CN100548485C - The oxygenate treated dewaxing catalyst is to improve the productive rate of dewaxed product - Google Patents
The oxygenate treated dewaxing catalyst is to improve the productive rate of dewaxed product Download PDFInfo
- Publication number
- CN100548485C CN100548485C CNB2003801011022A CN200380101102A CN100548485C CN 100548485 C CN100548485 C CN 100548485C CN B2003801011022 A CNB2003801011022 A CN B2003801011022A CN 200380101102 A CN200380101102 A CN 200380101102A CN 100548485 C CN100548485 C CN 100548485C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hydrocarbon
- oxygenatedchemicals
- hydrodewaxing
- fischer
- 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.)
- Expired - Fee Related
Links
Images
Abstract
Use synthetic being used for of Fischer-Tropsch hydrocarbon of non-Co catalysts from the synthesis gas preparation wax fuel and the lubricated petroleum hydrocarbon that come from natural gas.In the presence of hydrogen, by making waxy hydrocarbon and not vulcanizing catalyst for hydrogenation de-waxing and contact and make the waxy hydrocarbon Hydrodewaxing, change into low boiling hydrocarbon thereby reduce, this does not vulcanize catalyst for hydrogenation de-waxing and is reduced, then by itself and the logistics that contains one or more oxygenatedchemicals are handled.
Description
Invention field
The present invention relates to make the hydrocarbon Hydrodewaxing with the not sulfuration dewaxing catalyst of oxygenate treated.More particularly, the present invention relates to catalyst, also relate to by from the presence of Fischer-Tropsch (Fischer-Tropsch synthetic) catalyst, making the H that makes from natural gas
2The waxy hydrocarbon of synthesizing with the CO reaction is by making the waxy hydrocarbon Hydrodewaxing prepare the fuel and the lube cut of dewaxing through contacting the processed dewaxing catalyst that do not vulcanize with oxygenatedchemicals.
Background of invention
Can prepare fuel and lubricant by various additives are added in the basic material, it generally includes the dewaxing hydrocarbon fraction of the waxy hydrocarbon that comes from the boiling range of target fuel and lubricating oil.Dewaxing can be reduced to acceptable level with the pour point and the cloud point of waxy hydrocarbon.Relatively pure waxy hydrocarbon and the alkane synthetic by Fischer-Tropsch process are excellent materials for diesel fuel, jet fuel and the senior lubricant that preparation has low-sulfur, nitrogen and aromatics content.The sulphur of these waxy hydrocarbon, nitrogen and aromatics content are essentially 0, and therefore thick hydrocarbon can carry out updating operation, does not need hydrotreatment in advance.In Fischer-Tropsch process, H
2In the presence of hydrocarbon synthesis catalyst, react to form waxy hydrocarbon with CO.Those waxy hydrocarbon fractions that are solid under environmental condition are called as fischer-tropsch wax, are usually included in the hydrocarbon in fuel and the lubricating oil boiling range formula.Therefore yet its cloud point and pour point are too high can not to be used as fuel and lubricating oil, must further handle (for example dewaxing) so that cloud point and pour point have is acceptable low-level.Because the productive rate of dewaxing hydrocarbon in distillation fuel boiling range is lowered basically, and comprise the higher molecular weight (C for example of lube cut
16+) hydrocarbon is solid usually at ambient temperature, so can not make solvent dewaxing.The whole bag of tricks that is used to make the waxy hydrocarbon catalytic dewaxing is disclosed.Many methods make waxy hydrocarbon be dewaxed to product in being lower than fuel and lubricating oil boiling range as those that use the ZSM-5 catalyst by hydrocracking.Additive method comprises that hydrotreatment is to remove hetero atom, aromatic substance and other unsaturates.Exemplary but unrestriced various catalytic dewaxing process example is disclosed in for example United States Patent (USP) 6,179,994; 6,090,989; 6,080,301; 6,051,129; 5,689,031; 5,075,269 and EP 0 668 342 B1 in.
Recently, disclose the catalyst that mainly dewaxes (for example be disclosed in United States Patent (USP) 5,075,269 in), and because low these catalyst of cracking make dewaxed product have big productive rate by isomerization.Yet, even the dewaxed product loss that these best catalyst also have some lytic activities and follow.Catalyst with high lytic activity is especially unwanted for making the hydrocarbon dewaxing that does not contain a large amount of waxes, and this is because they use noncobalt fischer tropsch catalyst to make.The sulfuration dewaxing catalyst can reduce its lytic activity, and this is being known in the art, but vulcanizes the H-H reaction gas that can pollute dewaxed product and pass through dewaxing reactor.Even, can make improvements this area so if can find not need to vulcanize but still can obtain good Hydrodewaxing result's catalyst treatment to the waxy hydrocarbon that does not contain a large amount of waxes.In addition, catalyst should have lower lytic activity in making by the process of the synthetic hydrocarbon Hydrodewaxing that makes of non-cobalt Fischer-Tropsch hydrocarbon, thereby improves the productive rate of its isomerization dewaxing activity and impurity dewaxed product.
Summary of the invention
Have been found that the waxy hydrocarbon of using non-Co catalysts to make from the Fischer-Tropsch hydrocarbon synthesis process comprises the fuel and lubricant fraction, and can use and be reduced then and contain the not sulphurized catalyst that the oxygenatedchemicals hydrocarbon contacts and to change into low boiling hydrocarbon by Hydrodewaxing than the lowland.
In one embodiment, the present invention relates to (a) and prepare synthesis gas, (b) in the presence of noncobalt fischer tropsch catalyst, under the reaction condition that can effectively synthesize the waxy hydrocarbon that is included in the fraction in fuel and the lubricating oil boiling range, make the H in the gas from natural gas
2With CO reaction, and (c) make to the small part waxy hydrocarbon by updating apparatus, wherein with hydrogen with contain the not sulphurized catalyst that the oxygenatedchemicals hydrocarbon contacts and make its Hydrodewaxing.Wherein conversion of natural gas becomes synthesis gas, and then the method that changes into hydrocarbon is called the gas conversion method.Therefore, the present embodiment relates to gas conversion process and adds by Hydrodewaxing upgrading product.
Hydrodewaxing method comprises the dewaxing catalyst contact that waxy hydrocarbon and hydrogen are handled with catalyst is contacted with the hydrocarbon that contains one or more oxygenatedchemicals.Can choose wantonly, the waxy hydrocarbon for the treatment of Hydrodewaxing and containing one or more oxygenatedchemicals can contact with dewaxing catalyst.Dewaxing catalyst can be reduced and keep not vulcanizing, preferred reduction and not sulfuration.Because by reducing the lytic activity of dewaxing catalyst, material changes into low boiling hydrocarbon,, and carry out in position or in the dystopy Hydrodewaxing reactor so this processing reduces the loss of Hydrodewaxing product.The catalyst for hydrogenation de-waxing that experiment shows oxygenate treated for example ZSM-48 catalyst for hydrogenation de-waxing is equivalent to sulfureted catalyst, and material changes into low boiling hydrocarbon and low methane.Herein, ZSM-48 comprises EU-2, EU-11 and ZBM-30, and its structural equivalents is in ZSM-48.
Noncobalt fischer tropsch catalyst refers to that wherein the active catalyst composition is the catalyst that comprises at least a metal among Fe, Ni, Ru, Re and the Rh except cobalt.
One or more oxygenatedchemicals hydrocarbon that contain of handling usefulness comprise to the synthetic waxy hydrocarbon of small part expense-fischer-tropsch catalyst, can comprise that the waxy hydrocarbon material for the treatment of Hydrodewaxing does not comprise.Term " oxygenatedchemicals " refers to water and oxygenatedchemicals, and it forms water under the Hydrodewaxing condition.Used oxygenatedchemicals can comprise water or one or more oxygen-containing molecules in processing, and described oxygenatedchemicals preferably includes list or polyalcohol, ester, ether, ketone, aldehyde, carboxylic acid and composition thereof, preferably includes one or more alcohol.It can be intrinsic with the synthetic waxy hydrocarbon of catalyst in the Fischer-Tropsch hydrocarbon synthesis reactor, and/or it can be added to and is used on the waxy hydrocarbon handling.When oxygenate treated makes when using water as oxygenatedchemicals, after being reduced, dewaxing catalyst adds entry.After the processing, handle oxygenatedchemicals and continue to be present in the hydrodewaxed material, the product of catalyst, Hydrodewaxing reaction or Hydrodewaxing is not had adverse effect.Therefore, the waxy hydrocarbon fractions that contains oxygenatedchemicals that the Fischer-Tropsch hydrocarbon synthesis reaction by catalysis makes can be used for catalyst treatment, and Hydrodewaxing does not have adverse effect then, thereby oxygenatedchemicals continues to be present in the wax.In the following embodiments, preferred catalyst for hydrogenation de-waxing ZSM-48 continues to handle with the thick fischer-tropsch wax that contains oxygenatedchemicals, also be about the Fischer-Tropsch light oil processing that contains oxygenatedchemicals of 525 (274 ℃) with the terminal boiling point, each all is to use non-conversion cobalt hydrocarbon synthesis catalyst to synthesize.
The accompanying drawing summary
Fig. 1 shows that catalyst that the present invention handles compares hydrogenolysis and β fracture ratio with untreated catalyst.
Relatively for that handle and untreated catalyst, gas generates the function that transforms as material to Fig. 2.
Relatively for that handle and untreated catalyst, the oily productive rate of 700+(371 ℃) Hydrodewaxing is as the function of pour point for Fig. 3.
Fig. 4 handle with sulphurized catalyst between hydrogenolysis and β fracture than similar.
Fig. 5 shows similar with the generation of sulphurized catalyst gas for what handle.
Fig. 6 is the comparison figure with 700 (371 ℃) transforming degrees sulphurized catalyst that handle when given pour point.
Fig. 7 shows that the gas of catalyst when various 700 (371 ℃) level of conversion that oxygenated light oil and wax are handled generates.
Fig. 8 shows the pour point of catalyst when various 700 (371 ℃) level of conversion that oxygenated light oil and wax are handled.
Describe in detail
Dewaxing catalyst can be crystal or amorphous body.Crystalline material is to contain at least one 10 or 12 yuan ring passages and can be based on aluminosilicate (zeolite) or can be based on the molecular sieve of aluminum phosphate.The zeolite that is used for oxygenate treated can contain at least one 10 or 12 passage.The example of this zeolite comprises ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ferrierite, EU-1, NU-87, ITQ-13 and MCM-71.The example that contains the molecular sieve of 12 yuan of ring passages comprises β zeolite, ZSM-12, MCM-68, ZSM-18, modenite, faujasite and offretite.Should be noted that,, described in 077, can make dewaxing catalyst such as ZSM-5 have the dewaxing performance of variation by regulating catalyst performance, as acidity, metal dispersion catalyst particle size as at United States Patent (USP) 6,294.Molecular sieve is disclosed in United States Patent (USP) 5,246, in 566,5,282,958,4,975,177,4,397,827,4,585,747 and 5,075,269.MCM-68 is disclosed in United States Patent (USP) 6,310, in 265.MCM-71 and ITQ-13 are disclosed among PCT published application WO 0242207 and the WO 0078677.Preferred catalyst comprises ZSM-48, ZSM-22 and ZSM-23.Particularly preferably be ZSM-48.Molecular sieve is preferably in hydrogen.But the dewaxing step in the reduction original position carry out or in other containers dystopy carry out.
Amorphous dewaxing catalyst comprises with the metal-doped aluminium oxide of the 3rd family, fluorided alumina, silica-alumina, fluorinated silica-aluminium oxide and silica-alumina.This catalyst for example is disclosed in the United States Patent (USP) 4,900,707 and 6,383,366.
Dewaxing catalyst is bifunctional, and promptly they are filled with the metal hydrogenation composition, and this composition is at least a VI family metal, at least a group VIII metal or its mixture.Preferred metal is the group VIII metal.Particularly preferably be Pt, Pd or its mixture.These metals are in the ratio filling by catalyst 0.1～30wt.%.Preparation of Catalyst and metal filling method for example are disclosed in the United States Patent (USP) 6,294,077, comprise and for example use decomposable slaine to carry out ion-exchange and dipping.The control of metal dispersion and catalyst particle size is disclosed in United States Patent (USP) 5,282, in 958.The catalyst that has than the metal of small particle diameter and fine dispersion is preferred.
Molecular sieve mixes (adhesive patience is higher and can use to form refining dewaxing catalyst) usually or can not contain adhesive (autoadhesion) under the dewaxing condition with binder materials.Binder materials is inorganic oxide normally, as the binary composition of silica, aluminium oxide, silica-alumina, silica and other metal oxides such as titanium dioxide, magnesia, thorium oxide, zirconia etc. and ternary composition such as the silica-alumina-thorium oxide and the silica-alumina-magnesia of these oxides.The amount of molecular sieve counts 10～100 by catalyst, preferred 35～100wt.% in refining dewaxing catalyst.This catalyst can be by forming such as methods such as spray-dried, extruding.Dewaxing catalyst can use with the form of unsulfided.Dewaxing catalyst also preferably reduces form.
Can be used for illustrating with making by the ZSM-48 prepare zeolite in the preferred embodiment to further specifying of dewaxing catalyst.The dewaxing catalyst that comprises ZSM-48 zeolite component and hydrogenation component is known, and is disclosed in for example United States Patent (USP) 4,397,827; 4,585,747; 5,075,269 and EP 0142317 in, its disclosure is hereby incorporated by.The ZSM-48 zeolite is the acidic crystalline silica-alumina molecular sieve of median pore radius, and it has 10 side ring pore structures, and available organic directed agents preparation.After the preparation, it changes into hydrogen form by ion-exchange and calcining.When preparation is used for the catalyst of the inventive method, hydrogen form ZSM-48 zeolite and adhesive and/or matrix components, and one or more extra porous catalyst carrier compositions are compound when needing, and this porous catalyst carrier composition does not preferably have adverse effect maybe can improve its lytic activity to its isomerization activity.This composition can comprise nonacid form, clay such as the bentonite and the kaolinite etc. of silica for example, aluminium oxide and preferred nonacid gamma-alumina, amorphous and crystalline silica-aluminium oxide.Hydrogenation component can comprise at least a group VIII metal ingredient and preferred at least a group VIII noble metals composition, as Pt and Pd.Precious metal concentration is about the metal of 0.1-5wt.% by the total restatement of catalyst, more generally is about 0.2-1wt.%, comprises ZSM-48 zeolite component and any adhesive or is used for other carriers or the matrix components of catalyst composite.Group VIII refers to the group VIII in the Sargent-Welch periodic table of elements (being published in nineteen sixty-eight by Sargent-Welch ScientificCompany).One or more hydrogenation components can be deposited on ZSM-48 or other compositions or its complex by the method that is fit to, with its complex or with its ion-exchange.This method is known, comprises for example dipping or ion-exchange.Used ZSM-48 catalyst comprises the hydrogen form, alumina adhesive of ZSM-48 and as the noble metal of hydrogenation component among the following embodiment.But the aqueous solution of the salt decomposition of metal is immersed on the ZSM-48 Zeolite/alumina complex, and sintering decomposes the salt into metal then.The catalyst that reduction generates in hydrogen before oxygenate treated of the present invention then.Reduction and/or processing subsequently can be in isomerization reactor original position carry out or in separation container dystopy carry out.
Preferred with hydrogen reduction ZSM-48 catalyst before oxygenate treated.One or more oxygenatedchemicals that are used for handling catalyst can be carried at hydrocarbon, handle to comprise that the catalyst that makes reduction contacts with the hydrocarbon stream that contains one or more oxygenatedchemicals.Be to comprise material to be dewaxed or do not comprise in embodiment of the present invention by the synthetic hydrocarbon carrier of Fischer-Tropsch hydrocarbon synthesis reaction to the small part hydrocarbon products.Handling used all or part of oxygenatedchemicals can be added in the hydrocarbon, or it can be that hydrocarbon is intrinsic.For example thick untreated Fischer-Tropsch light oil and wax contain intrinsic oxygenatedchemicals usually because of the result of synthetic reaction.This light oil or wax can be used for handling catalyst, and wax is hydrodewaxed by the catalyst of handling then.
One aspect of the present invention shows that the fischer-tropsch wax that uses thick (untreated) to contain the 400-1500wppm oxygen of the oxygenatedchemicals form of having an appointment intrinsic handles, and uses the catalyst of handling to make the dewaxing of wax material then.Therefore, handling used oxygenatedchemicals exists in Hydrodewaxing subsequently.Also show and use the synthetic light oil fraction of thick (untreated) Fischer-Tropsch, it contains the oxygenatedchemicals of 15wt.% by the total restatement of oxygen-containing molecules.In the hydrocarbon products of Hydrodewaxing, do not find oxygenatedchemicals.Hydrodewaxing takes place in processing, but behind the processed long enough inactivation of catalyst, does not obtain the product productive rate of higher Hydrodewaxing at first.This is elucidated later herein below.Form wax and light oil with non-shifting cobalt catalyst by the Fischer-Tropsch hydrocarbon synthesis reaction.
If can being added to simply, intrinsic oxygenatedchemicals amount deficiency, so extra oxygenatedchemicals be used in the material handling.In another embodiment, can be except the hydrocarbon of the material for the treatment of Hydrodewaxing as the carrier of oxygenate treated.For handling, the oxygenatedchemicals amount is at least by oxygen and counts the 100wppm that handles used hydrocarbon, preferably is at least 200wppm, more preferably is at least 400wppm.(for example 〉=3,000wppm) excessive existence can not have adverse effect to the product of catalyst, method or Hydrodewaxing to oxygenatedchemicals.Preferred oxygenatedchemicals is oxygen-containing molecules, and described oxygen-containing molecules comprise alcohol, ester, ether, ketone, aldehyde, carboxylic acid and composition thereof, more preferably comprise one or more alcohol.Another kind of preferred oxygenatedchemicals is a water, and it can generate from other oxygenatedchemicals under the Hydrodewaxing condition.Handle in the used hydrocarbon stream if one or more oxygenatedchemicals are added to, they can be discarded behind catalysqt deactivation so, and this may need two thoughtful one month.Yet, in leaving them in the feed being hydrodewaxed Hydrodewaxing reaction or catalyst are not had adverse effect.Can measure inactivation by observing lytic activity, its reaction is that gas prepares material and changes into the degree of low boiling hydrocarbon or the reduction of the two.When lytic activity was reduced to more or less constant, catalyst was considered to inactivation.
Hydrodewaxing is removed oxygenatedchemicals, therefore is not found in the product of Hydrodewaxing usually.After handling catalyst, oxygenate treated with the identical or different condition of Hydrodewaxing subsequently under carry out.In the following embodiments, the Hydrodewaxing temperature that is lower than subsequently in temperature is that 300 °F (167 ℃) start catalyst treatment down.The Hydrodewaxing reaction condition comprises that temperature, hydrogen dividing potential drop, liquid hourly space velocity (LHSV), hydrogen processing gas speed are respectively 450-850 (232-454 ℃), 10-2,000psig (170-13891kPa), 0.1-5.0LHSV, 500-10000scf/B (89-1780m
3/ m
3).These conditions can be changed into 500-750 (260-399 ℃), 100-1,000psig (791-6996kPa), 0.5-3.0LHSV, 1000-5000scf/B (178-890m usually
3/ m
3), pressure is preferably 200-700psig (1480-4928kPa).
The catalyst that wax that makes by Fischer-Tropsch reaction or waxy hydrocarbon use the present invention to handle carries out the dewaxed product of Hydrodewaxing with the preparation depression of pour point, and it comprises at least a (i) distillation fuel fraction and (ii) lubricant fraction.Usually, Hydrodewaxing with the depression of pour point of the product of Hydrodewaxing to required specification, forming one or more distillation fuel that one or more (a) are used for blending, and (b) one or more lubricant base stock.One or more lubricant base stock can comprise heavy lubricant base stock or not comprise.In preferred embodiments, the lubricant product of Hydrodewaxing comprises one or more lubricant base stock, is more preferably heavy lubricant base stock.Distillation fuel refers to the hydrocarbon fraction of Hydrodewaxing, and boiling point is from about C
5Up to about 550-730 °F (288-388 ℃), comprise naphtha, diesel oil and jet fuel.In the present invention, heavy fraction comprises the heavy grease fraction, and when hydrodewaxed, it comprises heavy lubricant base stock.Lubricant base stock refers to that initial boiling point is higher than 600 °F (316 ℃) and more generally at least about the lubricating oil of 700-750 (371-399 ℃), it has been hydro-dewaxed to target pour point and cloud point.The initial boiling point of heavy lubricant base stock is about 850-1000 °F (454-538 ℃), and the terminal boiling point is higher than 1000 °F, preferably is higher than 1050 °F (566 ℃).Initial and terminal boiling point value is specified, refers to the T5 and the T95 fraction that use following method to obtain by gas-chromatography distillation (GCD).
Distillation fuel and lubricant basic material prepared in accordance with the present invention hydrofinishing under temperate condition usually, and can choose wantonly and take off muddiness, to improve color and stability, to form refining fuel and lubricant basic material.Be well known that muddiness is meant dark or unintelligible, is a kind of appearance factor.Usually remove these by catalysis or adsorption method and cause that muddy key element can realize taking off muddiness.Hydrofinishing is extremely gentle, cold relatively method of hydrotreating, and it uses catalyst, hydrogen and Wen Ge reaction condition to remove trace atomic compound, aromatic substance and alkene, to improve oxidation stability and color.The hydrofining reaction condition comprises that temperature is 302～662 °F (150～350 ℃) and be preferably 302～482 °F (150～250 ℃), and gross pressure is that (2859～20786kPa), liquid hourly space velocity (LHSV) is 0.1～5LHSV (hr to 400～3000psig
-1) and be preferably 0.5～3hr
-1It is 250～10000scf/B (44.5～1780m that gas speed is handled in the hydrogen Hour
3/ m
3).Catalyst comprises carrier components and at least a catalytic metal composition, metal be group vib (Mo, W, Cr) and/or iron group (Ni, Co) and the noble metal of group VIII (Pt, Pd).Group vib and group VIII refer to group vib and the group VIII in the Sargent-Welch periodic table of elements (being published in nineteen sixty-eight by Sargent-Welch Scientific Company).Metal can be the 0.1wt.% of carbon monoxide-olefin polymeric for noble metal, and base metal be can be 30wt.%.Preferred carrier material is low acidity, comprises for example amorphous or crystalline metal oxide such as aluminium oxide, silica, silica alumina and is called as the super big hole crystal material of mesoporous crystal material, and wherein MCM-41 is preferred carrier components.The preparation of MCM-41 and purposes are known, and for example are disclosed in the United States Patent (USP) 5,098,684,5,227,353 and 5,573,657.
The fuel and lubricant basic material is included in the fuel and lubricant fraction of the Hydrodewaxing in distillation fuel and the lubricating oil boiling range respectively, it has cryogenic property, comprise pour point and cloud point, enough low before Hydrodewaxing, make each fraction can satisfy required specification or requirement.At least a additive by raw material and effective dose separately or more generally contain additive group more than a kind of additive and form mixture and prepare fuel or lubricant.This additive of the lubricant that is used to make with extra care (lubricant) is exemplary but unrestricted example comprises one or more washing agent, dispersant, antioxidant, antiwear additive, EP agent, pour-point depressant, VI improver, friction modifiers, demulsifying agent, antioxidant, defoamer, corrosion inhibitor and sealing swelling control additive.Form the raw material used in the mixture normally behind the Hydrodewaxing through gentle hydrofinishing and/or take off muddy to improve the raw material of its color, outward appearance and stability.Cryogenic property requires and can change, and depends in part on the geographical position of wherein used fuel or lubricant.For example, the freezing point of jet fuel is not higher than-47 ℃.Diesel fuel in the cloud point in summer and winter in whole world change, for-15～+ 5 ℃ and-35-5 ℃.The cryogenic property of conventional lightweight and middle heavy lubricant base stock can comprise that pour point is about-20 ℃, cloud point be no more than usually 15 ℃+.Heavy lubricant base stock is normally transparent under the pressure condition of 75 of room temperatures (24 ℃) and 1 atmospheric pressure (101kPa).Yet cloud point can be higher than 75 °F (24 ℃) in some cases.
Wax material or the wax for the treatment of Hydrodewaxing comprise all or part of waxy hydrocarbon fractions for preparing in the Fischer-Tropsch hydrocarbon synthesis reactor, it is a liquid under reaction condition.Be well known that in the Fischer-Tropsch hydrocarbon synthesis process liquid and gaseous state hydrocarbon products are by comprising H
2Contact and form with Fischer-Tropsch catalyst with the synthesis gas of the mixture of CO, wherein H
2React to form hydrocarbon with CO.Synthesis gas contains usually less than 0.1vppm with preferably less than sulphur or the nitrogen of 50vppb, and it is the formation of one or more sulfur-bearings and nitrogen-containing compound.From synthesis gas, remove denitrification and sulphur so that these to be reduced to extremely low-level method be known and be disclosed in for example United States Patent (USP) 6,284,807; 6,168,768; In 6,107,353 and 5,882,614.
In the methods of the invention, noncobalt fischer tropsch catalyst is included at least a Fe, Ni, Ru, Re or the Rh of the catalytically effective amount on the suitable inorganic carrier material, preferred Fe and Ru, and can choose any one kind of them or multiple co-catalyst such as Mn, Ti, Mg, Cr, Ca, Si, Al, Cu, Th, Zr, Hf, U, Mg and La, preferably include the catalyst of one or more refractory metal oxides.Useful catalysts and preparation thereof are known, and it is exemplary but limiting examples can for example be disclosed in United States Patent (USP) 4,568,663; 4,663,305; 4,542,122; 4,621,072,5,545,674 and U.S.'s published application 20020128331 in.
Fixed bed, fluid bed and slurry hydrocarbon building-up process are well known and documented in the document.In all these processes, synthesis gas is in the presence of the Fischer-Tropsch type hydrocarbon synthesis catalyst that is fit to, react under the reaction condition that can effectively form hydrocarbon.Under the normal room temperature condition in (it is 1 atmospheric pressure (101kPa) with pressure that temperature is 25 ℃) these hydrocarbon some are liquid, and some are solid (for example wax), and some are gas.Slurry fischer-tropsch hydrocarbon synthesis process is normally preferred, because they can prepare the alkane of the more HMW that is used for lubricant and heavy lubricant base stock.In the present invention, waxy hydrocarbon or wax material can be in slurry, prepare in fixed bed or the fluid bed Fischer-Tropsch reaction device.
Fischer-tropsch wax contains intrinsic oxygenatedchemicals.For example, Table A has been listed to use and has been comprised that rhenium helps intrinsic oxygenatedchemicals that the synthetic wax of non-transformation catalyst of the cobalt catalyst component of catalysis makes by the scope of oxygen as the function of boiling range below.In Table A, oxygen obtains from oxygen-containing organic compound or oxygenatedchemicals, is unit with oxygen, and wppm or the wt.% with oxygenatedchemicals molecule itself is not unit.For example be called as when containing the 400-600wppm oxygenatedchemicals when wax, be meant that the oxygen amount is confirmed as 400-600wppm in the oxygenatedchemicals of wax by oxygen.Its boiling range of reactor wax in the table is about 500 °F (260 ℃), and at most greater than 1,000 °F (538 ℃), and heat separator wax boiling point is about 350-700 °F (177-371 ℃).
Table A
| Alcohol wppm | Ether wppm | Ester wppm | Total oxygen wt.% | |
| Reactor wax | 67-1259 | 86-270 | 67-109 | 0.06-0.2 |
| Heat separator wax | 1519-3394 | 0.17-0.39 |
Table B has listed the concentration of three types of oxygenatedchemicals when three different molecular carbon atoms in fischer-tropsch wax of the same race below, and this has represented three different molecular weight ranges.
Table B
Exemplary below but in the limiting examples, in the slurry Fischer-Tropsch reaction device that contains the Co catalysts (comprise the titania support composition, initial boiling point is about 450 (232 ℃)) that non-conversion rhenium helps catalysis, prepare wax.This wax generally includes 90 or the alkane of bigger percentage by weight, reaches the oxygenatedchemicals of 2-4wt.% and reaches the alkene of 2-5wt.%; Aromatic substance can not be analyzed with NMR and detect, and wax contains less than the sulphur of 1wppm with less than the nitrogen of 1wppm.Total oxygen wt.% activates by neutrality and measures.If water content is less than about 200ppm, total oxygen content can be measured then GC-MS by anhydrous definite total oxygen content by using calcium carbide (to form acetylene).For water content greater than 200ppm, the Karl-Fischer method among the available ASTM standard D4928.Total oxygenates level can be determined by high-resolution NMR, and primary alconol, ketone and aldehyde can be determined by GC-MS.Acid, ester and other two oxygenatedchemicals are by IR or GC-FID and GC-MS mensuration.Aromatic substance is determined by the x-ray fluorescence (XRF) that is disclosed among the ASTM standard D-2622, and alkene can use the bromine index of determining through the storehouse fractional analysis to measure according to ASTM standard D2710.D-2622 measures sulphur by XRF according to the ASTM standard, according to ASTM standard D4629 by inject/enter oxidizing fire and chemiluminescence detection is measured nitrogen.
In the integrated approach embodiment that is used for synthesizing waxy hydrocarbon and makes its dewaxing, this method is included in the existence of Fischer-Tropsch hydrocarbon synthesis catalyst and makes H down under the reaction condition that can effectively form waxy hydrocarbon
2React with CO, waxy hydrocarbon partly is a liquid under reaction condition, at hydrogen with do not make to these waxy hydrocarbon Hydrodewaxings of small part in the presence of the sulphurized catalyst (comprise hydrogenation component and dewaxing composition), wherein catalyst is reduced before Hydrodewaxing, handle with containing one or more oxygenatedchemicals hydrocarbon streams then, thereby (i) improve the selectivity of catalyst, (ii) be reduced in the gas that produces in the Hydrodewaxing, and (iii) prepare the dewaxing hydrocarbon of pour point and cloud point decline Hydrodewaxing.Hydrogen is meant following hydrogen: comprise that the hydrogen Hour that is at least 60, preferably is at least 80% hydrogen handles gas or hydrogen rich off gas, all the other are inertia with respect to catalyst for hydrogenation de-waxing and hydrocarbon synthesis catalyst.The hydrogen of low-sulfur level or hydrogen are handled gas and can be obtained from various sources, include but not limited to a small amount of logistics of the synthesis gas of handling (for example methanator or transport reaction device, TSA, PSA, methane separation etc., these are disclosed in for example United States Patent (USP) 6,147, in 126), be used for removing CO from synthesis gas, and preparation high-quality hydrogen.
Invention will be further understood with reference to the examples below.
Embodiment
In embodiment 1, the oxygenatedchemicals hydrocarbon that contains that is used to handle the ZSM-48 catalyst for hydrogenation de-waxing of reduction is a fischer-tropsch wax, and it is the light oil that contains oxygenatedchemicals in embodiment 2, and it also prepares in the Fischer-Tropsch hydrocarbon synthesis reactor.The two all is to prepare in slurry Fischer-Tropsch reaction device, wherein H
2Help at the rhenium of titania supported with CO that reaction is to form hydrocarbon in the presence of the Co catalysts of catalysis, wherein great majority are liquid under reaction condition.Oxygenatedchemicals in wax and light oil also forms in hydrocarbon synthesis reactor as the result of order synthetic reaction, therefore is that wax and oil are intrinsic.These oxygenatedchemicals major parts are alcohol, are ester and ether on a small quantity.In environmental condition is that the wax of solid comprises following 450+(232 ℃) wax fraction, and contains the oxygenatedchemicals by oxygen 400-600wppm.The light oil that is liquid under environmental condition comprises about C
5-C
20Molecule, its boiling range are about 97-526 °F (36-274 ℃), and contain the oxygenatedchemicals by the about 7010wppm of total oxygen content, as alcohol, ester and organic acid.The light oil of about 5.2wt.% comprises alcohol commonly used, as ethanol, propyl alcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, amylalcohol and hexadecanol.
Except being used to handle the containing oxygenatedchemicals wax and the light oil of reduction dewaxing catalyst, 320 °F+(160 ℃+) and 700+(371 ℃+) wax isomeric compound be used to the catalyst that (i) contacts reduction, make comparisons with oxygenate treated of the present invention, and (ii) as the wax material of Hydrodewaxing among the embodiment 1.The wax isomeric compound does not contain oxygenatedchemicals, and used wax makes and contains 450 of oxygenatedchemicals+(232 ℃+) fischer-tropsch wax Hydrodewaxing and obtain by being used in the catalyst that comprises 0.3wt.%Pd on the amorphous silica alumina carrier among the embodiment 1.For embodiment 2, use boiling range to be about the light isomerate of 700-950 (371-510 ℃).All oxygenatedchemicals are removed in isomerization from wax.Use the ZSM-48 catalyst to obtain light isomerate.Three kinds of isomeric compound fractions still contain some waxes after isomerization.For example, the light isomerate pour point is+14 ℃, when the wax that obtains 22wt.% with MIBK during-18 ℃ of solvent dewaxings.
Among all below embodiment, make wax material Hydrodewaxing with particle ZSM-48 catalyst, it is pure hydrogen that hydrogen is handled gas.ZSM-48 catalyst on the ZSM-48 of hydrogen form zeolite and alumina adhesive complex comprises that the Pt of 0.6wt.% is as hydrogenation component.According to United States Patent (USP) 5,075, the method in 269 prepares the hydrogen form ZSM-48 zeolite component of catalyst, and this patent content is hereby incorporated by.Calcine adding Pt composition then by dipping.The particle packing of sintering is in fixed bed pilot plant reactor, and with mobile hydrogen in-situ reducing in reactor.Reduce temperature then, slowly handle the catalyst (avoiding heat release) of reduction, in about 6 hours, hot liquid wax is added in the reactor,, therefore contact with oxygenatedchemicals to guarantee all reducing catalyst impregnated with particles in wax liquid.After this, the temperature in the reactor is elevated to the Hydrodewaxing temperature, and material to be dewaxed therefrom passes through.In processing and Hydrodewaxing subsequently, keep hydrogen to flow in the reactor.Usually behind about 30 days off-response devices, collect pour point and conversion data in the accompanying drawing.
The productive rate and the pour point of 700+(371 ℃+) fraction of (isomerized) that 700+(371 ℃+) productive rate in the accompanying drawing and pour point refer to Hydrodewaxing.CH
4/ different C
4H
10Than being mol ratio, be from hydrogenolysis (CH
4) and β fracture (different C
4H
10) record.Gas is to change into C
1-C
4The weight of material percentage of hydrocarbon.700 °F (371 ℃) transform is to change into the percentage by weight of 700+(371 ℃+) material that boiling point is lower than the hydrocarbon of 700 (700-/(371-℃)).700+(371 ℃+) productive rate refers to that to pour point boiling point is higher than the weight percent yield of the isomerized hydrocarbon of 700 (371 ℃), and the material level of conversion is corresponding to the pour point among the figure.700+(371 ℃+) conversion calculations is as follows:
700 °F+conversion=[1-(wt.%700 in the product+fraction)/(wt.%700 in the material+)] * 100
Use the improvement of the high temperature GCD method of ASTM D-5307 to carry out gas-chromatography distillation (GCD).Post is made of the single capillary post with thin liquid phase, less than 0.2 micron.Use external perimysium reference, form by the boiling point calibration of 5～100 carbon.The syringe of serviceability temperature control, sample hot water mild heat before injection.Use this method and T5 and T95GCD result to measure boiling range.Use ASTM D-5773 to press the lubricant process approach and measure cloud point values by Phase Two Tec Instruments.According to ASTM D-5950 pour point is measured in the measurement of the automatic pour point of ISL.Measure viscosity and viscosity index (VI) according to ASTM agreement D-445 and D-2270 respectively.The catalyst that embodiment 1-handles
In the hydrogen that flows, in temperature is that 500 (260 ℃) and pressure are the following reduction of 500psig (3549kPa) ZSM-48 catalyst 6 hours.The hydrogen flow velocity is a gas Hour air speed (GHSV), is 445.After the reduction, keep hydrogen to flow and pressure, temperature is reduced to 350 °F (177 ℃), slowly adds 450 of Fischer-Tropsch+(232 ℃) then in 6 hours and contain the oxygenatedchemicals liquid wax in reactor, to handle catalyst.Keeping pressure, the hydrogen in the reactor and containing oxygenatedchemicals wax flow velocity is under the 1LHSV, and temperature is risen to the Hydrodewaxing temperature range, is 610-630 °F (321-332 ℃), makes dewaxing continue 50 days.Then, material switch to 320 °F+(160 ℃) and 700+(371 ℃+) wax isomeric compound reach 45 days.These isomeric compounds are partial hydrogenation dewaxing before this, does not contain oxygenatedchemicals, and contains oxygenatedchemicals fischer-tropsch wax Hydrodewaxing and obtain by making.The result of the catalyst of handling shows in Fig. 1-6.
Fig. 1 shows the catalyst of in Hydrodewaxing the present invention being handled, and extremely low hydrogenolysis ruptures than (CH to β
4/ different C
4H
10), use the untreated catalyst of Comparative examples A to obtain bigger ratio.Containing beginning on the oxygenatedchemicals wax material at the 60th day square corresponding to the catalyst of handling.Behind only about 6 days of the Hydrodewaxing, β fracture ratio is less than 0.5.In of the beginning of the 115th day solid circles corresponding to the untreated catalyst of Comparative examples A.When untreated catalyst began, the material of the catalyst that is used to handle was switched to non-oxygenatedchemicals waxy isomerate feed.Switch the inactivation performance that does not change the catalyst that the present invention handles at about the 115th day material.On the contrary, the performance of untreated catalyst is far from it when beginning.The β fracture surpasses 6 than higher, and decline in time is slower.The untreated catalyst of Comparative examples A is observed data disperse, this is because variation of temperature.Yet identical variations in temperature takes place in catalyst that the present invention handles at this moment, but does not show dispersion.
The gas that Fig. 2 relatively generates makes 700+(371 ℃+) material change into the function of low boiling hydrocarbon (700-(371 ℃-)) as two kinds of catalyst.In whole conversion range, the catalyst height that the gas that the untreated catalyst of Comparative examples A generates (representing with circle) is handled than the present invention (with square).
The oily productive rate of relatively 700+(371 ℃+) dewaxing of Fig. 3 is as the function of pour point.For given pour point target, show that the productive rate of the dewaxed oil that uses the catalyst that the present invention handles is higher basically.
Comparative examples A-untreated catalyst
Present embodiment is similar to embodiment 1, except the processing of catalyst of reduction.In this experiment, replace handling with the fischer-tropsch wax that contains oxygenatedchemicals the catalyst of reduction, the catalyst soakage of reduction reaches 6 hours in the wax isomeric compound of 320+(160 ℃+) no oxygenatedchemicals.Then, by among the embodiment 1 temperature being risen to the Hydrodewaxing scope, be 570-620 °F (299-327 ℃).The Hydrodewaxing reaction was carried out 45 days, and material switches to 700+(371 ℃+) isomeric compound (also not containing oxygenatedchemicals) from 320+(160 ℃+) isomeric compound during this period.The result shows in Fig. 1-3, and discussed among the embodiment 1 in the above.
Comparative example B-sulphurized catalyst
In this experiment, press the catalyst of embodiment 1 reduction sintering, use 2%--hydrogen sulfide in hydrogen, under 700 (371 ℃+) and 500psig (3549kPa), to handle then and vulcanized in 4 hours.After the sulfuration, under the temperature of 540-580 (282-304 ℃), use the pure hydrogen of 2500SCF/B and 500psig (3549kPa), be placed in 320+(160 ℃+) wax isomeric compound logistics of no oxygenatedchemicals about 20 days.Waxy isomerate feed rate is 1LHSV.Then material switch to 450 °F+(232 ℃) contain the oxygenatedchemicals fischer-tropsch wax, and carried out 84 days under the same conditions again.The result shows in Fig. 4, Fig. 5 and Fig. 6, and the catalyst of handling with the present invention of embodiment 1 relatively.
Hydrogenolysis shows in Fig. 4 with the result of the ratio of β fracture.Sulphurized catalyst is expressed as the rhombus of sealing, and the catalyst of the oxygenate treated of the present invention of embodiment 1 is expressed as square.Sulphurized catalyst is than less than 0.5 o'clock inactivation immediately almost, and the catalyst that the present invention handles needed arrive mutually on year-on-year basis in several days.Yet behind the inactivation, two kinds of catalyst are approximately identical.
Fig. 5 shows that total gas of two kinds of catalyst generations is similar behind inactivation.At the 60th day, two kinds of catalyst all on the oxygenatedchemicals material, all experienced series of temperature and change.Yet, two kinds of catalyst undistinguishable experimentally behind inactivation.Pour point-conversion data that Fig. 6 shows two kinds of catalyst undistinguishable visually in experiment error code difference.
The catalyst that embodiment 2-handles
This experiment is similar to embodiment 1 in every respect, after (i) processing, waxy stone dewaxed under 600 (316 ℃) and 500psig (3549kPa) hydrogen only 6 days, then (ii) before material switches to above-mentioned light isomerate from waxy stone, it is in 600 (316 ℃) and 250psig (1724kPa) dewaxing down, pressure is reduced to 250psig (1825kPa), and continues dewaxing 25 days again.The dewaxing result of light isomerate is shown among Fig. 7 and Fig. 8.
The catalyst that embodiment 3-handles
This experiment is similar to embodiment 1 and embodiment's 2, except catalyst before Hydrodewaxing reduces down at 250 (121 ℃) and 250psig (1825kPa), replacement is in 500 (260 ℃) and 500psig (3549kPa) reduction down, replace containing oxygenatedchemicals wax, the above-mentioned oxygenated light oil that contains is used to handle the catalyst that reduces down at 250psig (1724kPa) and 350 (177 ℃).Temperature rises to 600 °F (316 ℃) then, and material slowly switches to 700-950 (371-482 ℃) fraction of isomerate feed, carries out only 14 days.By the catalyst of handling with the light oil of present embodiment the dewaxing result of light isomerate dewaxing is shown in Fig. 7-8.
With reference to figure 7 and Fig. 8, can see when use contains oxygenated light oil and contain oxygenatedchemicals wax processing ZSM-48 dewaxing catalyst, there is not difference basically.This is reflected in conversion pour point and gas are generated among the dewaxing result, and is substantially the same for the two.
Other catalyst of embodiment 4-
At 750psig (5272kPa) H
2, 1.0LHSV, gas treatment speed is 2500SCF/BBL (445m
3/ m
3) under carry out catalytic dewaxing.The 5cc catalyst is crushed to 14/35 order, and and mixing diluents.For all catalyst, material is the isomerized fischer-tropsch wax of hydrogen, its by fractionation with preparation be generally 700 °F+material, be 6.42% by the wax content that records with the 100%MIBK solvent dewaxing.
The catalyst of all tests all has the platinum of 0.5wt.% as the dehydrogenation composition, except Z-876A contains the Pt of 0.3wt.% and the Pd of 0.15wt.%.Operating temperature is 550 (288 ℃)～580 (304 ℃).The pour point and the viscosity of the product that analysis obtains from various catalyst are during data are listed in the table below.Productive rate in the table is corresponding to only operating those that above-mentioned catalyst obtains.These results show the performance of these catalyst, and oxygenate treated is not carried out in the dewaxing of Fisher-Tropsch derived isomeric compound.The lubricating oil that makes from these catalyst shows rational viscosity and pour point.Oxygenatedchemicals is added in these catalyst estimates to strengthen productive rate, this is similar with the embodiment that use ZSM-48 in the past prepares the optionally catalytic dewaxing in the lubricating oil.
Table C
| Catalyst | 700 °F+productive rate | KV@100℃ | VI | Pour point ℃ |
| Pt/TON | 94.49 | 5.1 | 148 | -21 |
| PT/ZSM-23 | 90.18 | 5.22 | 147 | -27 |
| Z-876(FER) | 64.9 | 4.74 | 141 | -44 |
| Pt/FER | 59.38 | 4.68 | 141 | -38 |
| Pt/LaFER | 89.24 | 4.76 | 142 | -33 |
In table C, TON is θ-1 (ZSM-22), and FER is a ferrierite.
Claims (21)
1. one kind makes the wax Fischer-Tropsch hydrocarbon Hydrodewaxing for preparing by non-Co catalysts to prepare the method for Hydrodewaxing hydrocarbon, its not sulfuration catalyst for hydrogenation de-waxing that is included in the processing that comprises group VIII metal ingredient and ZSM-48 molecular sieve exists down, can effectively make described waxy hydrocarbon Hydrodewaxing and reduce under the reaction condition of its pour point and cloud point, described hydrocarbon is contacted with hydrogen, wherein described catalyst is reduced before described Hydrodewaxing, handle with the hydrocarbon stream that contains one or more oxygenatedchemicals then, the amount of described oxygenatedchemicals is at least 100wppm by oxygen, to increase the Hydrodewaxing selectivity of described catalyst.
2. method according to claim 1, wherein said wax Fischer-Tropsch hydrocarbon are synthetic by the following method, and this method is included in the non-conversion Fischer-Tropsch hydrocarbon synthesis catalyst that contains non-cobalt catalyst component and exists down, makes H under the reaction condition that can effectively form waxy hydrocarbon
2React with CO.
3. method according to claim 1, wherein to described one or more oxygenatedchemicals of small part be that described processing hydrocarbons logistics is intrinsic, and its content is at least 200wppm by oxygen.
4. method according to claim 1, the wherein said hydrocarbon stream that contains one or more oxygenatedchemicals comprises wax Fischer-Tropsch hydrocarbon, described wax Fischer-Tropsch hydrocarbon produces on noncobalt fischer tropsch catalyst.
5. method according to claim 2, wherein said non-Co catalysts are at least a among Fe, Ni, Ru, Re or the Rh.
6. method according to claim 3, wherein said non-Co catalysts is Fe or Ru.
7. method according to claim 4, wherein said oxygenatedchemicals comprises one or more oxygen-containing molecules.
8. method according to claim 5, wherein said oxygenatedchemicals comprises one or more oxygen-containing molecules.
9. method according to claim 8, wherein said one or more oxygen-containing molecules are water.
10. method according to claim 8, wherein said one or more oxygen-containing molecules comprise list or polyalcohol, ester, ether, ketone, aldehyde, carboxylic acid and composition thereof
11. method according to claim 1, the content of wherein said one or more oxygenatedchemicals is at least 200wppm by oxygen.
12. method according to claim 1, wherein said Hydrodewaxing hydrocarbon comprise at least a (a) fuel feedstocks and (b) lubricant base stock.
13. method according to claim 12, wherein said raw material is by hydrofinishing.
14. method according to claim 12, wherein said raw material is by hydrofinishing and gone turbid.
15. according to claim 13 or 14 described methods, wherein said raw material comprises lubricant base stock, wherein said lubricant base stock combines with one or more lubricant additives to form lubricant.
16. method according to claim 1, wherein said hydrocarbon comprise one or more fuel and lubricant basic materials, and wherein said one or more raw materials are by hydrofinishing.
17. method according to claim 1, wherein said hydrocarbon comprise one or more fuel and lubricant basic materials, and wherein said one or more raw materials are gone turbid by hydrofinishing and quilt.
18. according to claim 16 or 17 described methods, wherein said raw material comprises lubricant base stock, wherein said lubricant base stock combines with one or more lubricant additives to form lubricant.
19. method according to claim 1, the wherein said effectively reaction condition of Hydrodewaxing comprise that temperature is 232-399 ℃, pressure is 170-13891kPa, and liquid hourly space velocity (LHSV) is 0.1-5.0hr
-1, it is 89-1789m that gas speed is handled in Hour
3/ m
3
20. method according to claim 1, wherein said catalyst for hydrogenation de-waxing also comprise aluminium oxide or salic metal oxide binder.
21. method according to claim 1, wherein before Hydrodewaxing wax Fischer-Tropsch hydrocarbon, handle described catalyst with the hydrocarbon stream that contains one or more oxygenatedchemicals, the amount of described oxygenatedchemicals is at least 100wppm by oxygen, starts under the temperature that is lower than the Hydrodewaxing temperature.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US41695002P | 2002-10-08 | 2002-10-08 | |
| US60/416,950 | 2002-10-08 | ||
| US10/652,390 | 2003-08-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101072639A CN101072639A (en) | 2007-11-14 |
| CN100548485C true CN100548485C (en) | 2009-10-14 |
Family
ID=36926893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801011022A Expired - Fee Related CN100548485C (en) | 2002-10-08 | 2003-10-07 | The oxygenate treated dewaxing catalyst is to improve the productive rate of dewaxed product |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN100548485C (en) |
| ZA (1) | ZA200502510B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105728023B (en) * | 2014-12-08 | 2018-11-16 | 中国石油天然气股份有限公司 | Molecular sieve catalyst and preparation method for the reaction of fischer-tropsch wax hydroisomerizing |
| CN106669810A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Alkane isomerization catalyst and preparation method and application thereof |
-
2003
- 2003-10-07 CN CNB2003801011022A patent/CN100548485C/en not_active Expired - Fee Related
-
2005
- 2005-03-29 ZA ZA200502510A patent/ZA200502510B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN101072639A (en) | 2007-11-14 |
| ZA200502510B (en) | 2006-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5147178B2 (en) | Oxygenation of dewaxing catalyst for high yield dewaxing products | |
| AU769997B2 (en) | Process for the reactivation of sulfur deactivated cobalt titania catalyst | |
| JP2011206649A (en) | Hydrogenation isomerization catalyst, method of producing the same, method of dewaxing hydrocarbon oil, method of producing hydrocarbon and method of producing base oil for lubricant | |
| US8685231B2 (en) | Process for conversion of paraffinic feedstock | |
| CA2285060C (en) | Processes, and catalyst for upgrading waxy, paraffinic feeds | |
| CA2498926C (en) | Oxygenate treatment of dewaxing catalyst for greater yield of dewaxed product | |
| CN100548485C (en) | The oxygenate treated dewaxing catalyst is to improve the productive rate of dewaxed product | |
| CN100428994C (en) | Oxygenate treatment of dewaxing catalyst for greater yield of dewaxed product | |
| JP2002503753A (en) | Manufacturing method of base oil for lubrication | |
| KR20230110653A (en) | Catalyst system for dewaxing | |
| JP4796508B2 (en) | Hydroisomerization using sulfurized catalyst |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091014 Termination date: 20201007 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |