CN1158377C - Dewaxing process - Google Patents

Abstract

The process of the invention for converting a hydrocarbon oil includes the following steps: (1) contacting a hydrocarbon oil feedstock in the presence of added hydrogen gas with a catalyst selected from the group consisting of a SAPO-11, SAPO-31 or SAPO-41 intermediate pore size silicoaluminophosphate molecular sieve and a hydrogenation component, and mixtures thereof, wherein at least a portion of the feedstock is converted; and (2) passing at least a portion of the converted feedstock to a fractionator, wherein at least a portion of the converted feedstock is fractionated, thereby producing at least one overhead fraction and one bottoms fraction; and (3) mixing at least a portion of the bottoms fraction with the hydrocarbon oil feedstock in step (1).

Description

Process for dewaxing

Invention field

The present invention relates to make the method for lubricating oil catalytic dewaxing.More precisely, this invention relates to the method that makes hydrocarbon oil feed dewaxing, wherein is recycled in the charging to small part separation column bottom product.

Background of invention

The method of some petroleum distillate dewaxing is known.When high paraffin oil was used at low temperatures, it must be a for example lubricating oil of mobile product, in the time of in oil fuel and the jet fuel, just needed dewaxing.The positive structure of higher molecular weight straight chain, that replace and the low side chain paraffinic hydrocarbons that is present in this oil is a wax, and this wax can cause the high pour point and the high cloud point of oil.If obtain enough low pour point, just must be fully or partly remove dewax.In the past, used all kinds of SOLVENTS to remove technology to remove these wax, such as propane dewaxing and methyl-ethyl-ketone dewaxing; Yet the process cost height of these technology, serious environmental influence and generation quality are inferior to the oil of catalysis-pressed oil.Catalytic dewaxing process is more economical, and removes dewax by selectivity isomerization and cracking paraffinic components, generation low molecular weight product, and wherein some low molecular weight product can be removed by distillation.

Because their selectivity, known dewaxing catalyst generally includes the aluminosilicate zeolites with following aperture, this aperture only receivability straight chain n-paraffin or therewith only be the paraffinic hydrocarbons of low side chain, but get rid of the material of higly branched chain more, big cycloaliphatic compounds and aromatic hydrocarbons.Advised for example ZSM-5 of zeolite, ZSM-11, ZSM-12, ZSM-23, ZSM-35 and ZSM-38 are used for process for dewaxing.The application of these zeolites is described in United States Patent (USP) 3,700,585; 3,894,938; 4,176,050; 4,181,598; 4,222,855; In 4,229,282 and 4,247,388, the content of these patent disclosures is incorporated herein by reference.

Because the many process for dewaxing with this function are by cracking reaction, therefore many useful product degradation become low molecular weight substance.For example, the paraffinic hydrocarbons of the content of wax can be cracked into butane, propane, ethane and methane, and they are the inoperative lighter n-paraffin of wax shape character to oil.Have lower value because these light products compare the high-molecular weight material usually, therefore need the cracking degree that takes place during the restriction catalytic dewaxing process.

European patent application 225,053 discloses a kind of method of producing lubricating oil, and this method comprises by isomerization dewaxing comes the basis charging of part dewaxing lubricant, then selects the dewaxing step.This isomerization dewaxing step used macropore supersiliceous zeolite dewaxing catalyst, such as high-silicon Y-Zeolite or β zeolite, these catalyzer make the content of wax component in the basic charging be isomerizated into side chain isoparaffin into the low content of wax.Selectivity dewaxing step or can be solvent dewaxing, for example methyl-ethyl-ketone dewaxing operation perhaps can be catalytic dewaxing, preferably uses the highly selective zeolite such as ZSM-22 or ZSM-23.

United States Patent (USP) 4,437,976 disclose two sections hydrocarbon dewaxing hydroprocessing processs, wherein by in the presence of zeolite catalyst, making the charging catalytic dewaxing, liquid portion is through hydrogenation at least to make it then in the presence of hydrotreating catalyst, and reducing boiling point is the pour point of 400-1050 hydrocarbon charging, and wherein said hydrotreating catalyst contains hydrogenation component and is selected from ZSM-5, ZSM-11, the siliceous porous crystalline material of ZSM-23 and ZSM-35 zeolite.

People's such as Chester United States Patent (USP) 4,575,416 discloses a kind of Hydrodewaxing method, and this method has been used to be had restricted index and be not less than 1, have second catalyst component of regulation character and first zeolite catalyst of hydrogenation component.

United States Patent (USP) 5,149,421 have proposed a kind of dewaxing catalyst, and this catalyzer provides the fine selectivity to the product characteristics that obtains in the process for dewaxing.By use intermediate pore size silicoaluminophosphamolecular molecular sieve catalyzer in process for dewaxing, hydrocarbon oil feed is dewaxed effectively, and the product that obtains has higher molecular weight than the product that uses other aluminosilicate zeolites to obtain.Compare with the prior art of above-mentioned use aluminosilicate zeolites, the product that is obtained by process for dewaxing has better viscosity and viscosity index under given pour point.

Yet, a kind of like this method advantageously is provided, this method provides the yield higher than currently known methods, and the reduction value of pour point has been increased.The present invention just provides such method.

Summary of the invention

The present invention has overcome these problems of the prior art and shortcoming, and the method for hydrocarbon ils catalytic dewaxing is provided, and this method has produced excellent lubrication oil yield.

The method that the present invention transforms hydrocarbon ils comprises following step: (1) is in the presence of the hydrogen that adds, hydrocarbon oil feed is contacted with catalyzer, this catalyzer is selected from SAPO-11, the intermediate pore size silicoaluminophosphamolecular molecular sieve of SAPO-31 or SAPO-41 and a kind of hydrogenation component and composition thereof have wherein transformed to the small part charging; (2) make the charging that transforms to small part by separation column, the charging that fractionation to small part has transformed in separation column, thus produce at least a overhead fraction and a kind of tower bottom distillate; (3) make to the small part tower bottom distillate and mix with the hydrocarbon oil feed of step (1).

The accompanying drawing summary

Fig. 1 has described the simplified flow chart of an embodiment of the inventive method.

                     Detailed Description Of The Invention

A. the step of method

The method that the present invention transforms hydrocarbon ils comprises following step: (1) is in the presence of the hydrogen that adds, hydrocarbon oil crude material is contacted with catalyst system, this catalyst system comprises and is selected from SAPO-11, the catalyst of the intermediate pore size silicoaluminophosphamolecular molecular sieve of SAPO-31 or SAPO-41 and a kind of hydrogenation component and composition thereof has wherein transformed at least part of charging; (2) make at least part of charging that has transformed by fractionating column, at least part of converted feed of fractionation in fractionating column, thus produce at least a overhead fraction and a kind of tower bottom distillate; (3) at least part of tower bottom distillate is mixed with the hydrocarbon oil feed of step (1).

Catalyst system also randomly comprises the catalyzer that is selected from intermediate pore size aluminosilicate zeolite catalyst, amorphous catalyst and composition thereof.For carrying out pre-treatment, this charging can be carried out hydrocracking or solvent extraction and hydrotreatment.These class methods and typical hydrocracking condition are described in the United States Patent (USP) 4,921,594 of the Miller that authorizes May 1 nineteen ninety, and this patent all is incorporated herein by reference.Aftertreatment can comprise following hydrofining.

Be not limited by theory, in one embodiment, dewaxing mechanism is the isomerization and/or the cracking of waxy compound.Usually, compare with solvent dewaxing, the catalytic dewaxing for example ISODEWAXING catalytic dewaxing process of Chevron has improved the pour point and the viscosity index of charging.

B. charging

The inventive method can be used for making various hydrocarbon oil feed dewaxings, is categorized as any waxy hydrocarbon charging usually, lube oil feedstocks, or intermediate oil.Charging comprises distillate, isocrackate for example, and the high boiling point lube stock is such as deasphalted oil and solvent extraction oil.Charging normally boiling point is higher than about 350 C ₁₀+ charging is not because lightweight oil contains a large amount of content of wax components usually.Yet it is useful especially that this method is used following raw materials according, and these raw materials comprise for example intermediate oil of distillate material, comprise gas oil, kerosene, and jet fuel, lube stock, oil fuel and its pour point and viscosity need remain on other distillates in certain specification limit scope.Usually, the boiling point of lube stock is higher than 230 ℃ (450 °F), more generally is higher than 315 ℃ (600 °F).

Hydrogen is handled the suitable source that oil plant is this oil plant and other distillates, because they contain the hydrogen richness higher than solvent treatment oil plant, and do not have heteroatoms (for example sulphur and nitrogen compound) usually comparatively speaking, these heteroatomss can damage the performance of dewaxing and Hydrobon catalyst.The charging of present method is C normally ₁₀+ charging contains paraffinic hydrocarbons, alkene, cycloalkanes, aromatic hydrocarbons and heterogeneous ring compound and a large amount of high molecular n-paraffin and offer the low side chain of charging content of wax character and the paraffinic hydrocarbons of replacement.During processing, the charging molecule forms the liquid substance that can be used for the low viscosity product through some crackings or hydrocracking.Yet, limit the cracked degree that takes place, to keep the yield of valuable liquid.

Typical charging comprises light gas oil, and heavy gas oil and boiling point are higher than 350 long residuum.In one embodiment, charging contain main amount, boiling point is higher than about 350 hydrocarbon oil feed and contains straight chain and low branched-chain hydrocarbon.Term " main amount " is meant and surpasses 50 weight percentage.

Though the inventive method still can practical application when charging contains organonitrogen (nitrogenous impurity), the organonitrogen content in the preferred feedstock is more preferably less than 10ppmw less than 50ppmw.When charging contains less than the 10ppmw organonitrogen, during with activity of such catalysts and Cycle Length (time between cyclic regeneration or startup and the regeneration first time) expression, obtained good especially effect.

C. silicoaluminophosphamolecular molecular sieve catalyst composition

1. Overview:

Intermediate pore size silicoaluminophosphamolecular molecular sieve (SAPO) is the catalyzer that is used for the inventive method.Suitable SAPO is the medium hole SAPO of any routine.This SAPO is independent use, or is used in combination with zeolite and/or amorphous catalyst.The example that can be used for silicoaluminophosphamolecular molecular sieve of the present invention is described in United States Patent (USP) 4,440, and in 871 and 5,149,421, the content of these patent disclosures is incorporated herein by reference.

This intermediate pore size silicoaluminophosphamolecular molecular sieve catalyzer is used for the inventive method, becomes not content of wax component to transform content of wax component, and with about 30 to about 60 of their depression of pour point.The amount of used catalyzer depends on reaction conditions.

In a preferred embodiment, final catalyzer will be a composition, and it comprises the intermediate pore size silicoaluminophosphamolecular molecular sieve, platinum or palladium hydrogenation metal component and inorganic oxide matrix.Be applicable to that the preferred intermediate pore size silicoaluminophosphamolecular molecular sieve in the inventive method comprises SAPO-11, SAPO-31 and SAPO-41.Most preferred aluminosilicophosphate is SAPO-11, and most preferred metal component is a platinum, and most preferred tackiness agent is an aluminum oxide; SAPO-11, the description of SAPO-31 and SAPO-41 and preparation method thereof is published in above-cited patent and R.Szostak's " handbook of molecular sieves " (Van NorstrandReinhold 1992), 410-413,415-416, in the 419-420 page or leaf, the disclosed content of these documents is incorporated herein by reference.

2. Special preparation:

Molecular sieve can be stable combinations of materials to the temperature used in the process for dewaxing and other conditions with other.Such substrate material comprises the zeolite of active and inactive material and synthetic or natural formation and inorganic materials such as clay, silicon-dioxide and metal oxide.Inorganic materials can be natural formation or with gelatinous precipitate, colloidal sol or gel, comprise the form of the mixture of silicon-dioxide and metal oxide.Non-active material is suitable as tackiness agent or as thinner, with the formation number in the control process for dewaxing, so that need not use the method for other control speed of reaction just can obtain product economically.

Aluminosilicophosphate can for example wilkinite and kaolin combine with the clay of natural formation.These materials are that the effect of clay, oxide compound or the like is the tackiness agent of part as catalyzer.Be desirable to provide a kind of catalyzer with good crushing strength, because in refining of petroleum, this catalyzer often stands the big imposed stress in rash-and-rough way of loading and unloading and the reactor, catalyzer can be broken into the fragment that may stop up reactor like this.

Can comprise polynite and kaolin families with the clay of the natural formation of aluminosilicophosphate compound, this kaolin families comprises inferior wilkinite, and the normally said Dixie of this kaolin, McNamee, Georgia and Florida clay, or other essential mineral composition is halloysite, kaolinite, dickite, the kaolin of nakrite or anauxite.Fibrous clay for example halloysite, sepiolite and attapulgite also can be used as carrier.Such clay can use with the unprocessed state of initial recovery, perhaps begins just through calcination, acid treatment or chemical modification.

Except that above-mentioned material, this aluminosilicophosphate can with the porous matrix combination of materials, for example, the mixture of inorganic oxide matrix and substrate material is such as silicon-dioxide, aluminum oxide, titanium dioxide, magnesium oxide, silica-alumina, silica-magnesia, silicon-dioxide-zirconium white, silica-thorium oxide, silica-beryllia, silica-titania, titanium dioxide titania-zirconia and ternary composition be such as silica-alumina-Thorotrast, silica-alumina-titanium dioxide, silica-alumina-magnesium oxide and silica-magnesia-zirconium white.This matrix can exist with the form of cogelled or close physical mixture.

Be used for the inventive method silicon aluminium phosphate catalyst can also with other combination of zeolites, for example synthetic and natural faujusite, (for example X and Y type) erionite and mordenite.They can also with pure synthetic zeolite those combination of zeolites such as ZSM series.The mixture of zeolite can also with the porous, inorganic substrate combination.

D. Zeolite

The example that is used for the suitable aluminosilicate zeolite catalyst of the inventive method comprises ZSM-22, ZSM-23 and ZSM-35.These are taught in R.Szostak's " handbook of molecular sieves " (Van NorstrandReinhold 1992), and as seen, this patent is incorporated herein by reference and in United States Patent (USP) 4,481,177 at this paper in 538-542 and the 545-546 page or leaf; 4,076,842; With 4,016, as seen, the content of these patent disclosures is incorporated herein by reference at this paper in 245.

Silicoaluminophosphamolecular molecular sieve catalyzer and aluminosilicate zeolite catalyst can be used for the inventive method with the effective weight ratio of the intermediate pore size silicoaluminophosphamolecular molecular sieve that improves the converted feed yield and intermediate pore size aluminosilicate zeolites molecular sieve.Preferred weight ratio is about 1: 5 to about 20: 1.The zeolite that is used for this method is about 4 to about 12 at about 400 ℃-Yue 454 ℃ of restricted indexs of measuring down.

In another embodiment of the invention, SSZ-48, preferably hydrogen form can be used for process for dewaxing of the present invention.Without being limited by theory, think that SSZ-48 dewaxes by selecting to remove linear paraffins.Usually, when wax feed contacts with SSZ-48 under isomerization dewaxing (also being called Hydrodewaxing) condition, the viscosity index of dewaxed product be improved (comparing) with the solvent dewaxing charging.

When preparation SSZ-48 zeolite, the decahydroquinoline positively charged ion is as the crystallization template.This decahydroquinoline positively charged ion can have following array structure:

The negatively charged ion relevant with positively charged ion (X-) can be any negatively charged ion harmless to the formation of zeolite.Representational negatively charged ion comprises halogen, fluorine root for example, chlorine root, bromine root and iodine root, hydroxide radical, acetate moiety, sulfate radical, tetrafluoroborate, carboxylate radical or the like.Hydroxide radical is most preferred negatively charged ion.

Usually, SSZ-48 is that one or more are selected from following oxide compound and contact with decahydroquinoline positively charged ion template and prepare, and described oxide compound is selected from monovalent element oxide, dyad oxide compound, trivalent element oxide compound and quadrivalent element oxide compound.

SSZ-48 is prepared by the reaction mixture with the component shown in the following table 1.

Table 1

Reaction mixture

	Typically	Preferably
			YO 2/W aO b	10-100	15-40
OH-/YO 2	0.10-0.50	0.20-0.30
			Q/YO2	0.05-0.50	0.10-0.20
M 2/n/YO 2	0.01-0.10	0.03-0.07
			H 2O/YO 2	20-80	30-45

Wherein Y is a silicon, germanium or its mixture; W is an aluminium, gallium, iron, boron, titanium, indium, vanadium or its mixture; C is 1 or 2; D is 2 (, W is a quaternary) when c is 1, or d is 3 or 5 (, d is 3 when W is trivalent, d is 5 when W is pentavalent) when c is 2; M is alkali metal cation, alkaline earth metal cation or its mixture; N is the valency (that is, 1 or 2) of M; Q is at least one decahydroquinoline positively charged ion, and a is 1 or 2, and (, W is a tetravalence) b is 2 when a is 1, and (, W is a trivalent) b is 3 when a is 2.

In practice, SSZ-48 is prepared by following method, and this method comprises:

(a) prepare a kind of aqueous solution, this aqueous solution contains at least a oxide source that can form crystalline molecular sieve and has the anion balance ionic decahydroquinoline positively charged ion harmless to the formation of SSZ-48;

(b) keep this aqueous solution being enough to form under the SSZ-48 crystalline condition; With

(c) reclaim the SSZ-48 crystal.

Therefore, SSZ-48 can contain this crystalline material and template and bonded metal and nonmetal oxide, and this metal and nonmetal oxide are combined into tetrahedral coordination by the Sauerstoffatom of sharing, to form the three-dimensional space crystalline structure of cross bracing.This metal and nonmetal oxide comprise a kind of first tetradic oxide compound or its mixture, a kind of first tetradic second quadrivalent element or its mixture, trivalent element, pentad, or their mixture of being different from.This first quadrivalent element is preferably selected from silicon, germanium and composition thereof.More preferably, first quadrivalent element is a silicon.Second quadrivalent element (being different from first quadrivalent element), trivalent element and pentad are preferably selected from aluminium, gallium, iron, boron, titanium, indium, vanadium and their mixture.More preferably, second trivalent or quadrivalent element are aluminium or boron.

The typical case source that is used for the aluminum oxide of reaction mixture comprises aluminate, aluminum oxide, and the aluminium glue body is coated in the aluminum oxide on the silica sol, and alumina hydrate gel is Al (OH) for example ₃With aluminum compound AlCl for example ₃And Al ₂(SO ₄) ₃Typical silica source comprises silicate, silica hydrogel, silicic acid, fumed silica, colloided silica, tetraalkyl orthosilicate and silicon oxyhydroxide.Can be adding boron corresponding to their aluminium and the form of the homologue of silicon, and gallium, germanium, titanium, indium, vanadium and iron.

The zeolite reagent source can provide the source of aluminium or boron.In most of the cases, the zeolite source also provides the source of silicon-dioxide.With its dealuminzation or take off the zeolite source of boron form also can be as the source of silicon-dioxide, additional silicon uses the routine source of for example listing above.Use the zeolite reagent source to be described in the United States Patent (USP) 5 of the people's such as Zones that authorized on February 16th, 1993 denomination of invention more completely for present method for " preparation borosilicate zeolites " as the source of aluminum oxide, 187, in 132, the content of this patent disclosure is incorporated herein by reference.

Usually, in reaction mixture, use alkali metal hydroxide and/or alkaline earth metal hydroxides, sodium for example, potassium, lithium, caesium, rubidium, the oxyhydroxide of calcium and magnesium; Yet,, can save this component as long as kept the basicity that equates.Template may be used to provide hydroxide ion.Therefore, this is of value to ion-exchange, and for example, the halogen root exchanges hydroxide ion, thereby has reduced or eliminated the demand of alkali metal hydroxide.Alkali metal cation or alkaline earth cation can be the parts of synthetic crystallization oxide compound, so that balance valence electron electric charge wherein.

This reaction mixture keeps at high temperature, crystal formation up to the SSZ-48 zeolite.Hydrothermal crystallization under autogenous pressure, is between 100 ℃ and 200 ℃ in temperature usually, preferably carries out under between 135 ℃ and 160 ℃.Crystallization time is usually greater than 1 day, and preferred about 3 arrive about 20 days.

Preferably, this prepare zeolite is used mild stirring or stirring.

During the hydrothermal crystallization step, allow from reaction mixture this SSZ-48 crystal of nucleation naturally.Use the SSZ-48 crystal as crystal seed, can help reducing complete crystallization time necessary.In addition, seeding can improve by nucleation that promotes SSZ-48 and/or the degree of purity of production that generation obtains, and this purity surpasses any undesirable phase.When as crystal seed, SSZ-48 crystalline add-on is the 0.1%-10% that is used for the reaction mixture silica weight.

In case zeolite crystal forms, by the mechanical separation method of standard, for example filtration method is isolated solid product from reaction mixture.Wash this crystal, drying was for example descended dry 8-24 hour at 90 ℃-150 ℃ then, obtained synthetic SSZ-48 zeolite crystal.This drying step can carry out at barometric point or under vacuum.

Among the prepared SSZ-48, be selected from silicon oxide, a kind of oxide compound of germanium oxide and their mixture be selected from aluminum oxide, gallium oxide, ferric oxide, boron oxide, titanium oxide, Indium sesquioxide, the mol ratio of a kind of oxide compound of vanadium oxide and their mixture is greater than about 40; And x-ray diffraction line with following table 2.

Table 2

Synthetic SSZ-48

2θ (a)	d	Relative intensity (b)
			6.55	13.5	S
8.0	11.0	VS
			9.4	9.40	M
11.3	7.82	M-W
			20.05	4.42	VS
22.7	3.91	VS
			24.1	3.69	VS
26.5	3.36	S
			27.9	3.20	S
35.85	2.50	M

^(a)±0.3

^(b)The X ray picture that provides is based on the relative intensity grade, and wherein the numerical value of strong line in X ray picture is that 100:W (weak) is less than 20; M (medium) is between 20 and 40; S (by force) is between 40 and 60; VS (very strong) is greater than 60.

SSZ-48 also has a kind of composition, is synthetic and anhydrous state, represents with mol ratio, is presented at following table 3.

Table 3

Synthetic SSZ-48

YO ₂/W _cO _d 40-100

M _2/n/YO ₂ 0.01-0.03

Q/YO ₂ 0.02-0.05

Wherein Y is a silicon, germanium or its mixture; W is an aluminium, gallium, iron, boron, titanium, indium, vanadium or its mixture; C is 1 or 2; When c is 1 d be 2 (, W is a quaternary) or when c is 2 d be 3 or 5 (, d is 3 when W is trivalent, d is 5 when W is pentavalent); M is an alkali metal cation, alkaline earth metal cation or its mixture; N is the valency (that is, 1 or 2) of M; With Q be at least a decahydroquinoline positively charged ion.

A kind of method that improves the mol ratio of silicon-dioxide and boron is to use the acidleach of standard to get or the chelation treatment method.By using aluminium is inserted into method in the crystallization skeleton, also can obtains the ratio of lower silicon-dioxide and aluminum oxide.For example, with alumina adhesive or dissolved alumina source thermal treatment zeolite, just can insert aluminium.Such method is described in the United States Patent (USP) of authorizing in 17 days December in 1985 of people such as Chang 4,559,315, and the content of this patent disclosure is incorporated herein by reference at this paper.

Synthetic SSZ-48 zeolite has the as above crystalline structure of the X-ray powder diffraction spectrogram of its characteristic curve of displaying shown in the table 2, thereby makes it be different from other known zeolites.

After the calcination, the SSZ-48 zeolite has the crystalline structure of the X-ray powder diffraction spectrogram that comprises characteristic curve shown in the table 4.

Table 4

Incinerating SSZ-48

2θ ^(a) d Relative intensity ^(b)

6.55 13.5 VS

8.0 11.0 VS

9.4 9.40 S

11.3 7.82 M

20.05 4.42 M

22.7 3.91 M

24.1 3.69 M

26.5 3.36 M

27.9 3.20 W

35.85 2.50 W

^(a)±0.3

Measure the X-ray powder diffraction spectrogram with standard method.Radiation is the K-α/dipole (alpha/doublet) of copper.Peak height and position, as the function of 2 θ, wherein θ is a Bragg angle, is that the relative intensity from peak value reads, and can calculates d, corresponding to the interplanar spacing (dust) of registration line.

Because the difference between instrumental error and the individual sample, the variation of scattering angle (2 θ) size estimate at ± 0.30 degree.

The X-ray diffraction spectral characterization of above-mentioned table 2 " synthetic " or " preparation " SSZ-48 zeolite.Because the variation of lattice parameter, the silicon-dioxide ratio aluminum oxide of specific sample or silicon-dioxide can cause the less variation of diffraction pattern than the variation of the mol ratio of boron.In addition, very little crystal will influence the shape and the intensity of peak value, cause significant peak broadening.

The representational peak value of burnt SSZ-48 is presented in the table 4.Compare with the spectrogram of " preparation " material, calcination can also cause the Strength Changes of peak value, and the less displacement of diffraction pattern.With other different positively charged ions (H for example ⁺Or NH ₄ ⁺) metal that exists in the exchanging zeolite or other positively charged ions and the zeolite for preparing has produced identical in essence diffraction pattern, even once exchange, the variation of the displacement of interplanar spacing and the relative intensity of peak value also is less again.Although these less fluctuations are arranged, handle basic lattice by these and still remain unchanged.

Crystal SSZ-48 can use with the synthetic form, but preferably through Overheating Treatment (calcining).Usually, wish by ion-exchange and use hydrogen, ammonium, or any required metal ion is replaced and is removed alkali metal cation.Zeolite can be with for example ethylenediamine tetraacetic acid (EDTA) or dilute acid soln leaching of sequestrant, to increase the mol ratio of silicon-dioxide and aluminum oxide. and zeolite can also feed steam; Feeding steam helps the stable crystal lattice to avoid the corrosion of acid.

Be used for SSZ-48 of present method and any other zeolite, can combine with hydrogenation component nearly, such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or precious metal are such as with palladium or platinum, to be used for those application of requirement hydrogenation-dehydrogenation functionality.Preferably use platinum and palladium.

Can be by the ion exchange technique of standard, with metallic cation replace some positively charged ions in the zeolite metal is incorporated in the zeolite (referring to, the United States Patent (USP) of authorizing people's such as Plank 7 days July in 1964 3,140,249 for example, authorize people's such as Plank 7 days July in 1964 3,140,251 and the United States Patent (USP) 3,140 authorized in 7 days July in 1964 of people such as Plank, 253, the content of these patent disclosures is incorporated herein by reference at this paper).The typical positively charged ion of replacing comprises metallic cation, rare earths for example, IA family, IIA family and VIII family metal, and their mixture.In the metallic cation of replacing, preference such as rare earths, manganese, calcium, magnesium, zinc, cadmium, platinum, palladium, nickel, cobalt, titanium, aluminium, tin, the metallic cation of iron.

With catalytically-active metals be incorporated in the molecular sieve technology openly in the literature, existing metal adds technology and handles technology that molecular sieve forms active catalyst such as all being applicable to present method at the exchange of molecular sieve preparation process intermediate ion, dipping or the technology that absorbs.Such technology is disclosed in United States Patent (USP) 3,236,761; 3,226,339; 3,236,762; 3,620,960; 3,373.109; 4,202,996; In 4,440,781 and 4,710,485, the content of these patent disclosures is incorporated herein by reference.The amount of metal is about 0.01%-10% of zeolite weight, preferably about 0.2%-about 5%.

Hydrogen, ammonium and metal component can enter in the zeolite through ion-exchange.Also can use the metal impregnation zeolite, or metal and zeolite physically and nearly be mixed with the means known in the art of standard.

Typical ion exchange technique comprises makes synthetic zeolite contact with one or more cationic solution that contain the needs replacement.Though can use various salt, especially preferably use muriate and other halogenide, acetate, nitrate and vitriol.Before ion-exchange step, want calcined zeolite usually, to remove the organic substance that exists on passage and the surface, because obtained more effective ion-exchange like this.Typical ion exchange technique is disclosed in many patents, comprises the United States Patent (USP) of authorizing in 7 days July in 1964 of people such as Plank 3,140,249; The United States Patent (USP) 3,140,251 that authorize people's such as Plank 7 days July in 1964; The United States Patent (USP) 3,140,253 that authorize people's such as Plank 7 days July in 1964; The content of these patent disclosures is incorporated herein by reference at this paper.

After the cationic salts solution of needs exchange contacts, normally wash zeolite with water and descend dry for about 200 ℃ at 65-.After the washing, zeolite is in air or rare gas element, about 200 ℃-Yue 800 ℃ temperature lower calcination 1-48 hour or longer time, with preparation especially effective catalytic activity product in hydrocarbon conversion process.

Irrelevant with the positively charged ion that exists in the synthesized form of SSZ-48, the atom spatial disposition that forms the basic lattice of zeolite remains unchanged basically.

Hydrogenation component exists with the appropriate amount of preferred about 0.05-5 weight %, so that effective Hydrodewaxing and catalyst for hydroisomerizing to be provided.Catalyzer can be that the mode of cost is moved with the cracking reaction, to strengthen isomerization dewaxing (isodewaxing).

Any two kinds or the multiple zeolite that are used for present method can be with the form of layered catalyst as dewaxing catalysts.That is, catalyzer comprises the first layer and the second layer, and the first layer for example contains zeolite SSZ-48 and at least a VIII family metal, and the second layer contains another kind of aluminosilicate zeolites, for example has a kind of zeolite that multiform shape is more selected than zeolite SSZ-48 arbitrarily.The use of layered catalyst is disclosed in the United States Patent (USP) of authorizing in 22 days September in 1992 of people such as Miller 5,149,421, and this patent is incorporated herein by reference fully at this paper.Layering also can comprise and the stratified zeolite beds of non-zeolitic component that designs for hydrocracking or hydrofining, for example, and SSZ-48.Intimately mixed in this sense catalyst system has been represented another kind of useful variant, to replace layering.

E. amorphous catalyst

Being used for amorphous catalyst of the present invention is any amorphous catalyst that charging is had hydrogenation and/or isomerization.Such amorphous catalyst for example is taught in the United States Patent (USP) 4,383,913, and the content of this patent disclosure is incorporated herein by reference at this paper.

These catalyzer comprise, for example, and unbodied catalytic inorganic oxide, for example, catalytic activity silica-alumina, clay, the clay of synthetic or acid activation, silicon-dioxide, aluminum oxide, silica-alumina, silicon-dioxide-zirconium white, silica-magnesia, aluminum oxide-boron oxide, aluminum oxide-titanium dioxide, column or crosslinked clay, or the like with their mixture.

F. process conditions

This method is carried out under catalytic dewaxing condition.Such condition is known and is taught in for example following United States Patent (USP) 5,591,322; 5,149,421; With 4,181, in 598, the content of these patent disclosures is incorporated herein by reference.Catalytic dewaxing condition depends primarily on used charging and desired pour point.In catalytic dewaxing process, preferably there is hydrogen in the reaction zone.The ratio of hydrogen and charging that is to say the cycle rate of hydrogen, is generally about 500 to about 30,000SCF/bbl (standard cubic feet per barrel), and preferably about 1000-is about 20,000SCF/bbl.Usually, hydrogen and product are separated and be recycled to reaction zone.

The per-cent that is recycled to the separation column bottom product in the charging is the significant quantity that improves total recovery.Preferably, the per-cent of recirculation is about 100 for about 1-, or 10-about 50 more preferably from about.The ratio of separation column bottom product and raw feed is to reduce effective ratio that pour point does not lose yield or raising total recovery, keeps pour point simultaneously again.Preferably, this ratio is about 1: about 60: 100 of 100-, or more preferably from about 1: about 40: 100 of 100-.

The aluminosilicate zeolite catalyst of intermediate pore size and/or amorphous catalyst as the silicoaluminophosphamolecular molecular sieve catalyzer, can randomly be used for identical reactor, maybe can be used for a reactor that separates.When two kinds or multiple catalyzer were used for identical reactor, they are layering or mixing in order.When layering in order, this SAPO at random is first or the second layer.When two kinds or multiple catalyzer were used for identical reactor, they also can mix nearly.The catalyst bed configuration of any routine can be used for the inventive method.

The charging that isoversion step of the present invention can will dewax as requested and catalyst fixed bed, carry out with fixed fluidized-bed or moving-bed contacting.Therefore, a kind of simple and preferred configuration is the trickle bed operation, and wherein charging can spray by fixed bed, preferably in the presence of hydrogen.

Used catalytic dewaxing condition depends on used charging and required pour point.For different catalytic processs, some common process conditionss are presented in the following table 5:

Table 5
				Method	Temperature ℃	Pressure	LHSV
Hydrocracking	175-485	0.5-350 crust	0.1-30
				Dewaxing	200-475 (250-450)	15-3000 pound/square inch (200-3000)	0.1-20 (0.2-10)
Aromatic hydrocarbons forms	400-600 (480-550)	Normal atmosphere-10 crust	0.1-15
				Catalytic cracking	127-885	Be lower than a normal atmosphere -1(normal atmosphere-5 normal atmosphere)	0.5-50
Oligomerisation	232-649 2 10-232 4 (27-204) 4	0.1-50 normal atmosphere 2，3	0.2-50 2 0.05-20 5 (0.1-10) 5
				Paraffinic hydrocarbons generates aromatic hydrocarbons	100-700	0-1000 pound/square inch	0.5-40 5
The condensation of alcohol	260-538	0.5-1000 pound/square inch	0.5-50 5
				Isomerization	93-538 (204-315)	50-1000 pound/square inch	1-10 (1-4)
Xylene isomerization	260-593 2 (315-566) 2 38-371 4	0.5-50 normal atmosphere 2(1-5 normal atmosphere) 2The 1-200 normal atmosphere 4	0.1-100 5 (0.5-50) 5 0.5-50

¹A hundreds of normal atmosphere

²Gas-phase reaction

³Hydrocarbon partial pressure

⁴Liquid phase reaction

⁵WHSV

In the methods of the invention, usually, temperature is about 200 ℃-Yue 475 ℃, is preferably about 250 ℃-Yue 450 ℃.Pressure is generally about 15 pounds/square inch-Yue 3000 pounds/square inch, is preferably about 200 pounds/square inch-3000 pounds/square inch.Liquid hourly space velocity (LHSV) is 0.1-20 preferably, preferably about 0.2-10.

In catalytic isomerization process, in reaction zone, preferably there is hydrogen.It is about 30 that the ratio of hydrogen and charging is generally about 500-, 000SCF/bbl (standard cubic feet per barrel), and it is about 20 to be preferably about 1000-, 000SCF/bbl.Usually, hydrogen will separate and be recycled to reaction zone with product.

G. aftertreatment

Usually wish the hydrogenation (being called hydrofining sometimes) of used gentleness.The hydrofining step helps preparing suitable stable product (for example, lubricating oil), because unsaturated product tends to air and photo-labile and tends to degraded.The hydrofining step can be carried out after isomerization steps.Hydrofining is carried out under following condition usually: temperature is about 190 ℃-Yue 340 ℃, pressure is about 400 pounds/square inch-Yue about 3000 pound/square inches, air speed (LHSV) is that about 0.1-about 20 and hydrogen recirculation rate are the about 1500SCF/bbl of about 400-.

Used hydrogenation catalyst must not only have enough activity to alkene in the hydrogenation lubricating oil distillate and diolefine, and to reducing existing any aromatic hydrocarbons enough activity is arranged.

Suitable hydrogenation catalyst comprises the common metal hydrogenation catalyst, and particularly VIII family metal is such as cobalt, nickel, palladium and platinum.This metal usually and carrier such as bauxite, aluminum oxide, silica gel, silica-alumina composition and crystal type aluminosilicate zeolites and other molecular sieve combination.Palladium is particularly preferred hydrogenation metal.If necessary, base metal VIII family metal can use with molybdate.Can use metal oxide or sulfide.Appropriate catalyst is disclosed in United States Patent (USP) 3,852,207; 4,157,294; 4,921,594; In 3,904,513 and 4,673,487, the content of these patent disclosures is incorporated herein by reference at this paper.

Detailed description to accompanying drawing

Fig. 1 has described the simplified flow chart of an embodiment of the inventive method.Lube oil feedstocks logistics 5 and hydrogen stream 10 are fed catalytic dewaxing unit 15, for example, isomerization dewaxing (ISODEWAXING) catalytic dewaxing unit.The effluent 20 of catalytic dewaxing unit 15 is fed hydro-refining unit 25.The effluent 30 feeding atmospheric distillation towers 35 of hydro-refining unit 25 are carried out initial fractionation.Take out various product logistics from atmospheric distillation tower 35, for example, light gas logistics 36, naphtha stream 37, jet fuel logistics 38 and bottom stream 40.The bottom stream 40 feeding vacuum stills 45 of atmospheric distillation tower 35 are carried out further fractionation.Take out various product logistics from vacuum still 45, for example, 55, No. 100 neutral oil logistics 60 of 50, No. 60 neutral oil logistics of diesel-fuel logistics, and bottom stream (or No. 300 neutral oils) 65.The a part of bottom stream 65 that takes out is as No. 300 neutral oil logistics 70, and a part is by logistics 75 recirculation, mixes with fresh lube oil feedstocks logistics 5.

Illustrative embodiment

Further illustrate the present invention by the following example, these embodiment are in order to demonstrate the invention purely.

The verified benefit of separation column bottom product recirculation operation in extensive pilot plant test.For the driving of demonstrating, the isomerization dewaxing reactor is equipped with the SAPO-11 catalyzer of about 5,000 cubic centimetres precious metal dipping, and hydrofining reactor is equipped with the proprietary Hydrobon catalyst of about 5,000 cubic centimetres Chevron.Online distillation has produced 3 kinds of lubricating oil distillates and middle runnings.This pilot plant is configured to simulate process flow sheet shown in Figure 1.

Test 2 wide boiling point hydrocracking chargings.Detected value to these chargings is presented at table 6.After isomerization dewaxing and the hydrofining, whole product liquids are fractionated into 3 finished product base oil fractions-No. 60 neutral oils, No. 100 neutral oils and No. 300 neutral oils.Table 7 has been summarized recirculation part separation column bottom product and the improved performance that obtains.

For test 1 to 4, fresh feed speed is kept roughly constant, and the weighted average bed temperature (WAT) of the per-cent of separation column bottom product recirculation and isomerization dewaxing tower changes.At run duration hydrofining tower is roughly to operate under the constant temperature.

A. comparison test 1 and test 2 have shown when a large amount of separation column bottom product of recirculation, can reduce the WAT of isomerization dewaxing tower, though the dewaxing severity is slightly different under two kinds of situations, has remarkably improved total yield of lubricating oil-be increased to 80% from 70%.The difference that recirculation also is changed to the pour point of 100N and 300N between the pour point in very close to each other-test 2 is 18 ℃, and tests have only 9 ℃ in 1.This means and utilize recirculation, 100N is not dewaxed by transition and becomes the acceptable pour point of 300N.

B. testing 3 has reached and test 2 identical 300N pour points.Utilize recirculation (test 3), we can improve whole yield of lubricating oil 3% and improve the yield 4% of low pour point high value 100N.In addition, utilize recirculation to reduce the excessive dewaxing degree of 100N.

C. test 4 be with test 2 identical isomerization dewaxing tower weighted average bed temperatures under move, and in test 4, the charging of isomerization dewaxing tower contains 13 separation column bottom products (recirculation).Though total yield of lubricating oil is identical, the test 4 in, have 2% less than 300N and more than 2% 60N.The more important thing is that in test 4, the pour point of finished lube cut comes down to lower.Therefore, recirculation can improve the product performance of finished lube, and does not change total recovery.

For test 5 to 7, the per-cent of fresh feed speed and fractionator changes.In addition, the hydrofining tower is roughly to operate under the constant temperature.

A. for test 6, fresh feed speed has improved 23%, and without any recirculation.For keep above-mentioned near pour point at 300N, the WAT of isomerization dewaxing tower is essential to improve 5 °F, but (does not have recirculation) in this case, it is identical that total yield of lubricating oil keeps, and some raising (degenerating) a little of the pour point of lubricating oil distillate.

B. for test 7, keep fresh feed speed in fact, the charging of isomerization dewaxing tower contains 14% separation column bottom product.In this case, we can reduce isomerization dewaxing tower catalyst temperature a little, keep near above-mentioned product pour point simultaneously, and we see that total yield of lubricating oil has improved 2%.Perhaps the more important thing is that the yield of 100N improves 4%, and the 100N pour point there is decline a little.

Top comparing embodiment has shown, when recirculation part separation column bottom product, can obtain the unexpected performance of improving.To limit the quantity of accessible fresh feed at last because increase the recirculation volume of residue, restriction economically will be pointed out the maximum quantity of recirculation usually.

Table 6

The pilot plant test charging

Charging A charging B

Waxy nature

Api gravity 35.9 33.7

Nitrogen ppm 1.6 1.3

Sulphur, ppm 7.3 6.3

Aromatic hydrocarbons 6.04 7.7

Viscosity, cSt@

65C 9.110 11.766

100C 4.24 5.137

The viscosity index 121 118 of wax

Pour point, ℃ 39 39

Wax content, weight % 22.96 18.09

Distillation, °F

10％ 640 678

50％ 787 819

90％ 960 970

Solvent

Pressed oil

Viscosity, cSt@

40C 21.418 30.327

100C 4.306 5.309

Viscosity index 107 108

Pour point, ℃-18-21

Table 7

Pilot plant is summarized

Test charging combined feed total feed advances circulation % W.A.T. in the IDW 100N 300N sequence number LHSV material at reactor, pour point, and ℃ pour point, ℃	Gauged yield of lubricating oil, %
		60N 100N 300N amounts to
	1 charging A, 1.39 37 683-18-9 2 charging A, 1.03 0 700-31-13 3 charging A, 1.18 15 696-28-13 4 charging A, 1.17 13 700-33-18 5 charging B, 1.00 0 694-27-11 6 charging B, 1.23 0 699-25-10 7 charging B 1.11 14 689-30-9		27 39 14 80 24 31 15 70 24 35 14 73 26 31 13 70 17 39 25 81 18 40 23 81 19 44 20 83

Two kinds of chargings all help recirculation yield and/pour point.

Claims (39)

1. method that transforms hydrocarbon ils comprises:

(a) in the presence of the hydrogen that adds, hydrocarbon oil feed is contacted with catalyst system, this catalyst system contains a kind of intermediate pore size silicoaluminophosphamolecular molecular sieve and a kind of hydrogenation component, and wherein said charging is that lube stock and the described charging of at least a portion are transformed;

(b) charging that at least a portion has been transformed feeds separation column, the charging that wherein fractionation at least a portion is described have been transformed, thus produce at least a overhead fraction and a kind of tower bottom distillate; With

(c) at least a portion tower bottom distillate is mixed with the hydrocarbon oil feed of step (a), to improve the pour point of yield or reduction product.

2. according to the process of claim 1 wherein that described catalyzer is to be selected from SAPO-11, SAPO-31 or SAPO-41.

3. according to the process of claim 1 wherein that described catalyzer also comprises a kind of intermediate pore size aluminosilicate zeolite catalyst that is selected from, the catalyzer of amorphous catalyst and their mixture.

4. according to the method for claim 2, wherein said silicoaluminophosphamolecular molecular sieve comprises SAPO-11, and said hydrogenation component comprises platinum.

5. according to the method for claim 4, wherein said catalyst system mainly is made up of SAPO-11.

6. according to the process of claim 1 wherein that the amount of described hydrogenation component is 0.01%-10%, in the weight of molecular sieve.

7. according to the method for claim 2, wherein this catalyst system also comprises a kind of intermediate pore size aluminosilicate zeolite catalyst and mainly is the form of hydrogen.

8. according to the method for claim 7, wherein said catalyzer also comprises a kind of hydrogenation component.

9. method according to Claim 8, wherein said hydrogenation component comprise a kind of VIII family metal.

10. according to the method for claim 9, wherein said hydrogenation component is selected from platinum, palladium, and composition thereof.

11. according to the method for claim 7, the restricted index of wherein said intermediate pore size aluminosilicate zeolites is measured as 4-12 under 400 ℃-454 ℃.

12. according to the method for claim 7, wherein said intermediate pore size aluminosilicate zeolites is selected from ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, SSZ-48 and their mixture.

13. according to the method for claim 7, wherein said intermediate pore size aluminosilicate zeolite catalyst also contains to be selected from and comprises platinum, the VIII family metal of palladium and nickel and composition thereof, or comprise molybdenum, chromium, the group vib metal of tungsten and their mixture.

14. according to the method for claim 7, the weight ratio of wherein said intermediate pore size silicoaluminophosphamolecular molecular sieve and described intermediate pore size aluminosilicophosphate zeolite molecular sieve is 1: 5-20: 1.

15. according to the process of claim 1 wherein that described method is a process for dewaxing, wherein said contact is carried out under the dewaxing condition.

16. according to the method for claim 15, wherein said contact is carried out under following condition: temperature is 200 ℃-475 ℃, and pressure is 15 pounds/square inch-3000 pounds/square inch, and liquid hourly space velocity is 0.1 hour ^-1-20 hours ^-1With the hydrogen cycle rate be 500-30,000 SCF/bbl.

17. according to the method for claim 15, wherein the amount with described hydrocarbon oil feed blended separation column bottom product is the significant quantity that improves the yield of converted feed or reduced the pour point of converted feed.

18. according to the method for claim 17, wherein the separation column bottom product of 1 weight %-80 weight % mixes with hydrocarbon oil feed.

19. according to the method for claim 15, wherein the weight ratio with hydrocarbon oil feed blended separation column bottom product and hydrocarbon oil feed is the effective weight ratio that improves the yield of converted feed or reduce the pour point of converted feed.

20. according to the method for claim 19, wherein the weight ratio with hydrocarbon oil feed blended separation column bottom product and hydrocarbon oil feed is 1: 100-60: 100.

21. according to the process of claim 1 wherein that described hydrocarbon oil feed contains the organonitrogen less than 50ppmw.

22. according to the method for claim 21, wherein said hydrocarbon oil feed contains the organonitrogen less than 10ppmw.

23. according to the process of claim 1 wherein that described hydrocarbon oil feed is a content of wax bright stock.

24. method according to claim 1, wherein said hydrocarbon oil feed comprises the raffinate oil of lube range, wherein this method is a kind of method that makes the raffinate oil Hydrodewaxing, and the hydrogen that is included in adding exists down, raffinate oil is contacted with catalyst system.

25. method according to claim 1, wherein said hydrocarbon oil feed comprises the waxy hydrocarbon charging, wherein this method is, for conventional solvent dewaxing process, improved the method for viscosity index of the dewaxed product of waxy hydrocarbon charging, be included in catalyzer is contacted with the waxy hydrocarbon charging.

26. method according to claim 1, wherein the boiling point of the hydrocarbon oil feed of major portion is higher than 350 °F at least, and contain straight chain and slight branched-chain hydrocarbon, wherein this method is to make boiling point be higher than 350 °F and contain straight chain and the method for the hydrocarbon oil feed catalytic dewaxing of slight branched-chain hydrocarbon, the hydrogen that is included in adding exists down, be under 15-3000 pound/square inch and the dewaxing condition at hydrogen pressure, hydrocarbon oil feed is contacted with catalyst system.

27. according to the process of claim 1 wherein that this method is a kind of method for preparing lubricating oil:

(a) wherein said hydrocarbon oil feed be make hydrocarbon matter charging hydrocracking at hydrocracking zone, to obtain a kind of effluent that contains hydrocrackates; With

(b) wherein said contact procedure comprises, in the presence of temperature at least 200 ℃, pressure is 15 pounds/square inch one 3000 pounds/square inch and the hydrogen that adding, makes described effluent catalytic dewaxing with said catalyzer.

28. the method that hydrocarbon ils is dewaxed comprises:

(a) in the presence of the hydrogen that adds, lube oil feedstocks is contacted with catalyst system, this catalyst system contains a kind of intermediate pore size silicoaluminophosphamolecular molecular sieve and a kind of hydrogenation component, wherein in the weight of silicoaluminophosphamolecular molecular sieve, the amount of described hydrogenation component is 0.01%-10%, and contains a kind of zeolite that is selected from, amorphous catalyst, and composition thereof catalyzer, wherein at least a portion charging is dewaxed;

(b) at least a portion is dewaxed charging feeds a separation column, the described dewaxing charging of wherein fractionation at least a portion, thus produce at least a overhead fraction and a kind of tower bottom distillate; With

(c) tower bottom distillate of significant quantity is mixed with the hydrocarbon oil feed of step (a), with the yield that improves the dewaxing charging or reduce its pour point.

29. according to the method for claim 28, wherein said silicoaluminophosphamolecular molecular sieve comprises SAPO-11, hydrogenation component comprises platinum.

30. according to the method for claim 29, wherein said silicoaluminophosphamolecular molecular sieve mainly is made up of SAPO-11.

31. according to the method for claim 28, wherein said aluminosilicate zeolite catalyst also comprises a kind of VIII family metal hydrogenation component.

32. according to the method for claim 31, wherein said intermediate pore size aluminosilicate zeolite is selected from ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, SSZ-48 and their mixture.

33. according to the method for claim 28, the weight ratio of wherein said intermediate pore size silicoaluminophosphamolecular molecular sieve and described intermediate pore size aluminosilicophosphate zeolite molecular sieve is 1: 5-20: 1.

34. according to the method for claim 28, wherein said method is a process for dewaxing, wherein said contact is carried out under the dewaxing condition.

35. according to the method for claim 34, wherein said contact is to carry out under following condition: temperature is 200 ℃-475 ℃, and pressure is 15 pounds/square inch-3000 pounds/square inch, and liquid hourly space velocity is 0.1 hour ^-1-20 hours ^-1With the hydrogen cycle rate be 500-30,000SCF/bbl.

36. according to the method for claim 28, wherein the separation column bottom product of 1 weight %-80 weight % mixes with hydrocarbon oil feed.

37. according to the method for claim 36, wherein the weight ratio with hydrocarbon oil feed blended separation column bottom product and hydrocarbon oil feed is 1: 100-60: 100.

38. according to the method for claim 28, wherein said hydrocarbon oil feed contains the organonitrogen less than 50ppmw.

39. the method that hydrocarbon ils is dewaxed comprises:

(a) be that 200 ℃ of-475 ℃ of temperature, pressure are that 15 pounds/square inch-3000 pounds/square inch, liquid hourly space velocity are 0.1 hour in temperature ^-1-20 hours ^-1With the hydrogen cycle rate be 500-30, under the condition of 000SCF/bbl, in the presence of the hydrogen that adds, the lube oil feedstocks that contains less than the 50ppmw organonitrogen is contacted with catalyzer, this catalyzer mainly is made up of the SSZ-32 zeolite catalyst of a kind of SAPO-11 intermediate pore size silicoaluminophosphamolecular molecular sieve and a kind of hydrogenation component and a kind of VIII of containing family metal hydrogenation component, wherein, weight in silicoaluminophosphamolecular molecular sieve, this hydrogenation component amount is 0.01%-10%, wherein the weight ratio of SAPO-11 and SSZ-32 is 1: 5-20: 1, and wherein the described charging of at least a portion is dewaxed;

(b) charging that at least a portion has been dewaxed feeds separation column, the described dewaxing charging of wherein fractionation at least a portion, thus produce at least a overhead fraction and a kind of tower bottom distillate; With

(c) the dewaxing charging with the tower bottom distillate of 1 weight %-80 weight % contacts with the hydrocarbon oil feed of step (a).

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