram (dry basis) silicon oxide-aluminum oxide powder (Condea company products, silica content 40 heavy %), 40 gram (dry basis) aluminum oxide powders (Chang Ling refinery catalyst plant product) and 150 ml deionized water that contain 4 milliliters of concentrated nitric acids mix, mix and pinch, be extruded into circumscribed circle diameter then and be 1.4 millimeters trilobal bar, wet bar is 120 ° of dryings after 4 hours, in 560 ℃ of roastings 4 hours, obtain support of the catalyst Z3.The composition of carrier Z3 is listed in (calculated value) in the table 1.
Get 100 gram carrier Z3, with nickelous nitrate [Ni (NO
3)
26H
2O] and ammonium metawolframate [(NH
4)
2W
4O
1318H
2O] nickeliferous (in oxide compound) 4.0 gram of preparation, 80 milliliters of dippings of the aqueous solution of tungsten (in oxide compound) 15.0 grams, in 3 hours, 480 ℃ roastings of 120 ℃ of oven dry 4 hours, obtain catalyzer C3 afterwards.The composition of catalyzer C3 is listed in (calculated value) in the table 2.
Example 4
This example illustrates catalyzer provided by the invention and preparation thereof.
With 90 gram (dry basis) beta-molecular sieve (Chang Ling refinery catalyst plant products, the mol ratio of silicon oxide and aluminum oxide is 31.0), 10 gram SAPO-11 molecular sieves (Chang Ling refinery catalyst plant product), 60 gram (dry basis) amorphous silicon oxide-aluminum oxide powder (Chang Ling refinery catalyst plant Industrial products, silica content 41 heavy %), 40 gram (dry basis) aluminum oxide powders (Chang Ling refinery catalyst plant product) and 150 ml deionized water that contain 4 milliliters of concentrated nitric acids mix, mix and pinch, be extruded into circumscribed circle diameter then and be 1.4 millimeters trilobal bar, wet bar is in 120 ° of dryings after 4 hours, in 560 ℃ of roastings 4 hours, obtain support of the catalyst Z4.The composition of carrier Z4 is listed in (calculated value) in the table 1.
Get 100 gram carrier Z4, with nickelous nitrate [Ni (NO
3)
26H
2O] and ammonium metawolframate [(NH
4)
2W
4O
1318H
2O] nickeliferous (in oxide compound) 4.0 gram of preparation, 80 milliliters of dippings of the aqueous solution of tungsten (in oxide compound) 15.0 grams, in 3 hours, 480 ℃ roastings of 120 ℃ of oven dry 4 hours, obtain catalyzer C4 afterwards.The composition of catalyzer C4 is listed in (calculated value) in the table 2.
Comparative Examples 1
This Comparative Examples explanation reference catalyst and preparation thereof.
With 36 gram (dry basis) beta-molecular sieve (Chang Ling refinery catalyst plant products, the mol ratio of silicon oxide and aluminum oxide is 50.2), 124 gram (dry basis) ZSM-5 molecular sieve (Chang Ling refinery catalyst plant products, the mol ratio of silicon oxide and aluminum oxide is 50), 40 gram (dry basis) aluminum oxide powders (Chang Ling refinery catalyst plant product) and 150 ml deionized water that contain 4 milliliters of concentrated nitric acids mix, mix and pinch, be extruded into circumscribed circle diameter then and be 1.4 millimeters trilobal bar, wet bar is in 120 ° of dryings after 4 hours, in 560 ℃ of roastings 4 hours, obtain support of the catalyst ZB1.The composition of carrier is listed in (calculated value) in the table 1.
Get 100 gram carrier ZB1, with nickelous nitrate [Ni (NO
3)
26H
2O] 80 milliliters of dippings of the aqueous solution of nickeliferous (in oxide compound) 1.4 gram of preparation, in 3 hours, 480 ℃ roastings of 120 ℃ of oven dry 4 hours, obtain catalyzer CB1 afterwards.The composition of catalyzer CB1 is listed in (calculated value) in the table 2.
Comparative Examples 2
This Comparative Examples explanation reference catalyst and preparation thereof.
Get 100 gram carrier ZB1, with nickelous nitrate [Ni (NO
3)
26H
2O] and ammonium metawolframate [(NH
4)
2W
4O
1318H
2O] nickeliferous (in oxide compound) 3.0 gram of preparation, 80 milliliters of dippings of the aqueous solution of tungsten (in oxide compound) 12.0 grams, in 3 hours, 480 ℃ roastings of 120 ℃ of oven dry 4 hours, obtain catalyzer CB2 afterwards.The composition of catalyzer CB2 is listed in (calculated value) in the table 2.
Comparative Examples 3
This Comparative Examples explanation reference catalyst and preparation thereof.
With 65.8 gram (dry basis) beta-molecular sieve (Chang Ling refinery catalyst plant products, the mol ratio of silicon oxide and aluminum oxide is 50.2), 4.6 gram (dry basis) ZSM-5 molecular sieve (Chang Ling refinery catalyst plant product, the mol ratio of silicon oxide and aluminum oxide is 50), 61.2 gram (dry basis) silicon oxide-aluminum oxide powder (Condea company product, silica content 40 heavy %), 68.5 gram (dry basis) aluminum oxide powder (Chang Ling refinery catalyst plant product) and 150 ml deionized water that contain 4 milliliters of concentrated nitric acids mix, mix and pinch, be extruded into circumscribed circle diameter then and be 1.4 millimeters trilobal bar, wet bar is in 120 ° of dryings after 4 hours, in 560 ℃ of roastings 4 hours, obtain support of the catalyst ZB2.The composition of carrier is listed in (calculated value) in the table 1.
Get 100 gram carrier ZB2, with nickelous nitrate [Ni (NO
3)
26H
2O] and ammonium metawolframate [(NH
4)
2W
4O
1318H
2O] nickeliferous (in oxide compound) 3.0 gram of preparation, 80 milliliters of dippings of the aqueous solution of tungsten (in oxide compound) 12.0 grams, in 3 hours, 480 ℃ roastings of 120 ℃ of oven dry 4 hours, obtain catalyzer CB3 afterwards.The composition of catalyzer CB3 is listed in (calculated value) in the table 2.
Table 1
| Example number | Bearer number | The heavy % of beta-molecular sieve | The heavy % of ZSM-5 | The heavy % of SAPO-11 | The heavy % of silica-alumina | Al 2O 3Heavy % | The beta-molecular sieve silica alumina ratio |
| 1 | Z1 | 39.4 | 5.0 | 40.6 | 15 | 31.0 | |
| 2 | Z2 | 64 | 16 | 12 | 8 | 50.2 | |
| 3 | Z3 | 45 | 5 | 30 | 20 | 31.0 | |
| 4 | Z4 | 45 | 5 | 30 | 20 | 31.0 | |
| Comparative Examples 1 | ZB1 | 18 | 62 | 20 | 50.2 | ||
| Comparative Examples 3 | ZB2 | 32.9 | 2.3 | 30.6 | 34.2 | 50.2 |
Table 2
| Example number | The catalyzer numbering | The heavy % of beta-molecular sieve | The heavy % of ZSM-5 | The heavy % of SAPO-11 | The heavy % of silica-alumina | Al 2O 3Heavy % | The heavy % of NiO | WO 3Heavy % |
| 1 | C1 | 31.0 | 3.9 | 32.0 | 11.8 | 1.6 | 19.7 | |
| 2 | C2 | 55.7 | 13.9 | 10.4 | 7.0 | 2.6 | 10.4 | |
| 3 | C3 | 37.8 | 4.2 | 25.2 | 16.8 | 3.4 | 12.6 | |
| 4 | C4 | 37.8 | 4.2 | 25.2 | 16.8 | 3.4 | 12.6 | |
| Comparative Examples 1 | CB1 | 17.8 | 61.1 | 19.7 | 1.4 | - | ||
| Comparative Examples 2 | CB2 | 15.7 | 53.9 | 17.4 | 2.6 | 10.4 | ||
| Comparative Examples 3 | CB3 | 28.6 | 2.0 | 26.6 | 29.8 | 2.6 | 10.4 |
Example 5-8
Following example illustrates the catalytic dewaxing performance of catalyzer provided by the invention.
Dewax with the catalytic cracking diesel oil shown in the catalyzer C1-C4 his-and-hers watches 3 provided by the invention.Be reflected on 20 milliliters of hydrogenation reaction devices and carry out, the granules of catalyst diameter is the 0.30-0.45 millimeter, reactor top filling 10 milliliters of Hydrobon catalyst RN-10 (production of Chang Ling refinery catalyst plant), and the bottom is loaded 10 milliliters of C1-C4 catalyzer respectively.Catalyzer is vulcanized 300 ℃ of curing temperatures, curing time 4 hours with the kerosene that contains dithiocarbonic anhydride 2 heavy % before the reaction.Sulfuration finishes the catalytic cracking diesel oil shown in the switching table 3 of back, is 370 ℃ in temperature of reaction, and reaction pressure is 6.0 MPas, and total liquid hourly space velocity is 1.0 hours
-1, hydrogen to oil volume ratio is under 500 the condition stock oil to be dewaxed.Reacted liquid product is distilled cutting, measure boiling point, the results are shown in Table 4 greater than olefiant yield of 170 ℃ life and condensation point.
Comparative Examples 4-6
The catalytic performance of this Comparative Examples explanation reference catalyst.
Method by example 5 dewaxes to identical stock oil, and different is to replace catalyzer C1 with reference catalyst CB1, CB2 and CB3 respectively, and the results are shown in Table 4.
Table 3
| The stock oil title | Catalytic cracking diesel oil |
| Density (20 ℃), g/cm 3 | 0.9140 |
| Condensation point, ℃ | +3 |
| Cold filter clogging temperature, ℃ | +7 |
| S，w％ | 0.90 |
| N，w％ | 0.15 |
| Boiling range, ℃ | |
| Initial boiling point/5% | 202/218 |
| 10％/20％ | 230/246 |
| 30％/50％ | 260/286 |
| 70％/80％ | 319/334 |
| 90%/do | 349/368 |
Table 4
| Example number | Catalyst system therefor | Liquid is received, heavy % | Greater than 170 ℃ of olefiant yields of life, heavy % | Condensation point ℃ |
| 5 | C1 | 94.0 | 86.0 | -29 |
| 6 | C2 | 94.5 | 86.6 | -26 |
| 7 | C3 | 95.0 | 87.2 | -25 |
| 8 | C4 | 94.8 | 86.7 | -22 |
| Comparative Examples 4 | CB1 | 90.3 | 85.8 | -26 |
| Comparative Examples 5 | CB2 | 91.0 | 86.0 | -23 |
| Comparative Examples 6 | CB3 | 95.0 | 88.5 | -18 |
The result of table 4 shows, compares with reference catalyst, and activity of such catalysts provided by the invention and selectivity improve.
Claims (8)
1. catalytic dewaxing catalyst, by molecular sieve, matrix and hydrogenation active metals component are formed, wherein, described molecular sieve is beta-zeolite molecular sieve and at least a molecular sieve with central hole structure, matrix is aluminum oxide and silica-alumina, the hydrogenation active metals component is selected from the metal component of at least a group vib and at least a group VIII, with the catalyzer is benchmark, the content of beta-zeolite molecular sieve is＞30 weight % to 70 weight %, content with molecular sieve of central hole structure is 2-20 weight %, the content of aluminum oxide is 2-30 weight %, the content of silica-alumina is 5-50 weight %, in oxide compound, the content of group vib metal component is 5-30 weight %, the content of group VIII metal component is 1-6 weight %.
2. catalyzer according to claim 1, it is characterized in that, with the catalyzer is benchmark, the content of described beta-zeolite molecular sieve is 31-60 weight %, content with molecular sieve of central hole structure is 4-20 weight %, and the content of aluminum oxide is 5-20 weight %, and the content of silica-alumina is 10-40 weight %, in oxide compound, the content of group vib metal component is that the content of 10-25 weight %, group VIII metal component is 1-5 weight %.
3. catalyzer according to claim 1 is characterized in that, the silicon oxide of described beta-zeolite molecular sieve and the mol ratio of aluminum oxide are 30-200.
4. catalyzer according to claim 1 is characterized in that, described have the molecular screening of central hole structure from the aluminosilicate zeolite type molecular sieve of mesopore, in the non-zeolitic molecular sieves one or more.
5. catalyzer according to claim 4 is characterized in that, described aluminosilicate zeolite type molecular screening with central hole structure is from ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, one or more in ZSM-48 and the TMA offretite.
6. catalyzer according to claim 4 is characterized in that, described non-zeolitic molecular sieves with central hole structure is selected from one or more in SAPO-11, SAPO-31, the SAPO-41 molecular sieve.
7. catalyzer according to claim 1 is characterized in that, described silica-alumina is the silica-alumina with gama-alumina phase structure of feature.
8. catalyzer according to claim 1 is characterized in that, described aluminum oxide is a gama-alumina.
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| US4696732A (en) * | 1984-10-29 | 1987-09-29 | Mobil Oil Corporation | Simultaneous hydrotreating and dewaxing of petroleum feedstocks |
| CN1031558A (en) * | 1987-08-20 | 1989-03-08 | 无比石油公司 | The method of catalytic dewaxing |
| CN1448484A (en) * | 2002-03-29 | 2003-10-15 | 中国石油化工股份有限公司 | Zeolite containing catalytic dewaxing catalyst |
| CN1552818A (en) * | 2003-05-30 | 2004-12-08 | 中国石油化工股份有限公司 | Monox-alumina containnig hydrocracking catalyst |
-
2005
- 2005-11-16 CN CN2005101153471A patent/CN1966620B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4568655A (en) * | 1984-10-29 | 1986-02-04 | Mobil Oil Corporation | Catalyst composition comprising Zeolite Beta |
| US4696732A (en) * | 1984-10-29 | 1987-09-29 | Mobil Oil Corporation | Simultaneous hydrotreating and dewaxing of petroleum feedstocks |
| CN1031558A (en) * | 1987-08-20 | 1989-03-08 | 无比石油公司 | The method of catalytic dewaxing |
| CN1448484A (en) * | 2002-03-29 | 2003-10-15 | 中国石油化工股份有限公司 | Zeolite containing catalytic dewaxing catalyst |
| CN1552818A (en) * | 2003-05-30 | 2004-12-08 | 中国石油化工股份有限公司 | Monox-alumina containnig hydrocracking catalyst |
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| Publication number | Publication date |
|---|---|
| CN1966620A (en) | 2007-05-23 |
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