CN100425678C - Dewaxing catalyst containing compound molecule sieve and preparation method thereof - Google Patents
Dewaxing catalyst containing compound molecule sieve and preparation method thereof Download PDFInfo
- Publication number
- CN100425678C CN100425678C CNB2005100020557A CN200510002055A CN100425678C CN 100425678 C CN100425678 C CN 100425678C CN B2005100020557 A CNB2005100020557 A CN B2005100020557A CN 200510002055 A CN200510002055 A CN 200510002055A CN 100425678 C CN100425678 C CN 100425678C
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- weight
- catalyzer
- content
- metal component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to dewaxing catalyst containing a compound molecule sieve. The catalyst is provided with a molecule sieve with a one-dimensional middle hole structure, and a molecular sieve with a big hole structure, wherein the weight ratio of the molecular sieve with the one-dimensional middle hole structure to the molecular sieve with the big hole structure is 80 to 99: 1 to 20; the molecular sieve with the big hole structure contains non-framework silicon and is metered by oxide, and the content of the silicon is 1 to 20 weight % on the basis of the molecular sieve.
Description
Technical field
The present invention relates to a kind of dewaxing catalyst and preparation method thereof, more specifically to a kind of dewaxing catalyst that contains composite molecular screen and preparation method thereof.
Background technology
By molecule cracking of selectivity wax and/or isomerization dewaxing, can change the low temperature flowability of oil product to waxy petroleum distillate oil effectively.The catalyzer that can be used for the dewaxing of waxy petroleum distillate oil selectivity is a lot, wherein contains the catalyzer of composite molecular screen, because the existence on performance of differing molecular sieve is complementary and collaborative, with respect to containing single molecular sieve catalyst, its performance improves.
US 4,575,416 disclose a kind of lubricating oil distillate catalytic dewaxing process, comprise stock oil is contacted with dewaxing catalyst, described catalyzer contains a kind of restriction index greater than 1 zeolite molecular sieve, a kind of acidic components that are selected from Mordenite, TEA, Dealuminized Y, Ultrastable Y, Rare Earth Y, amorphous silicon oxide-aluminum oxide, chlorinated aluminas, ZSM-4 and ZSM-20, a kind of hydrogenation active metals component.Compare with the dewaxing catalyst that contains single zeolite molecular sieve such as Ni/ZSM-5 and Pt/ZSM-5, reach at product oil under the condition of same pour point, adopt the viscosity index VI of this method products therefrom and yield all higher.
US 6,652,735B2 discloses a kind of hydrocarbon ils isomerization dewaxing method, be included under hydrogen existence and the hydrotreatment reaction conditions, hydrocarbon oil feed is contacted with a kind of catalyzer, described catalyzer contain a kind of restriction index less than 2, the alpha value less than 100, crystalline size is less than 1 micron macropore crystalline molecular sieve, a kind of restriction index greater than 2, the alpha value less than 100, crystalline size is less than 1 micron the mesoporous molecular sieve with one dimension or non-intersection two dimension pore structure (a non-intersecting two dimensional pore structure); Wherein, the selection of described hydrotreatment reaction conditions should help obtaining 165-345 ℃ intermediate oil, and the productive rate that makes this intermediate oil is greater than 30 weight %.
Introduce large pore molecular sieve in selecting the shape dewaxing catalyst, it is favourable that the straight-chain paraffin isomery is converted into the low highly-branched chain isomerous alkane of condensation point.But when its shortcoming was that isomery transforms this heavy raw oil of lubricating oil distillate, the yield of lubricant base was low.
Summary of the invention
The objective of the invention is the hydrocarbon isomerization catalyzer that contains large pore molecular sieve at existing, when being used for the lubricating oil distillate oil dewaxing, the shortcoming that the yield of lubricant base is low, provide a kind of new activity and selectivity all higher contain dewaxing catalyst of composite molecular screen and preparation method thereof.
Catalyzer provided by the invention contains heat-resistant inorganic oxide, at least a group VIII metal component and molecular sieve, with the catalyzer total amount is benchmark, the content of heat-resistant inorganic oxide is 10-90 weight %, in oxide compound, the content of group VIII metal component is 0.1-10 weight %, the content of molecular sieve is 9.9-89.9 weight %, it is characterized in that, described molecular sieve is a kind of molecular sieve and a kind of molecular sieve with macroporous structure with one dimension central hole structure, wherein, described molecular sieve with one dimension central hole structure is 80-99: 1-20 with the weight ratio with molecular sieve of macroporous structure, described molecular sieve with macroporous structure contains non-framework silicon, is benchmark in oxide compound and with this molecular sieve, and the content of described silicon is 1-20 weight %.
Preparation of catalysts method provided by the invention comprises: heat-resistant inorganic oxide or its precursor are mixed with a kind of molecular sieve and a kind of molecular sieve with macroporous structure with one dimension central hole structure, moulding and roasting, be selected from least a group VIII metal component in introducing afterwards, with the catalyzer total amount is benchmark, it is 10-90 weight % that the consumption of each component makes the content of heat-resistant inorganic oxide in the final catalyzer, in oxide compound, the content of group VIII metal component is 0.1-10 weight %, the content of molecular sieve is 9.9-89.9 weight %, it is characterized in that, described molecular sieve is a kind of molecular sieve and a kind of molecular sieve with macroporous structure with one dimension central hole structure, wherein, described molecular sieve with one dimension central hole structure is 80-99: 1-20 with the weight ratio with molecular sieve of macroporous structure, described molecular sieve with macroporous structure contains non-framework silicon, in oxide compound and with this molecular sieve is benchmark, and the content of described silicon is 1-20 weight %.
Compare with existing catalyzer, catalyzer provided by the invention is when being used for the lubricating oil distillate isomerization dewaxing, and the condensation point of lubricant base is low, yield is high.
For example, adopting catalyzer C4 provided by the invention, is that the three-way sweat oil of 19 ℃ subtract carries out catalytic dewaxing to a kind of pour point, and when temperature of reaction was 330 ℃, reaction generated in the oil＞and the yield of 320 ℃ of cuts is 85.02%, and viscosity index is 112, pour point is-9 ℃; Estimate reference catalyst D2 with same materials oil and reaction conditions, in its reaction generation oil＞yield of 320 ℃ of cuts only is 80.30%, and viscosity index only is 109, and pour point only is-6 ℃.
Embodiment
According to catalyzer provided by the invention, wherein said molecular screening with one dimension central hole structure one or more in ZSM-22, ZSM-23, ZSM-35, SAPO-31, SAPO-41, preferred SAPO-1 and/or SAPO-41 wherein, more preferably SAPO-1.About the pore structure of above-mentioned zeolite-type molecular sieves and non-zeolitic molecular sieves respectively in J.M.Benett et al, Zeolites, 1,160 (1987), G.T.Kokotailo, et al, Zeolites, 5,349 (1985), W.M.Meier, and D.H.Olsen, Atlas of Zeolite Structure Types, Butterworths, (87), R.M.Kircher, and J.M.Bennett, Zeolites, disclose in detail in 14,523 (1994), do not give unnecessary details here.
Described molecular screening with macroporous structure one or more in L zeolite, y-type zeolite, X type zeolite, β zeolite, mordenite, ZSM-3, ZSM-4, ZSM-18, ZSM-20, SAPO-5, be preferably in y-type zeolite, β zeolite, the mordenite one or more, more preferably the β zeolite.
In oxide compound and with described molecular sieve total amount is benchmark, and the content of described non-framework silicon is preferably 2-10 weight %.
Described non-framework silicon is contacted with the solution of silicon-containing compound by described molecular sieve and the method for roasting is introduced.For example, with described molecular sieve silicon-containing compound solution impregnation and roasting, maturing temperature is 350-650 ℃, is preferably 450-550 ℃, roasting time 1-24 hour, is preferably 2-8 hour.
Described silicon-containing compound is selected from the various organosilicons that are commonly used for the modification of molecular sieve silicon, in the inorganic silicon compound one or more.For example; can be selected from the phenmethyl siloxanes; the styroyl siloxanes; the hydrocinnamyl siloxanes; hexamethyldisiloxane; the decamethyl trisiloxanes; the phenylbenzene tetramethyl disiloxane; tetraethyl orthosilicate; trimethylchlorosilane; CMDMCS chloromethyl dimethyl chlorosilane; the N-trimethyl-silyl-imidazole; adjacent; between-two (trimethyl silyl) ethylidine imidazoles; the N-methyl-just-the trimethyl silyl ethanamide; instead-butyl dimetylsilyl imidazoles; N-trimethyl silyl ethanamide; methyltrimethoxy silane; vinyltriethoxysilane; ethyl trimethoxy silane; propyl trimethoxy silicane; (3; 3; the 3-trifluoro propyl) Trimethoxy silane; (3-(2-amino-ethyl) aminopropyl) Trimethoxy silane; the cyano ethyl Trimethoxy silane; TSL 8330; phenyl trimethoxy silene; (3-chloropropyl) Trimethoxy silane; (3-thiohydroxy propyl group) Trimethoxy silane; (3-glycidyl propyl group) Trimethoxy silane; vinyl three (B-methoxy ethoxy) silane; (r-methacryloyl propyl group) Trimethoxy silane; (4-aminopropyl) Trimethoxy silane; (r-(B-aminoethylamino) propyl group l) Trimethoxy silane; (r-glycidyl propyl group) Trimethoxy silane; (B-(3, the 4-epoxycyclohexyl) ethyl) Trimethoxy silane; (r-thiohydroxy ethyl) Trimethoxy silane; (r-chloropropyl) Trimethoxy silane; methyl silicate; tetraethoxy; SiCl4; in the silicon sol one or more.In the preferred methyl silicate, tetraethoxy, SiCl4 wherein one or more.In oxide compound and with the molecular sieve total amount is benchmark, and the introducing amount of described silicon is 1-20%, be preferably 2-10%.
To the grain size of described molecular sieve with macroporous structure without limits, but for the catalyzer of optimum performance, preferably the crystal grain of this molecular sieve is less than 300 nanometers, and further preferred crystal grain is the 50-200 nanometer.
Described crystal grain can be by any one existing method preparation less than the molecular sieve of 300 nanometers.For example, crystal grain can adopt the synthetic method preparation of the applicant's disclosed beta zeolite in small crystal grain in CN 1108213A, CN 1108214A, CN 1100004C less than the β zeolite of 300 nanometers.Details about these synthetic methods discloses in above-mentioned patent (application) in detail, does not give unnecessary details herein.
According to catalyzer provided by the invention, wherein can also contain heat-resistant inorganic oxide, described heat-resistant inorganic oxide plays binding agent, support of the catalyst in catalyzer, it can improve the intensity of catalyzer, and can improve and reconcile the physico-chemical property of catalyzer, as improving the pore structure of catalyzer.Described heat-resistant inorganic oxide is selected from one or more in the various heat-resistant inorganic oxides that are commonly used for support of the catalyst and/or matrix.For example, in the optional self-alumina of described heat-resistingization thing, silicon oxide, titanium oxide, magnesium oxide, aluminum oxide-magnesium oxide, silica-alumina, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-Thorotrast, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, silicon oxide-zirconium white, oxidation titania-zirconia, silica-alumina-Thorotrast, silica-alumina-titanium oxide, silica-alumina-magnesium oxide, silica-alumina-zirconium white, natural zeolite, the clay one or more, preferred aluminum oxide.With the catalyzer total amount is benchmark, and the content of described heat-resistant inorganic oxide is that 10-90 weight % is preferably 20-80 weight %.
According to catalyzer provided by the invention, wherein also contain at least a group VIII metal component, one or more in preferred nickel, platinum and the palladium wherein, more preferred platinum and/or palladium, in oxide compound and with the catalyzer is benchmark, and the content of group VIII metal component is the heavy % of 0.1-15.The heavy % of preferred 0.1-5, the more preferably heavy % of 0.1-1.5.
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.
Described maturing temperature is 300-700 ℃, is preferably 350-600 ℃, and roasting time is 2-8 hour, is preferably 3-6 hour.
When catalyzer contains heat-resistant inorganic oxide, comprise and described molecular sieve is mixed moulding and roasting with described heat-resistant inorganic oxide or its precursor.Wherein, the precursor of described heat-resistant inorganic oxide refers to can form after the roasting compound of described heat-resistant inorganic oxide, typically refers to oxyhydroxide, hydrous oxide, contains the gel of its oxide compound, oxyhydroxide and in the colloidal sol one or more.For example, the precursor of aluminum oxide can be selected from one or more in various hydrated aluminum oxides, the aluminium colloidal sol.
When containing the group VIII metal component in the catalyzer, can at first in described molecular sieve, introduce group VIII metal component, mixing afterwards, moulding and roasting; Also can introduce the group VIII metal component afterwards earlier with described molecular sieve (containing or do not contain heat-resistant inorganic oxide) mixing, moulding and roasting.The method of described introducing group VIII metal component is an ordinary method, as adopting ion-exchange, dipping, mixing method such as pinch.
Catalyzer provided by the invention can be used as cracking reaction, isomerization reaction, the hydrocracking of various hydro carbons, the catalyzer of hygrogenating isomerization reaction.Contain the catalyzer provided by the invention of VIII family metal, be especially suitable for use as the lubricating oil distillate hydroisomerization dewax, to produce low pour point, base oil of high viscosity index lubricant.Wherein, described content of wax hydrocarbon oil crude material is selected from hydrocracking tail oil, the solvent-refined oil through hydrotreatment, deasphalted oil, slack wax, soft wax, Fischer-Tropsch synthetic wax etc.
The following examples will the invention will be further described.
Agents useful for same in the example except that specifying, is chemically pure reagent.
The grain size of molecular sieve adopts scanning electronic microscope to measure.
Embodiment 1
Present embodiment illustrates Catalysts and its preparation method provided by the invention.
According to patent U.S.Pat.No.4, the synthetic SAPO-11 molecular sieve of example 16 methods in 440,871.Be specially: take by weighing the phosphoric acid of 420 grams, 85 heavy %, add 880 gram distilled water, 276 gram pseudo-boehmites (alumina content 74.2 heavy %, water-content 25.8 heavy %) stir, and obtain mixture S1.Taking by weighing concentration is the hydroxyl four n-Butyl Amine 99 aqueous solution 1298.4 grams of 40 heavy %, and the silica gel of being fuming (silica content 92.8 heavy %, water-content 7.2 heavy %) 52 grams stir, and obtain mixture S2.Mixture S1 and S2 are mixed, under agitation add 204 gram di-n-propylamines, obtain reaction mixture.Reaction mixture is packed in the reactor of teflon seal, and 200 ℃ of crystallization 24 hours filter that also the washing solid product is to neutral, and 120 ℃ of oven dry obtain SAPO-11 molecular sieve (SAPO-11 net content 85.0 heavy %).
Preparation contains the β zeolite of non-framework silicon in accordance with the following methods, (mol ratio of silicon oxide and aluminum oxide is 36 will to take from the β zeolite of Chang Ling refinery, crystal grain is the 230-280 nanometer) 21 grams, 550 ℃ of roastings 3 hours, after in air, being cooled to room temperature, get 20 grams with 100 milliliters of the cyclohexane solutions dipping that contains 5.9 gram tetraethoxys 10 hours, filter and under 60 ℃ of temperature dry 2 hours, 550 ℃ of following roastings 2 hours, obtain the β zeolite of silicon modification afterwards.In oxide compound and with the molecular sieve total amount is benchmark, and calculating the amount of introducing silicon in this zeolite is 7.6 weight %.
With 19.95 gram alumina hydrate powder (C1 powder, Germany Condea company product), 87.68 gram SAPO-11 molecular sieves and 3.89 gram β zeolites mix (SAPO-11: β=87.68: 3.89), be extruded into circumscribed circle diameter and be 1.4 millimeters trilobal bar, wet bar was in 120 ℃ of air dryings 4 hours, 560 ℃ of roastings 4 hours obtain catalyzer C1.SAPO-11 content is 82 weight % among the catalyzer C1, and the content of β zeolite is 3 weight %, and aluminum oxide is 15 weight %.
Embodiment 2
Present embodiment illustrates Catalysts and its preparation method provided by the invention.
Prepare the β zeolite according to the CN1108231A method.Add polyether oil (commercial goods, trade mark is called 50HB-260, U.S. combinating carbide company, molecular weight 1000-1200) on the basis of CN1108231A example 2 synthetic β zeolites, the mol ratio of each component is SiO
2/ Al
2O
3=30, Na
2O/SiO
2=0.065, TEAOH/SiO
2=0.10, H
2O/SiO
2=6.5, polyether oil/SiO
2(weight %)=0.8; With gained mixture 120 ℃ of crystallizations 24 hours in autoclave, be warming up to 140 ℃ of reactions 40 hours again, isolate solid product after the reaction, washing, 110 ℃ are drying to obtain the β zeolite.This product grains is the 70-80 nanometer.With this zeolite 550 ℃ of roastings 3 hours, be cooled to and get 20 grams after the room temperature with 100 milliliters of dippings of the cyclohexane solutions that contain 1.7 gram tetraethoxys 10 hours, filter and under 60 ℃ of temperature dry 2 hours, afterwards 550 ℃ of following roastings 2 hours, obtain the β zeolite of silicon modification, in oxide compound and with the molecular sieve total amount is benchmark, and calculating the amount of introducing silicon in this zeolite is 2.3 weight %.
With 19.95 gram alumina hydrate powder (C1 powder, Germany Condea company product), 85.54 gram SAPO-11 molecular sieves (with embodiment 1) and 6.67 gram β zeolites mix (SAPO-11: β=85.54: 6.67), be extruded into circumscribed circle diameter and be 1.4 millimeters trilobal bar, wet bar was in 120 ℃ of air dryings 4 hours, following 4 hours of 560 ℃ of air atmospheres obtain catalyzer C2.SAPO-11 content is 80 weight % among the catalyzer C2, and the content of β zeolite is 5 weight %, and alumina host is 15 weight %.
Embodiment 3
Present embodiment illustrates Catalysts and its preparation method provided by the invention.
Present embodiment adopts raw material and the method identical with embodiment 1 to prepare catalyzer C3, different is that SAPO-11 content is 65 weight % among the catalyzer C3, the content of β zeolite is 15 weight %, and alumina host is 20 weight %, SAPO-11: β=69.50: 19.45.
Embodiment 4
Present embodiment illustrates Catalysts and its preparation method provided by the invention.
Get the catalyzer C1 of 100 gram embodiment 1 preparations, with 84 milliliters of dippings of dichloro four ammino platinum solution of platiniferous 0.4 gram 4 hours, afterwards in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours obtained catalyzer C4.The content of platinum is 0.4 weight % among the catalyzer C4.
Embodiment 5
Present embodiment illustrates Catalysts and its preparation method provided by the invention.
Get the catalyzer C2 of 100 gram examples 2 preparations, with 80 milliliters of dippings of dichloro four ammino platinum solution of platiniferous 0.8 4 hours, afterwards in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours obtained catalyzer C5.The content of platinum is 0.8 weight % among the catalyzer C5.
Embodiment 6
Present embodiment illustrates Catalysts and its preparation method provided by the invention.
Get the catalyzer C3 of 100 gram embodiment 3 preparations, with the dichloro four ammino platinum of platiniferous 0.15 gram and the dichloro four ammino palladium solution that contain palladium 0.05 gram totally 84 milliliters flooded 4 hours, afterwards in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours obtain catalyzer C6.The content of platinum is 0.15 weight % among the catalyzer C6, and the content of palladium is 0.05 weight %.
Comparative Examples 1
This Comparative Examples explanation reference catalyst and preparation method thereof.
This Comparative Examples adopts the method identical with embodiment 1 to prepare catalyzer D1, the β zeolite that different is is not wherein introduced non-framework silicon, SAPO-11 content is 82 weight % among the catalyzer D1, the content of β zeolite is 3 weight %, alumina host is 15 weight %, SAPO-11: β=87.68: 3.69.
Comparative Examples 2
This Comparative Examples explanation reference catalyst and preparation method thereof.
Get the catalyzer D1 of 100 gram Comparative Examples 1 preparations, with 85 milliliters of dippings of dichloro four ammino platinum solution of platiniferous 0.4 gram 4 hours, afterwards in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours obtained catalyzer D2.The content of platinum is 0.4 weight % among the catalyzer C2.
Example 7
The present embodiment explanation the invention provides the lubricating oil distillate isomerization dewaxing performance of catalyzer.
Raw materials used oil is for subtracting three-way sweat oil, and its character sees Table 1.
Catalyzer C4 is broken into the particle of diameter 0.5-1.0 millimeter, in 20 milliliters of small stationary bed bioreactors, pack into 20 milliliters of this catalyzer, earlier catalyzer is reduced under nitrogen atmosphere before the reaction, reduction temperature is 400 ℃, hydrogen dividing potential drop 2 MPas, 6 hours recovery times, switch reaction raw materials then, reaction conditions is: reaction pressure 6Mpa, weight space velocity 1h-1, and hydrogen to oil volume ratio 500: 1, temperature of reaction is respectively 330 ℃, 350 ℃, 370 ℃.Generate oily underpressure distillation, calculate the yield of＞320 ℃ of cuts, and measure 100 ℃, 40 ℃ kinematic viscosity and pour point of＞320 ℃ cut, the results are shown in Table 2.
Comparative Examples 3
Estimate reference catalyst according to example 7 same procedure.The results are shown in Table 2.
Table 1
| Project | Subtract three-way sweat oil character |
| Density (20 ℃), g/ml | 0.8628 |
| v 40，mm 2/s | 36.480 |
| v 100，mm 2/s | 6.229 |
| VI | 119 |
| Pour point, ℃ | 19 |
Table 2
The result that table 2 provides shows, the invention provides catalyzer when being used for the lubricating oil distillate oil dewaxing, no matter be the yield of product, or the pour point depression effect all is better than reference catalyst.
Claims (16)
1, a kind of dewaxing catalyst that contains composite molecular screen, this catalyzer contains heat-resistant inorganic oxide, at least a group VIII metal component and molecular sieve, with the catalyzer total amount is benchmark, the content of heat-resistant inorganic oxide is 10-90 weight %, the content of molecular sieve is 9.9-89.9 weight %, in oxide compound, the content of group VIII metal component is 0.1-10 weight %, it is characterized in that, described molecular sieve is a kind of molecular sieve and a kind of molecular sieve with macroporous structure with one dimension central hole structure, wherein, described molecular sieve with one dimension central hole structure is 80-99: 1-20 with the weight ratio with molecular sieve of macroporous structure, and described molecular sieve with macroporous structure contains non-framework silicon, in oxide compound and with this molecular sieve is benchmark, and the content of described silicon is 1-20 weight %.
2, catalyzer according to claim 1, it is characterized in that, described have the molecular screening of one dimension central hole structure from SAPO-11 and/or SAPO-41, described molecular screening with macroporous structure one or more in y-type zeolite, β zeolite, mordenite, described weight ratio is 90-99: 1-10.
3, catalyzer according to claim 2 is characterized in that, described molecular sieve with one dimension central hole structure is SAPO-11, and described molecular sieve with macroporous structure is the β zeolite.
4, catalyzer according to claim 1 is characterized in that, the content of described silicon is 2-10 weight %.
5, catalyzer according to claim 1 is characterized in that, the crystal grain of described molecular sieve with macroporous structure is less than 300 nanometers.
6, catalyzer according to claim 5 is characterized in that, described crystal grain with molecular sieve of macroporous structure is the 50-200 nanometer.
7, catalyzer according to claim 1 is characterized in that, described heat-resistant inorganic oxide is an aluminum oxide, and its content is 20-80 weight %.
8, catalyzer according to claim 1 is characterized in that, described group VIII metal component is platinum and/or palladium, is benchmark in oxide compound and with the catalyzer total amount, and its content is 0.1-5.0 weight %.
9, catalyzer according to claim 8 is characterized in that, is benchmark in oxide compound and with the catalyzer total amount, and the content of described group VIII metal component is 0.1-1.5 weight %.
10, the described Preparation of catalysts method of claim 1, this method comprises mixes heat-resistant inorganic oxide or its precursor with a kind of molecular sieve and a kind of molecular sieve with macroporous structure with one dimension central hole structure, moulding and roasting, be selected from least a group VIII metal component in introducing afterwards, with the catalyzer total amount is benchmark, it is 10-90 weight % that the consumption of each component makes the content of heat-resistant inorganic oxide in the final catalyzer, the content of molecular sieve is 9.9-89.9 weight %, in oxide compound, the content of group VIII metal component is 0.1-10 weight %, it is characterized in that, described molecular sieve is a kind of molecular sieve and a kind of molecular sieve with macroporous structure with one dimension central hole structure, wherein, described molecular sieve with one dimension central hole structure is 80-99: 1-20 with the weight ratio with molecular sieve of macroporous structure, described molecular sieve with macroporous structure contains non-framework silicon, in oxide compound and with this molecular sieve is benchmark, and the content of described silicon is 1-20 weight %.
11, method according to claim 10 is characterized in that, described molecular sieve with one dimension central hole structure is 90-99: 1-10 with the weight ratio with molecular sieve of macroporous structure, and the content of described silicon is 2-10 weight %.
12, method according to claim 10 is characterized in that, the crystal grain of described molecular sieve with macroporous structure is less than 300 nanometers.
13, method according to claim 12 is characterized in that, described crystal grain with molecular sieve of macroporous structure is the 50-200 nanometer.
14, method according to claim 10 is characterized in that, it is 20-80 weight % that the introducing amount of described heat-resistant inorganic oxide or its precursor makes the content of heat-resistant inorganic oxide in the final catalyzer.
15, method according to claim 10 is characterized in that, it is 0.1-5 weight % that the introducing amount of described group VIII metal component makes the content of group VIII metal component in the final catalyzer.
16, method according to claim 15 is characterized in that, it is 0.1-1.5 weight % that the introducing amount of described group VIII metal component makes the content of group VIII metal component in the final catalyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100020557A CN100425678C (en) | 2005-01-14 | 2005-01-14 | Dewaxing catalyst containing compound molecule sieve and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100020557A CN100425678C (en) | 2005-01-14 | 2005-01-14 | Dewaxing catalyst containing compound molecule sieve and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1803998A CN1803998A (en) | 2006-07-19 |
| CN100425678C true CN100425678C (en) | 2008-10-15 |
Family
ID=36866146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100020557A Active CN100425678C (en) | 2005-01-14 | 2005-01-14 | Dewaxing catalyst containing compound molecule sieve and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100425678C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105586074B (en) * | 2014-11-04 | 2017-07-11 | 北京安耐吉能源工程技术有限公司 | A kind of method of waxy feeds oil hydrodewaxing |
| CN105618155B (en) * | 2014-11-04 | 2018-09-21 | 北京安耐吉能源工程技术有限公司 | Hydrogenation catalyst carrier and its application and hydrogenation catalyst and its application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4575416A (en) * | 1984-07-16 | 1986-03-11 | Mobil Oil Corporation | Hydrodewaxing with mixed zeolite catalysts |
| CN1033757A (en) * | 1984-12-18 | 1989-07-12 | 联合碳化公司 | The dewaxing catalyst of silicon-aluminum containing phosphate molecule sieve |
| US6652735B2 (en) * | 2001-04-26 | 2003-11-25 | Exxonmobil Research And Engineering Company | Process for isomerization dewaxing of hydrocarbon streams |
-
2005
- 2005-01-14 CN CNB2005100020557A patent/CN100425678C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4575416A (en) * | 1984-07-16 | 1986-03-11 | Mobil Oil Corporation | Hydrodewaxing with mixed zeolite catalysts |
| CN1033757A (en) * | 1984-12-18 | 1989-07-12 | 联合碳化公司 | The dewaxing catalyst of silicon-aluminum containing phosphate molecule sieve |
| US6652735B2 (en) * | 2001-04-26 | 2003-11-25 | Exxonmobil Research And Engineering Company | Process for isomerization dewaxing of hydrocarbon streams |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1803998A (en) | 2006-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2362623C2 (en) | Gydroprocessing zeolite-containig catalyst with high mesoporosity | |
| EP3342844A1 (en) | Method for manufacturing lubricant base oil | |
| KR101883017B1 (en) | Integrated hydrocracking and dewaxing of hydrocarbons | |
| TWI409105B (en) | Hydrogenation isomerization catalyst, dewaxing method of hydrocarbon oil, manufacturing method of base oil and manufacturing method of lubricating base oil | |
| EP1973654B1 (en) | Hydroprocessing with blended zsm-48 catalysts | |
| KR100851143B1 (en) | Process for isomerization dewaxing of hydrocarbon streams | |
| US9988585B2 (en) | Method for producing base oil for lubricant oils | |
| JP4860861B2 (en) | Method for producing a lubricating base oil | |
| CN109311001A (en) | Organic silica polyalcohol catalyst and its manufacturing method | |
| CN102533329B (en) | Method for producing base oil of lubricating oil by using Fischer-Tropsch synthesis wax | |
| JP2011508049A (en) | Method for preparing lubricating base oil with high VI and excellent low temperature characteristics | |
| AU768382B2 (en) | Catalytic composition for the upgrading of hydrocarbons having boiling points within the naphtha range | |
| CN103031144A (en) | Isomerization process using metal-modified small crystallite mtt molecular sieve | |
| JP2019513175A (en) | Production of Lubricant Basestocks with Enhanced Aromatic Saturation | |
| US9868912B2 (en) | Method for producing lubricant oil base oil | |
| US9156748B2 (en) | Process for conversion of paraffinic feedstocks obtained from the biomass of middle distillate bases employing at least one IZM-2 zeolite-based catalyst | |
| RU2345123C2 (en) | Method for making medium distillates and lubricant bases relying on synthetic hydrocarbon materials | |
| ITMI990504A1 (en) | CATALYTIC COMPOSITION FOR UPGRADING OF HYDROCARBONIC MIXTURES | |
| CN101722037A (en) | Catalyst for hydrogenation de-waxing of lubricating oil distillate, preparation and application thereof | |
| CN103387848B (en) | Solvent oil, lubricant base and pyroparaffine is produced from Fischer Tropsch waxes | |
| CN106669810A (en) | Alkane isomerization catalyst and preparation method and application thereof | |
| KR102104139B1 (en) | A titania-bound zeolite eu-2 catalyst composition and method of making and using such composition | |
| CN100425678C (en) | Dewaxing catalyst containing compound molecule sieve and preparation method thereof | |
| CN103100413A (en) | Isomerization catalyst and its application | |
| CN107418618A (en) | Reduce the method for the turbidity in heavy basestock and the hydroisomerization catalytic system with the turbidity reduced |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |