CN1128860C - Integrated lubricant upgrading process - Google Patents

Abstract

The present invention relates to a modification method of raw oil containing more than 50% of straight run oil. In the method, firstly, the raw oil is hydrocracked to adjust the hydrogen content thereof, and the raw oil is evaporated in a flash mode and/or distilled; secondly, residual oil is distilled at reduced pressure to adjust the viscosity and the volatility thereof; thirdly, a refined raw material is dewaxed with mesopore zeolite, such as HZSM-5, or a mesoporous molecular sieve at high pressure; fourthly, the dewaxed material is connected with a hydrorefining step in series to contact hydrogen and an effective aromatic saturation catalyst having the function of metal hydrogenation at the temperature between 230 DEG C and 330 DEG C (between 450 and 575 DEG F) so as to produce a lubricating oil product having the advantages of high viscosity index, low aromatic content, low volatility and high light stability in the presence of oxygen after proper flash evaporation and distillation, wherein the hydrogen and the effective aromatic saturation catalyst are jointly added. A plurality of steps are contained in the hydrocracking step, the dewaxing step and the hydrorefining step.

Description

Integrated lubricant upgrading process

The present invention relates to the hydrocracking of petroleum and catalytic dewaxing thereafter.More particularly, the present invention relates to a kind of fuel hydrogen processing scheme of associating, this scheme comprises hydrocracking, distillation, catalytic dewaxing and hydrofining step.Production improves viscosity Z exponential stability, color and than the dewaxed product of low volatility.Hydroeracking unit has increased the hydrogen richness of hydroeracking unit charging, has reduced viscosity and has reduced boiling spread.Catalytic dewaxing unit is the isocrackate of cracking and/or this content of wax of hydroisomerization optionally.Hydro-refining unit makes aromatic hydrocarbons and hydrogenation of olefins.It has reduced the ultraviolet light absorbing of pressed oil.Adjust volatility with distillation.The lubricant base product that generates is water white, and it has cold flow performance, high viscosity index (HVI), low volatility and the fabulous oxidative stability of low arene content, low pour point, improvement.

Use the various process for purification of the lube oil base stocks that directly obtains suitable boiling point, viscosity, pour point, viscosity index (VI), stability, volatility and other characteristic, obtain mineral oil lubricating oil from various crude oil materials.Usually,, then remove unwanted aromatic component by solvent treatment by distilling the crude oil at normal pressure and vacuum still, at last by dewaxing and various purification step, can be from this oil base stock of crude production.Because the polycyclic aromatic hydrocarbons component causes thermostability and light stability, the color of difference and the viscosity index of extreme difference of difference, so do not wish to use the crude oil or the pitch type crude oil of low hydrogen content, because isolate a large amount of aromatic component contained in the lube stock from such crude oil after, the productive rate of acceptable lube stock will be extremely low.Therefore, paraffinic base and naphthenic base crude are preferred, still, need contain the raw material of polycyclic aromatic hydrocarbons with the aromatic hydrocarbons disposal methods, so that remove the aromatic component that does not meet the requirements.

Under the lubricating oil distillate situation, generally refer to neutral oil, for example heavy neutral oil and light neutral oil or the like can use solvent for example furfural, N-N-methyl-2-2-pyrrolidone N-, phenol or other other chemical that optionally extracts aromatic component, can extract aromatic hydrocarbons by solvent extraction.If lube stock is the residual oil lube stock, at first to remove bituminous matter in the propane deasphalting step, follow the aromatic hydrocarbons of solvent extraction remnants, so that produce the lubricating oil that generally is called bright stock.But, under each situation, need the dewaxing step usually, under cryogenic influence so that make lubricating oil have satisfied low pour point and low cloud point, so that not too soluble alkane component does not solidify or do not precipitate.

Can produce the lubricant base of high viscosity index (HVI) (VI) by oil at the bottom of the fabricate fuel hydroeracking unit tower.This scheme provides produces that to have VI be 115 or the potentiality of higher oil base stock.Oil fuel hydrocracking scheme of the present invention has not only been improved VI, and provides a kind of and satisfy about than the oil base stock of the low volatility method of the new international rule of ILSAC GF-2 for example.The volatility condition of this new proposition need be removed than common resulting lubricating oil distillate lubricating oil distillate light, that boiling point is lower in the reduced pressure distillation process of preparation lubricant base, and this can increase their viscosity.Therefore, also must in distillatory technology, remove material higher, viscosity higher, so that keep viscosity.General this can cause lower yield and narrower lubricant base oil fraction, and this can increase their viscosity.As described herein, because the material of non-lube range turns back to the hydrocracking tower as circulation (perhaps leading to the second hydrocracking tower), thus at the bottom of the hydrocracking tower distillation of oil by remove the component that do not meet the requirements for example polycyclic aromatic hydrocarbons also can improve the processing property and the efficient of hydrocracking tower.Then, can be resulting lubricating oil distillate catalytic dewaxing, hydrotreatment, distillation then is with the lube product that manufactures a finished product.

At U.S.P.4, disclose among 983,273 (Kennedy etc.) and had partially liq round-robin oil fuel method for hydrogen cracking.In the method, in hydrotreating reactor, process charging (normally vacuum gas oil (VGO)) or light cycle oil (LCO), in hydrocracking reactor, process then, then enter separation column.Oil circulation at the bottom of the part separation column then to the hydrocracking tower.But oil did not carry out additional hydrotreatment or hydrocracking then to additional underpressure distillation step at the bottom of it resembled and proposes separation column the present invention.

Yukong Limited discloses (a kind of method of producing high-quality lubricant base from the unconverted oil (UCO) of the oil fuel hydrocracking tower operated in the round-robin mode of International Application PCT/KR94/00046).As in the present invention, use vacuum distillation apparatus after the fractionation.The various UCO cuts that obtain from vacuum distillation apparatus (UCO) are recycled to the reactor of hydroeracking unit then.In the present invention, any cut of vacuum distillation apparatus can be recycled to the first hydrocracking tower, leads to the second hydrocracking tower, even or enters FCC apparatus.The cut that vacuum distillation apparatus obtains does not need to be recycled to the hydrocracking tower.The application of Yukong is not open must operation fuel hydrocracking tower, has oil at the bottom of the waxy fuel hydrocracking tower of suitable hydrogen richness with production, so that obtain having the oil base stock of the dewaxing of VI at least 115 thereafter.Also claimed general dewaxing of Yukong and stabilizing step, still, it does not have to introduce or claimed specific catalytic dewaxing of the present invention and hydrotreatment technology thereafter.

For producing the lubricating oil oil plant, the method for catalytic dewaxing becomes more favourable.These methods relatively have many advantages with the method for the solvent dewaxing of routine.The method of operation catalytic dewaxing, the optionally positive structure of cracking and the waxy hydrocarbon of side chain a little, the product of production lower molecular weight, this product can be removed from the lube stock of higher by distillation then.Side by side, with identical or different catalyzer, the selectivity catalytic cracking of content of wax molecule, isomerization, the straight-chain molecule that can transform obvious amount becomes the branched-chain hydrocarbon structure of the cold flowability with improvement.Usually use thereafter hydrofining or hydrotreating step, stablize this product by the alkene of the saturated lubricating oil boiling spread that produces by the optionally hydrocracking that in dewaxing technique, takes place.For the introduction of these methods, with reference to U.S.P.3,894,938 (Gorring etc.), 4,181,598 (Gillespie etc.), 4,360,419 (Miller), 5,246,568 (Kyan etc.) and 5,282,958 (Santilli etc.).Hydrocarbon Processing (1986.9) relates to Mobile lubricating oil dewaxing method, this method also is presented in " Industrial Application of Shape-Selective Catalysis " Catal.Rev.-Sci.Eng.28 (283) of people such as Chen, among the 185-264 (1986), with reference to its further introduction to this method.Also referring to " Lube Dewaxing Technology andEconomics ", Hydrocarbon Asia4 (8), 54-70 (1994).

In such catalytic dewaxing process, along with the dewaxing round-robin carries out, the catalyzer inactivation that becomes gradually.For this is compensated, the temperature of dewaxing reactor improves gradually, so that satisfy the requirement of the target pour point of product.But, a restriction is arranged, the character of product, particularly oxidative stability become cannot accept before, its temperature can improve.For this reason, usually in ramp cycle technology as follows, operate WITH CATALYTIC DEWAXING TECHNIQUE, the low beginning of such round-robin (SOC) value is generally 232 ℃-274 ℃ (450 °F-525 °F), last loop ends (EOC) value is generally 354-385 ℃ (670-725 °F), thereafter, activate this catalyzer or this catalyzer of regenerating, so that carry out new circulation.Usually, can activate with hot hydrogen as the dewaxing catalyst of active ingredient with ZSM-5.Other dewaxing catalyst can with air or, come decoking with nitrogen or stack gas blended oxygen.The catalyzer that contains active ingredient, for example ZSM-23 or SAPO-11 (it is lower than the activity of such catalysts that contains ZSM-5, the temperature of its circulation beginning (SOC) and loop ends (EOC) than contain ZSM-5 the high 25-50 of temperature ℃).

Had to have introduced in dewaxing catalyst and used metal hydrogenation component as the means that meet the requirements very much, it is for the dewaxing circulation that obtains prolonging with in order to improve activation method, even dewaxing reaction itself is not the reaction that needs stoichiometric quantity equilibrated hydrogen.U.S.P.4,683,052 disclose the use noble metal component for example Pt or Pd for example Ni is good than using base metal for this purpose.For example at U.S.P.5,282,958,4,859,311,4,689,138,4,710,485,4,859,312,4,921,594,4,943,424,5,082,986,5,135,638,5,149,421,5, having introduced in 246,566,4,689,138 is used to dewax can contain the Pt of 0.1-0.6 (weight) % with the appropriate catalyst of isomerization or hydroisomerization raw material.In the present invention, the Pt of 0.2-1 (weight) % is preferred, though Pd also is an acceptable.

Close contact between chemical reaction between the liquid and gas reactant will obtain mutually is very difficult.When needed reaction is a catalyzed reaction and when needing two kinds of moving phases to contact with solid catalyst, such reaction is more complicated.Under situation operating routine and that flow heterophase reactor operation, gas and liquid are often by different flow path in some cases.Gas phase can flow in the direction of the pressure resistance of minimum, and liquid phase is to pass through by granules of catalyst with around granules of catalyst by the drip road by gravity.Under the situation of low liquid and gas ratio, parallel channel and gas friction may make liquid stream inhomogeneous, therefore, owing to lack suitable wettingly, just leave the part catalyst bed and utilize fully.Under these circumstances, the industrial reactor performance may be than far short of what is expected by the performance of breadboard result of study expection, and the flow condition in breadboard research in little pilot plant can be more uniform.

In the fractionation by crude oil from the refining of lubricating oils that oil obtains, can placed in-line catalyzed reaction be used for one or more catalyticreactor the lube stock component harshness hydrotreatment, conversion and remove desulfuration and nitrogen impurity, hydrocracking and isomerization.By the known polycyclic technology of opening, the optionally hydrocracking of polycyclic aromatic hydrocarbons raw material.Then under various reaction conditionss, with different catalyzer contact Hydrodewaxing and/or hydrogenation (mild hydrogenation processing).At people's such as Garwood U.S.P.4, three step lube oil finishing technologies of disclosed associating are suitable in the present invention in 283,271.

In a typical heterogeneous Hydrodewaxing reactor, under process conditions, be about 1 at the average gas-volume ratio of catalyst area: 4-20: 1.Preferably the speed with the 10-50% that occupies about void volume is added to liquid in the catalyst bed.When liquid starting material and gas during by reactor, because consumption reaction hydrogen, so the volume of gas may reduce.Form the steam that methane, ethane, propane and butane produce by the dewaxing reaction, adiabatic heating or expansion also can influence volume.

A kind of hydrocracking of high boiling point content of wax paraffinic base liquid petroleum lube stock and the improved integrated processes of Hydrodewaxing have now been found.In the fuel hydroeracking unit of the vacuum distillation apparatus that comprises the downstream, can be vacuum gas oil, light cycle oil even or deasphalted oil hydrocracking.Contain the catalytic dewaxing unit raw material of the hydrogen that is higher than about 13.5% (weight), its dewaxing, hydrofining and distillation then from the production of oil fuel hydroeracking unit.The feedstock conversion of at least 50% (weight) becomes boiling point to be lower than the hydrocarbon product of the initial boiling point of raw material.This improved method may further comprise the steps:

(a) raw material that comprises vacuum gas oil (VGO) or light cycle oil (LCO) or deasphalted oil is led to oil fuel hydrocracking system, therein, raw material is hydrotreatment under high pressure, hydrocracking under high pressure then, its aftercut, the product of meet the requirements viscosity and volatility is produced in residual oil underpressure distillation at the bottom of the separation column then;

(b) under the temperature of the rising that is up to 425 ℃ (797), in the presence of the common hydrogen that feeds, at least 10, the pressure of 000kpa (1450psi) with acid, select type, the mesoporous molecular sieve catalyst for hydrogenation de-waxing exists down, by distributing equably and contacting of liquid starting material can dewax stage with hydroisomerization simultaneously, by the cut fraction hydrogenation dewaxing that vacuum distillation apparatus obtains, the lubricating oil that obtains dewaxing;

(c) in the hydrofining stage, under the saturated condition of aromatic hydrocarbons, the aromatic hydrocarbon saturation catalyst of strong metal hydrogenating function contacts with effectively having very with the hydrogen of common feeding, with the lube hydrotreating of dewaxing.

The hydrofining temperature that use begins circulation (SOC) is 230 ℃ (446 °F)-343 ℃ (650 °F), pressure at least 10,000kpa (1450psi), the lube products that obtains dewaxing (boiling point is higher than about 370 ℃).After distillation thereafter, the aromaticity content of pressed oil is less than 5% (weight), and improved oxidative stability, ultraviolet light stability and thermostability.The NOACK number of this product is 20 or less than 20, VI is 115 or higher, is 3-10cst 100 ℃ viscosity.

Preferred catalyst for hydrogenation de-waxing comprises having the molecular sieve of mainly being made of the hole 10 Sauerstoffatoms of Siliciumatom replacement, the aluminosilicate zeolite that for example has ZSM-5, ZSM-23 or ZSM-35 or ZSM-48 structure.Other the non-zeolite molecular sieve with smaller aperture due for example SAPO-11 also is an appropriate catalyst.Except ZSM-5, desirable is the precious metal that this catalyzer contains 0.1-1% (weight).The preferred Hydrobon catalyst that will be used to dewax thereafter comprises VIIIA family metal and a kind of VIA family's metal (IUPAC) or Pt on porous solid carrier or the Pd at least a porous solid carrier.The bimetallic catalyst that contains nickel and tungsten metal on porous alumina carrier is good example.This carrier can be a fluorizated.

As mentioned previously, the preferred charging of fuel hydroeracking unit is a straight run gas oil, for example light vacuum gas oil (LVGO), vacuum gas oil (VGO) and heavy vacuum gas oil (HVGO).Usually, VGO and HVGO contain the polycyclic aromatic hydrocarbons of significant quantity.After hydrocracking and the underpressure distillation, want the common VI of content of wax material of catalytic dewaxing to be at least 125, preferred 130 or greater than 130, contain the aromatic hydrocarbons of about 1-15% (weight), the boiling point of 10% (body) is higher than about 315 ℃ (600 °F), and contains the nitrogen that is not more than 30ppm.Its hydrogen richness is greater than about 14.0% (weight).100 ℃ of its viscosity greater than 3cS.

Hydrofining and distillation are carried out in the logistics of Hydrodewaxing, separate then, and that reclaims that boiling point is higher than 370 ℃ (698 °F) is the lube products of 3-10cSt in 40 ℃ of kinematic viscosity (KV) for 10-160cSt or at 100 ℃.Less than 0.001L/g-cm (L represents and rises), aromaticity content is 5% (weight) or lower to this product lubricating oil in the UV of 325nm absorptivity.

Very advantageously, this dewaxing stage and hydrofining stage operate under same pressure basically, and the whole pressed oil logistics in dewaxing stage can directly be led to the hydrofining stage under the situation of tandem operation.

Description of drawings

Fig. 1 is the synoptic diagram that is applicable to oil fuel hydroeracking unit of the present invention.It comprises hydrotreatment tower, hydrocracking tower, separator, vacuum distillation apparatus and hydrofining tower.The unconverted material of fractionation plant can be recycled to the hydrocracking tower, perhaps can deliver to the vacuum distillation apparatus for catalytic dewaxing reactor cutting raw material of wanting suitable.

Fig. 2 is the simplified flow chart that the expression of expression main streams has the placed in-line vertical reactor of stationary catalyst bed.

Fig. 3 is that explanation is for the boiling point of pure component that obtains from Arabian light and vacuum gas oil and the relation between the viscosity.

Fig. 4 is that expression aperture, mesopore and large pore zeolite are the comparison diagram of the feature of molecular sieve.

Fig. 5-the 21st is for the various processing parameters of this improved method and the graphic representation of lube product product performance relatively.

Preferred reactor system is shown in Fig. 1 and 2.

In the following description, except as otherwise noted, unit all is a metric system.

I. raw material-the general introduction of integrated processes

The hydrocarbon feed of integrated processes of the present invention is a raw material of selecting to produce the lube range of the initial boiling point with lubricating oil of lube stock of proper lubrication performance and final boiling point.These raw materials mainly be 10% to distillate o'clock greater than 345 ℃ (653 °F), 100 ℃ viscosity be about 3-40cSt (as can with Fig. 3 and similarly relation determine) hydro carbons.This raw material normally cut of the crude oil of adequate types is produced by underpressure distillation.Usually will carry out air distillation to crude oil, normal pressure residue (residual oil for a long time boils) will carry out underpressure distillation, to produce initial unpurified lube stock.The reduced pressure distillate material that obtains from the propane deasphalting of vacuum residuum or " neutral material " and light expect to be used for producing the product of range of viscosities.General for light neutral oil, 100 ℃ viscosity can be 4cSt; For heavy neutral oil, 100 ℃ viscosity is about 12cSt; For bright stock, 100 ℃ viscosity is about 40cSt.In the solvent refined oil factory of routine, raw material is carried out solvent extraction, by use to the solvent of aromatic-selective for example furfural, phenol or N-methyl-pyrrolidone optionally remove aromatic hydrocarbons, improve their V.I. and other quality.For the present invention, before dewaxing and hydrofining, need carry out hydrocracking to raw material, so that obtain needed product performance.

By hydrocracking or harsh hydrotreatment, unpurified vacuum distillate and propane deasphalting (PDA) raffinate oil are made with extra care, transforming unwanted aromatic hydrocarbons and heterogeneous ring compound becomes naphthenic hydrocarbon and the paraffinic hydrocarbon that more meets the requirements.(referring to the following examples 3).The sulphur of these purified wax-containing mixtures and the content of nitrogen are low, as previously mentioned, can adjust its viscosity after the distillation.

At U.S.P.4,414,097 (people such as Chester), 4,283,271 (people such as Garwood), 4,283,272 (people such as Garwood), 4,383,913 (people such as Powell), 4,347,121 (people such as Mayer), 3,684,695 (people such as Neel) and 3, introduced full catalysis lubricating oil processing technology among 755,145 (Orkin) with the associating of hydrocracking and catalytic dewaxing.

II. hydrocracking step

The raw material of A. hydrotreatment/hydrocracking system

With boiling point all greater than about 340 ℃ heavy hydrocarbon feeds for example straight run light vacuum gas oil, heavy vacuum gas oil and deasphalting raffinate oil or their mixture operation hydrocracking process.Though these virgin oils are preferred,, for example light and heavy cracked gasoil of cracking stock and light and heavy FCC gas oil can be to be no more than 20% amount adding, because their hydrogen richness is low.(they are high aromatic hydrocarbons.) because lubricating oil usually is to sell according to their viscosity, and because hydrocracking reduces viscosity, so the raw material that joins hydroeracking unit must be 3cS or greater than 3cS 100 ℃ of kinematic viscosity that have preferably.This just means that preferred boiling spread is (referring to following Fig. 3, pure component that its expression obtains from Arabian light and 50% boiling point of vacuum gas oil and the relation between the viscosity) more than 340 ℃.Boiling point is lower than 340 ℃ raw material and can be included in the raw material of hydrocracking tower, but even their lighter product in separator 20, be removed.(referring to Fig. 1).These heavy oil comprise high molecular long chain alkane and high molecular naphthenic hydrocarbon and aromatic hydrocarbons.These aromatic hydrocarbons will comprise some condensed-nuclei aromatics, and it is disadvantageous to lubricating oil stability.In this course of processing, condensed-nuclei aromatics and naphthenic hydrocarbon are by an acidic catalyst cracking, and the alkane component of alkane crackate and initial feed just changes into low-molecular-weight material through certain cracking.Hydrogenation of polycyclic aromatic hydrocarbons is by hydrogenation component catalysis, and promotes the cracking of these compounds.The hydrogenation of the unsaturated terminal chain on the monocycle cracking resistates of primary polynuclear compound provides the mononuclear aromatics of replacement, and it is the final product that meets the requirements very much.The heavy-hydrocarbon oil raw material will contain the cut that a large amount of boiling points is higher than 340 ℃ (644) and is higher than 3cS 100 ℃ of viscosity usually.Its initial boiling point more generally is higher than about 450 ℃ (842 °F) usually above about 400 ℃ (752 °F).Boiling spread can be that 340-700 ℃ (644-1292 °F) is so wide.Certainly, can process the oil of narrower boiling spread, the oil of for example the about 400-500 of boiling spread ℃ (about 752-932).The normally such oil of heavy gas oil is as turning oil and other non-salvage stores.The turning oil of Hydrocarbon Content by Catalytic Cracking Operation (FCC) and the turning oil of coking operation are not suitable for being used for producing lubricating oil especially, because they are so highly unsaturated, but they can be blended in the above-mentioned virgin oil, as long as they satisfy desired same boiling point of virgin oil and viscosity.The charging of hydrocracking that suitable is does not contain and surpasses 20% cracking material.The charging of hydrocracking tower must contain 80% or the straight run component of volume more.

Use conventional hydrotreating catalyst to remove denitrification and sulphur, and aromatic hydrocarbons is saturated to naphthenic hydrocarbon, basically do not have the initial hydrocracking step of the variation of boiling spread will improve catalyst performance usually, and allow to use lower temperature, higher air speed, lower pressure or the combination of these conditions.Suitable hydrotreating catalyst generally contains metal hydrogenation component, and normally above-mentioned group vib or VIII family metal, for example cobalt-molybdenum, nickel-molybdenum, metal are loaded in non-acid basically porous support for example on silica-alumina or the aluminum oxide.These catalyzer are listed in table 1.

Table 1

Be applicable to the catalyzer of initial hydrotreating step

Seller's catalyst type

UOP HCH NiMo/A1203

Crossfield 594 NiMo/A1203

Crossfield 504-K NiMo/A1203

C riterion HDN60 NiMo/A1203

Criterion C-411 NiMo/A1203

Criterion C-424 NiMo/A1203

Acreon HR348 NiMo/A1203

Acreon HR360 NiMo/A1203

Akzo KF843 NiMo/A1203

The introduction of II.B preferred embodiment

Fig. 1 is the simple declaration figure of the preferred reactor assembly of oil fuel hydroeracking unit of the present invention.Use conventional hydrotreating catalyst to remove denitrification, sulphur and oxygen, and saturation of olefins and aromatic hydrocarbons, basically do not have the initial hydrocracking step of the variation of boiling spread will improve the hydrocracking catalyst performance usually, and allow to use higher air speed, lower pressure or the combination of these conditions.Suitable hydrotreating catalyst generally contains metal hydrogenation component, and normally VIII family and group vib metal, for example cobalt-molybdenum or nickel-molybdenum, metal are loaded in low tart porous support for example on silica-alumina or the aluminum oxide.Be applicable to that suitable industrial hydrotreating catalyst of the present invention comprises the catalyzer of carrying alumina nickel-molybdenum, for example UOPHCH, Crossfield 594 and Criterion HDN60 and USY carry the catalyzer of nickel-molybdenum, for example UOPHC-24.

Vertical reactor housing 10 is sealed with and is supporting the fixed porosu solid bed of overlapping placed in-line hydrotreating catalyst, as 12A-12E describes.The stock oil 6 that comprises the mixture arbitrarily of vacuum gas oil, light cycle oil, deasphalted oil or these oil mixes with hydrogen rich stream 8, is incorporated into reactor 10 after through 9 heating of suitable heating installation.This raw materials mixed and hydrogen rich stream pass through beds downwards.Though in this example, drawn 5 beds, more bed can have been arranged or 2 so few beds are arranged.By the method for any routine, for example divider tower tray 13A, 13B, 13C, 13D, 13E are distributed in liquid in each bed, and they are injected in liquid among catalyst bed laminar surface 12A, 12B, 12C, 12D, the 12E equably.General is incorporated into gas phase and liquid phase in the reactor under required inlet pressure and temperature.By adding rich hydrogen chilling gas 14A, 14B, 14C, 14D, pass through the heat exchange of the liquid in the flows outside loop perhaps arbitraryly, can adjust gas and fluid temperature between the beds, allow the temperature in any beds of independent control thus.Can use the liquids and gases logistics between static mixer 15A, 15B, 15C, 15D or other the suitable contact device mixed catalyst zone, comprise quench gas, so that obtain uniform temperature.

The outflow logistics 16 of hydrotreatment tower is by heat exchanger (not shown), separator 18 and stripping or fractionation apparatus 20, the logistics 22 of partitioning cycle gas and light converted product 24.By product NH3 and H2S are removed in these separation, otherwise it can make the hydrogenation catalyst in downstream poison.Sweeping gas logistics 28 generally will be extracted out from circulation gas, so that locate the lighter hydrocarbons product.Generally to use the gas scrubbing system (not shown), so that from circulating current, remove NH ₃And H ₂S.Add hydrogen make-up 26 and replenish hydrogen that consumes in the hydrotreatment reaction and the hydrogen that in gas and liquid product stream 28,24 and 30, washs.

Vertical reactor housing 34 is sealed with and is supporting the fixed porosu solid bed of overlapping placed in-line hydrocracking catalyst, as 36A-36E describes.Discuss below can be more than a kind of catalyzer or blended or the hydrocracking catalyst in dividing other bed.Hydrotreatment bottom product 30 mixes with hydrogen-rich gas 32, through being incorporated into hydrocracking reactor 34 after 33 heating of suitable heating installation.This raw materials mixed and hydrogen rich stream pass through beds downwards.Though in this example, drawn 5 beds, more bed can have been arranged or 2 so few beds are arranged.By the method for any routine, for example divider tower tray 37A, 37B, 37C, 37D, 37E are distributed in liquid in each bed, and they are injected in liquid among catalyst bed laminar surface 36A, 36B, 36C, 36D, the 36E equably.General is incorporated into gas phase and liquid phase in the reactor under required inlet pressure and temperature.By adding rich hydrogen chilling gas 38A, 38B, 38C, 38D, pass through the heat exchange of the liquid in the flows outside loop perhaps arbitraryly, can adjust gas and fluid temperature between the beds, allow the temperature in any beds of independent control thus.Can use the liquids and gases logistics between static mixer 39A, B, C, D or other the suitable contact device mixed catalyst zone, comprise quench gas, so that obtain uniform temperature.

Heat exchanger (not shown), separator 40 and fractionation apparatus 42 are passed through in the outflow logistics 38 of hydrocracking tower, the cut 46 of the hydrocracking of partitioning cycle gas logistics 44 and conversion.Sweeping gas logistics 50 generally will be extracted out from circulation gas, so that remove the lighter hydrocarbons product.Generally to use the gas scrubbing system (not shown), so that from circulating current, remove NH ₃And H ₂S.Add hydrogen make-up 48 and replenish hydrogen that consumes in the hydrocracking reaction and the hydrogen that in gas and liquid product stream 50 and 46, washs.A new feature of the present invention is that unconverted bottom product 52 goes to lubricating oil vacuum distillation apparatus 54.This additional distilation steps can make the various narrow lubricating oil distillate 56,58,60,62,64 of producing special viscosity (for example 60N, 100N, 150N) and volatility.Can produce the low volatility lube stock of VI at least 115.Though show 5 kinds of lubricating oil distillates, can be more than 5 kinds or 2 kinds of so few cuts.As shown in Figure 2, these lubricating oil distillates lead to WITH CATALYTIC DEWAXING TECHNIQUE from vacuum distillation apparatus 54.

In some cases, what meet the requirements is some unconverted hydrocracking bottom product 52 of circulation, and perhaps the cut of the not usefulness of this logistics is got back to hydrocracking tower 34 from vacuum distillation apparatus 56,58,60,62,64.This is shown in logistics 66.In addition, what meet the requirements is that these unconverted hydrocracking tower base streams are delivered to the second hydrocracking tower, delivers to FCC apparatus or sends to and make fuel.

How as described in the present invention table 3 and 4 (seeing the following examples 1) illustrates can obtain lube product by the hydrocracking tower by adding the lubricating oil vacuum distillation apparatus like that.

The II.c hydrocracking catalyst

Used catalyzer can be conventional hydrocracking catalyst in hydrocracking process of the present invention, and this catalyzer uses the acid large aperture zeolite in the porous support material that belongs to adding metal hydrogenation/dehydrogenation functionality.Operable concrete industrial hydrocracking catalyst comprises UOP HC-22 and UOPHC-24.They are the NiMo catalyzer that are loaded on the USY carrier.ICR209, the Chevron catalyzer that contains Pd on the USY carrier also can use.Table 2 has been listed suitable hydrocracking catalyst.In hydrocracking catalyst, by the unformed material of macropore for example aluminum oxide, silica-alumina or silicon oxide, perhaps by the wide aperture crystalline material, for example X zeolite, Y, ZSM-3, ZSM-18, ZSM-20 or zeolite beta provide acid function to preferred wide aperture aluminosilicate zeolite.Can use various positively charged ions and other form, the zeolite of the form of preferred higher stability is so that the loss of degradation resistant and the acid function ensued under the influence of the hydrothermal condition that is run in the technology of hydrocracking.Therefore, the form that improves stability is the large pore zeolite of rare earth exchanged for example, for example REX and REY, and for example the Y of dealuminzation or the mordenite of dealuminzation are preferred to be called super steady zeolite Y (USY) and high oxidation silicon zeolite.

Zeolite ZSM-3 is disclosed in U.S.P.3, and in 415,736, zeolite ZSM-18 is disclosed in U.S.P.3, and in 950,496, zeolite ZSM-20 is disclosed in U.S.P.3, and in 972,983, the description of these zeolites, their performance and preparation as a reference.Zeolite USY is disclosed in U.S.P.3, and in 293,192, RE-USY is disclosed in U.S.P.4, in 415,438.The hydrocracking catalyst that contains zeolite beta is disclosed in EP94827 and U.S.P.4, and in 820,402, the description of these catalyzer is with reference to these documents.

Preferred catalyzer comprise tackiness agent for example, silicon oxide, silica or aluminum oxide or other metal oxide for example magnesium oxide, titanium oxide, the ratio of tackiness agent and zeolite is generally 10: 90-90: 10, be more typically about 30: 70-70: 30 (weights).

Table 2

Be applicable to the catalyzer of dewaxing hydrocracking step before

Seller's catalyst type

UOP HC-24 NiMo/USY

Chevron ICR209 Pd/USY

Acreon HYC632 NiMo/ zeolite

Acreon HYC642 NiMo/ zeolite

Acreon HYC652 NiMo/ zeolite

Akzo Kc-2000 NiMo/ zeolite

Akzo Kc-2100 Pd/ zeolite

Criterion Z-703 NiW/ zeolite

Criterion Z-753 NiW/ zeolite

Criterion Z-763 NiW/ zeolite

II.D hydrocracking process condition

This hydrocracking process carries out being similar under those used conditions of conventional hydrocracking.The technological temperature that can use very easily is about 260-480 ℃ (500-896 °F), though will not use the temperature that is higher than 445 ℃ (833) usually, because the thermodynamics of the temperature hydrocracking reaction more than this point becomes very unfavorable.The general temperature of using is 315-425 ℃ (599-797 °F).Total pressure is generally 1200-3000psi (8274-20685kpa), will preferably be higher than the higher pressure of 1800psi (12600kpa) scope usually.This technology is operated in the presence of hydrogen, and the hydrogen dividing potential drop is 1200psig (8274kpa) at least normally.The ratio of hydrogen and hydrocarbon feed (hydrogen recycle ratio) is 2000-5000SCF/Bbl normally.(about 18-980n.l.l ^-1).The air speed of charging is 0.1-10LHSV (hr normally ^-1), preferred 0.5-5LHSV.Under the situation of low-conversion, the normal paraffin in the raw material will be turned to isoparaffin by isomery, but under the situation than the higher conversion of severe condition, isoparaffin will change into lighter material.

Raw material can carry out this conversion by touching with fixed stable catalyst bench grafting.A kind of simple configuration is the trickle bed operation, wherein allows the raw material drip by stationary bed (Fig. 1 has illustrated this situation).According to such configuration, desirable is to begin reaction with fresh catalyzer under moderate moisture, and certainly, temperature will raise when catalyst aging, to keep catalytic activity.For example, under the temperature that improves, can be by contacting with hydrogen, perhaps by this hydrocracking catalyst of regenerating that in the presence of the mixture of air, nitrogen and stack gas, burns.

III. WITH CATALYTIC DEWAXING TECHNIQUE (perhaps Hydrodewaxing or hydroisomerisation process)

Fig. 2 illustrates general embodiment of the present invention, but whether will limit the present invention.Vertical reactor housing 10 is sealed with and is supporting the fixed porosu solid bed of overlapping placed in-line dewaxing catalyst, as 12A-12C describes.The stock oil 6 that comprises content of wax liquid oils mixes with hydrogen-rich gas 8, is incorporated into reactor 10 after through 9 heating of suitable heating installation.This raw materials mixed and hydrogen rich stream pass through beds downwards.Though in this example, drawn 3 beds, more bed can have been arranged or 2 so few beds are arranged.By the method for any routine, for example divider tower tray 13A, 13B, 13C distribute liquid, and they are injected in liquid on catalyst bed laminar surface 12A, 12B, the 12C equably.General is incorporated into gas phase and liquid phase in the reactor under required inlet pressure and temperature.By adding rich hydrogen chilling gas 14A, 14B or, can adjusting gas and fluid temperature between the beds, allow the temperature in the arbitrary beds of independent control thus at random by the heat exchange of the liquid in the flows outside loop.Can comprise quench gas, so that obtain uniform temperature with the liquids and gases logistics between static mixer 15A, 15B or other the suitable contact device mixed catalyst zone.

As required, by the outflow logistics 24 of heat exchanger or stove 25 heating or cooling Hydrodewaxing reactor, and hydrofining reactor 30 is directly arrived in series connection.Vertical reactor housing 30 is sealed with and is supporting the fixed porosu solid bed of overlapping placed in-line Hydrobon catalyst, as 32A-32C describes.Long-pending the flowing downward of liquids and gases passed through beds.Though in this example, drawn 3 beds, more bed can have been arranged or 2 so few beds are arranged.By the method for any routine, for example divider tower tray 33A, 33B, 33C distribute liquid, and they are injected in liquid on catalyst bed laminar surface 32A, 32B, the 32C equably.General is incorporated into gas phase and liquid phase in the reactor under required inlet pressure and temperature.By adding rich hydrogen chilling gas 34A, 34B or, can adjusting gas and fluid temperature between the beds, allow the temperature in the arbitrary beds of independent control thus at random by the heat exchange of the liquid in the flows outside loop.Can comprise quench gas, so that obtain uniform temperature with the liquids and gases logistics between static mixer 35A, B or other the suitable contact device mixed catalyst zone.

The hydrofining tower flows out logistics 36 by heat exchanger (not shown), separator 40 and fractionation apparatus 42, partitioning cycle gas logistics 44, the cut 46 and the finished lube oil base stock 48 that transform.Sweeping gas logistics 50 generally will be extracted out from circulation gas, so that remove the lighter hydrocarbons product.Generally to use the gas scrubbing system (not shown), so that from circulating current, remove NH ₃And H ₂S.Add hydrogen make-up 52 and replenish hydrogen that consumes in Hydrodewaxing and the hydrotreatment reaction and the hydrogen that in gas and liquid product stream 50 and 46, washs.

For the continuous multi-stage reactor system that contacted by the agency of of gas phase and liquid phase and placed in-line porous catalyst bed, still, what meet the requirements can be the reactor configuration that has 2-5 bed that other will be arranged.Catalyst composition in all beds of each reactor can be identical, still, different catalyzer and reaction conditions is arranged also in notion of the present invention in the separated catalyst bed.According to the custom of normal chemical engineering,, can revise design and operation for special processing request.

For various catalytic dewaxings operation, particularly under the temperature that improves with the heavy oil of hydrogenous gas processing lube range, present technique can adopt.Use the industrial technology, particularly refining of petroleum of hydrogen, use and contain 10-30% (mole) or more impurity, be generally the impure gas of round-robin of lighter hydrocarbons and nitrogen.Such gas is available and is useful at this, particularly for high temperature hydrogenation dewaxing under the pressure that improves.

Advantageously, catalyst bed has the void volume part greater than 0.25.Use leafy object or cylinder extrusion thing, bead or the sheet of loose filling, provide suitable flow rate of liquid component, can obtain the gap of 0.3-0.5, to promote mass transfer and katalysis for even wetting catalyzer.The height of catalyst bed can be 2-6 rice.

In this technology, in the presence of hydrogen, the lube stock of the content of wax, it generally is the 321 ℃+raw material of (about 610+), be added in the mesopore pore size molecular sieve catalyzer with dewaxing and/or isomerization or hydroisomerization function, produce the product (ASTM D-97 or the method that is equal to be Autopour for example) of lubricating oil boiling spread of the dewaxing of low pour point.For general waxy feeds, the hydrogen feed speed at the dewaxing reactor top is about 267-534n.l.l. ^-1(1500-3000SCF/BBL).For the stability of the material of the lubricating oil boiling spread of the dewaxing in the logistics that improves dewaxing, usually carry out the hydrofining step.

The Hydrodewaxing processing condition

In general, when ZSM-5 is the activity of such catalysts component, under the temperature condition that improves, usually about 205-400 ℃ (401-752 °F), preferred 235-385 ℃ (455-725 °F) operates the WITH CATALYTIC DEWAXING TECHNIQUE step, and it depends on the severity of the needed dewaxing of target pour point that reaches product.When using the lower catalyzer of other activity, high 25-50 ℃ of the comparable ZSM-5 of temperature.

When the target depression of pour point of product, increase the severity of dewaxing technique by the temperature that increases reactor, so that increase the transformation efficiency of normal paraffin greatly, so, the relatively large in succession selective cracking process of passing through dewaxing catalyst of normal paraffin in raw material (wax) transforms, when generating boiling point and exceeding the lighter product of lubricating oil boiling spread, along with the general lube oil yield of reduction of product pour point will reduce.When depression of pour point, the V.I. of product also will reduce because high V.I. normal paraffin and a little the isoparaffin of side chain little by little transformed.

In addition, in the middle of dewaxing circulation, each increases dewaxing temperature, with the reduction of compensation owing to the catalyst aging catalyst activity.When temperature reaches about 400 ℃ (about 750 °F), when still preferred about 385 ℃ (725 °F),, circulate so will end dewaxing usually owing to the disadvantageous effect of viscosity under higher temperature and product stability.When ZSM-5 was active catalytic composition than low activity catalyst, these temperature can high 25-50 ℃.

By being reduced in the speed of sedimentation of coke on the dewaxing catalyst, hydrogen promotes to prolong life of catalyst.(" coke " is high carbonaceous hydrocarbon, and in dewaxing technique, it often accumulates on the catalyzer.) therefore, in the presence of hydrogen, general in about 2758-20685kpa hydrogen dividing potential drop (400-3000psia), preferred 9653-17238kpa (1400-2500psi), more preferably carry out this technology under the 1600-2200psi (11032-15169kpa), although also can use higher pressure.Hydrogen circulation rates generally is the 180-710 at the reactor inlet liquid feeding, normally 355-535n.l.l ^-1(1000-4000SCF/bbl, 2000-3000SCF/bbl usually) can add additional hydrogen at chilling point.Air speed changes according to the severity that raw material and needs reach the target pour point, still, for all catalyzer general be 0.25-5LHSV (hr ^-1), preferred 0.5-3LHSV.

Catalyst for hydrogenation de-waxing

Exploitation aspect zeolite technology in recent years provides one group of siliceous material of mesopore with qualification of similar pore structure.Preferred catalyst for hydrogenation de-waxing contains the porous acidic molecular sieve, the hole that this molecular sieve mainly is made up of by the Siliciumatom replacement 10 Sauerstoffatoms, for example aluminosilicate zeolite.In the middle of the zeolite of hole, the most important thing is ZSM-5, ZSM-23, ZSM-35 and ZSM-48 in these, it is for example Al, Ga or Fe and bronsted acid avtive spot synthetic of the metal by adding tetrahedral coordination in zeolite framework normally.For selecting the effect of type acidic catalyst, the mesoporous molecular sieve with the about 3.9-6.3 in aperture is favourable; But have the high silicon matter of one or more tetrahedron materials of different acidity or the advantage that crystalline molecular sieve can utilize central hole structure by use.These selecting property materials have at least one by contain useful silicon/or the 10-person of displaced 10 Sauerstoffatoms of atoms metal encircle the hole path of formation.

The catalyzer of having recommended for the type WITH CATALYTIC DEWAXING TECHNIQUE of selecting contains molecular sieve usually, and this molecular sieve has can be allowed or independent straight chain wax normal paraffin or the alkane that only has side chain a little enter, but gets rid of the material and the cycloalphatic hydrocarbon of higher side chain.Representational mesoporous molecular sieve is ZSM-5 (U.S.P.3,702,886), ZSM-11 (U.S.P.3,709,979), ZSM-22, ZSM-23 (U.S.P.4,076,842), ZSM-35 (U.S.P.4,016,245), ZSM-48 (U.S.P.4,375,573), ZSM-57 and MCM-22 (U.S.P.4,954,325) and SAPO-11 (U.S.P.4,859,311).ZSM-24 is the synthetic ferrierite.(see figure 4).The content of these patent disclosures is classified reference as at this.

The advantage that molecular sieve provides in catalytic dewaxing surpasses noncrystalline catalyzer.Molecular sieve is categorized into aperture, mesopore and macropore material widely, as shown in Figure 4.Ring by Sauerstoffatom fixes the aperture.Pore zeolite has 8-person and encircles opening, and mesopore zeolite has 10-person's system, and large pore zeolite has 12-person's system.The pore structure of catalyzer also can influence the catalytic dewaxing performance, and no matter its classification that has list or two-way channel and its passage to intersect.The pore zeolite of strict restriction is inoperative in lubricating oil dewaxing, because they only allow little normal paraffin to enter the duct.By contrast, large pore zeolite allows some nonselective cracking of lubricating oil component that needs, and makes lower than the resulting yield of mesopore zeolite.

HZSM-5 is a kind of in many mesopore zeolites, and it can select the shape dewaxing.Other example comprises ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48 and ZSM-57.The pore structure of ZSM-5 provides the reactant shape selective, reduces the trend of coking and has got rid of the balance of the nitrogenous poisoning of catalyst of main body.In the present invention, HZSM-5, Pt/ZSM-23, Pd/ZSM-23, Pt/ZSM-48 and the Pt/SAPO-11 with physical and chemical performance of suitable adjustment is preferred, because their channel system and aperture can make effectively dewaxing of oil at the bottom of the fuel hydrocracking tower.

Can use and have the coordination metal oxide and the silicon oxide mol ratio is 20: 1-200: 1 or higher suitable molecular sieve.For example for HZSM-5, advantageously use to have silicon oxide: alumina molar ratio about 25: 1-70: the silico-aluminate ZSM-5 of 1 routine, also can use though be higher than 70: 1 mol ratio.General zeolite catalyst components with bronsted acid site can be made up of silicon oxide, clay and/or alumina binder with the zeolite structured crystal aluminosilicate of ZSM-5 and 5-95% (weight) basically.Know, other mesopore acidic molecular sieve for example salicylate, aluminosilicophosphate (SAPO) material can be used as catalyzer, particularly mesopore SAPO-11.

U.S.P.4,908,120 (Bowes etc.) disclose a kind of catalysis process useful to the raw material with high paraffinicity or high nitrogen-containing.This method is used the zeolite dewaxing catalyst of binder free, preferred ZSM-5.

In this technology, mesopore zeolite is useful especially, because they have the life-span and the stability of good regenerability, length under extreme operational condition.The crystallographic dimension that common this zeolite crystal has is about 0.01 to surpassing 2 microns or bigger, and the 0.02-1 micron is preferred.For selective cracking, though can there not be the ZSM-5 (〉=40 α) of metallic forms with it, but under the situation of other above-mentioned mesopore acid metal silicate, necessary is that they will use 0.1-1.0% (weight) precious metal to improve, so that as the hydroisomerization dewax catalyzer.

ZSM-5 is best mesoporous molecular sieve, i.e. mesopore acidic molecular sieve, and it does not add precious metal, in fact is used for industrial selectivity dewaxing.In order to reduce catalyst aging speed, need precious metal and other mesoporous molecular sieve to practical level.But precious metal is added among the ZSM-5, makes it that the hydroisomerization activity be arranged, and this has just increased the yield of dewaxing lubricant.Have been found that when precious metal is added among ZSM-23, ZSM-35, SAPO-11 and the ZSM-5, for the general product yield of ZSM-23, ZSM-35 and SAPO-11 and VI than ZSM-5 height.Will with selection of catalysts become economic problems.

The catalyzer size can have very big variation range in notion of the present invention, it depends on processing condition and structure of reactor.Finished catalyst with average largest dimension 1-5mm is preferred.

Catalytic dewaxing condition

In the example of most of catalytic dewaxings herein, used catalyzer is to have 105 acid cracking (α) value, and 65% (weight) ZSM-5 that forms with the extrusion of 1.6mm diameter; But, can use the α value of about 1-300.Structure of reactor is the consideration of particularly important when the system of design operate continuously.In its simplest form, provide the vertical pressure vessel of the overlapping catalyst bed that placed in-line (at least 2) uniform section is housed.The ratio (L/D direction) that usually has total catalyst bed lengths and width is about 1: 1-20: 1 vertical reactor is preferred.Overlapping placed in-line bed can be placed in the same reactor shell, still, uses reactor vessel side by side separately can obtain similar result.The reactor of homogeneous cross section is preferred, still, also can use uneven structure, as long as suitable adjustment in bed velocity of flow and corresponding speed of circulation.

Be higher than at boiling point that the present invention is useful especially in the catalytic hydrodewaxing of non-refinable crude gas oil lube stock of 315 ℃ (599).Extruded catalyst bed with the mesothyrid molecular sieve catalyst of random filling is not more than 5hr in liquid hourly space velocity ^-1, preferably about 0.5-3hr ^-1Condition under can finish catalytic dewaxing and handle.The hydrocarbon feed that is added to the catalytic dewaxing tower is 3-12cSt 100 ℃ viscosity.Advantageously, for total input speed (comprising the optional liquid circulation), liquid flow velocity maintains 2441-17088, preferred 4882-14647kg/m ²/ hr (500-3500 pound/foot ²-hr, preferred 1000-3000 pound/foot ²-hr).With uniform volumetric velocity/every barrel of oil, add reactant gas.

IV. The catalytic dewaxing back end hydrogenation is refining

Quality for the lube products of improving dewaxing, carry out hydrofining step (see figure 2) after the catalytic dewaxing, so that the alkene of saturated lube range and remove heteroatoms, color bodies, if the sufficiently high words of hydrofining pressure, it can make remaining aromatic hydrocarbons saturated.Hydrofining after the dewaxing is usually to carry out with the placed in-line form of dewaxing step.Usually, in circulation beginning, hydrofining will be at about 230-330 ℃, and preferably 246-274 ℃, the temperature of most preferably 260-302 ℃ (450-625,475-600, most preferably 500-575) is carried out.Total pressure is typically 9653-20685kpa (1400-3000psi is arranged approximately).Liquid hourly space velocity in hydrotreating reactor is generally 0.1-5LHSV (hr ^-1), preferred 0.5-3hr ^-1

At U.S.P.4, use successive lubricating oil catalytic dewaxing-hydrorefined method is disclosed in 181,598,4,137,148 and 3,894,938.At U.S.P.4, the method for using the reactor that has other dewaxing-hydrofining bed is disclosed in 597,854.The detailed introduction of these methods is with reference to these patent documentations.The hydrofining step of dewaxing after the step improved the quality of product and do not influenced its pour point significantly.The metal function of Hydrobon catalyst is being effective aspect the saturated aromatic component.So hydrofining (HDF) catalyzer with very strong hydrogenating desulfurization/hydrogenating function that can be provided by precious metal, nickel-tungsten or nickel-molybdenum will be more effective than the catalyzer that contains for example independent molybdenum of more weak metal function.The preferred Hydrobon catalyst of the saturated usefulness of aromatic hydrocarbons will comprise at least a metal with more intense hydrogenating function that is loaded on the porous support.Because desired hydrogenation reaction needs seldom acid function, and because wish not change into more lower boiling product in this step, the carrier of Hydrobon catalyst is low tart.General carrier substance comprises amorphous or crystalline oxide materials for example aluminum oxide, silicon oxide and low tart silica-alumina.For non-precious metal catalyst, usually high about 20% (weight) of the metal content of catalyzer.The common amount of precious metal is not more than 1.0% (weight).Such Hydrobon catalyst is easy to buy from catalyzer supply merchant.Nickel-tungsten catalyst can be a fluorizated.

The control of the reaction parameter of hydrofining step provides a kind of useful method that changes product stability.Life cycle Table VIII A and VIA family (IUPAC periodictable) metal, the mixture of nickel/tungsten for example, the about 230-300 of the temperature of Hydrobon catalyst ℃ (446-572 °F) will make mononuclear aromatics and polycyclic aromatic hydrocarbons reduce to minimum.This also will provide the product with good oxidative stability, UV light stability and thermostability.To influence the saturated lower air speed control aromatic hydrocarbons of aromatic hydrocarbons saturated with bigger, and the air speed of hydrofining reactor also provides a kind of potentiality.Hydrorefined product preferably contains the aromatic hydrocarbons that is not more than 10% (weight).

Embodiment

The following examples only are illustrative, and do not think restrictive.

Embodiment 1

Table 3 has provided the analytical data of the atmospheric tower bottom product that the two-stage hydrocracking device by industry obtains.Such hydroeracking unit has a hydrotreating reactor and a hydrocracking reactor, but need not be as at the described vacuum distillation apparatus of hydroeracking unit of the present invention.Product approximately is the cut of 330-538 ℃ (625-1000), and heteroatoms wherein and aromaticity content, particularly nitrogen content are very low.The hydrocracking catalyst that uses is fresh.The gamut analytical data of oil is listed in " oil at the bottom of total tower " hurdle at the bottom of the barreled atmospheric tower that is reclaimed.Oil content at the bottom of the tower is become isopyknic 5 cuts and analyzes main performance, and these analytical data also are listed in the table 3.

Comprising the Hydrodewaxing of catalytic dewaxing, after hydrofining and the distil process, the finished product must have following performance:

Viscosity index 〉=115

NOACK＞6≤20

Viscosity (being 100 ℃ of 4-5cSt)

Colourity 〉=20

Pour point≤-4 ℃ (25)

Aromatic hydrocarbons≤5% (weight)

Color and luster is stable under daylight

In order to obtain having the finished product of these characteristics, what meet the requirements is the raw material that begins with high as far as possible VI and alap NOACK (perhaps high flash point) as far as possible.Hydrodewaxing technology reduces pour point.In table 3, the high more pour point of the volatility of cut is low more, and the heavier cut than low volatility has higher VI.The cut of the volatility maximum that steams at 0-20% has low viscosity (100 ℃ of 2.77cSt) and is lower than 115 VI, so it is inapplicable.

In order to obtain the performance of above-mentioned product, just need obtain having the raw material of acceptable ranges of characteristics.In the present invention, use the underpressure distillation step.As shown in table 4, even hydrocracking and bottoms fraction underpressure distillation the lightest, the volatility maximum is suitable for, its VI that has is greater than 115,100 ℃ viscosity greater than 4cSt.

Table 3

Industry hydrocracking tower long residuum distillation becoming 5 equal-volume cuts

Residual oil at the bottom of the full tower 0-20% 20-40% 40-60% 60-80% 80-100%Distillation yield wt.% 19.4 19.0 18.7 19.9 23.1vol% 19.5 19.1 18.6 19.8 22.9 proportions, ° API 38.4 39.4 39.5 37.7 37.8 37.2Sp.Gr.60/60 0.8329 0.8280 0.8275 0.8363 0.8358 0.8388 pour point, ℃ (°F) 38 (100) 16 (60) 24 (75) 32 (90) 38 (100) 49 (120) ASTM color＜0.5COC flash-points, °F 216.11 (421) KV@40 ℃, KV@100 ℃ of cSt 19.33 10.23 13.72 17.34----, cSt 4.370 2.770 3.456 4.144 4.972 7.365KV@300 ℃, cSt 2.285 1.521 1.824 2.062 2.460 3.278SUS@38 ℃, (100) 101 62 76 92 113 216VI 141 114 132 147----

Table 4

At the bottom of the vacuum still of vacuum gas oil hydrocrackates

Oil is distilled into branch equal-volume cut

Vacuum still 0-20% 20-40% 40-60% 60-80% 80-100%

End oilDistillation yield wt.% 19.1 18.7 18.7 18.9 24.5vol% 19.2 18.7 18.7 18.7 24.1 proportions, ° API 35.6 35.9 35.5 34.9 34.1 32.9Sp.Gr.60/60 0.8468 0.8453 0.8473 0.8504 0.8545 0.8607 pour point, ℃ (°F) 43 (110) 27 (80) 29 (85) 29 (85) 29 (85) 38 (100) ASTM color 3.5COC flash-points, 260 ℃ (500) KV@40 ℃, cSt--23.76--------KV@100 ℃, cSt 7.115 4.898 5.50 5 6.354 7.480 10.42KV@300 ℃, cSt 3.308 2.373 2.626 2.933 3.359 4.308SUS@38 ℃, (100) 182 123 137 170 212 364VI--133--------

Embodiment 2

Fig. 5 explanation has pour point and is-7 ℃ oil body index and the relation between the hydrogen richness, wherein, and this oil or made with extra care by solvent treatment or by hydrocracking.Each various waxy feeds relatively are that solvent dewaxing is to-7 ℃ of pour points.Along with the increase that is present in the weight percentage of hydrogen in the lubricant base, then the VI viscosity index improves.The raw material of hydrocracking and solvent-refined raw material ratio VI some improvement a little.Empty circle representative is not had the further lube stock of processing by lube oil hydrogenation cracking, distillation and solvent dewaxing.The circle representative that contains interlacing line is by fuel hydrocracking, distillation and solvent dewaxing purified lube stock.Square is represented the lube stock of solvent treatment and solvent dewaxing.The vacuum distillate that axial trilateral representative is obtained by paraffinic crude.The vacuum distillate that the del representative is obtained by naphthenic base crude.

Obviously, the hydrocracking of vacuum gas oil will provide the high VI lube stock of lube stock that obtains than lube oil hydrogenation cracking or solvent treatment, because the vacuum gas oil hydrocracking is more violent than lube oil hydrogenation cracking.In the present invention, the lube stock of dewaxing must have at least 115 VI.As seen from Figure 5, in order to obtain 115 VI, the pressed oil product must have the hydrogen richness at least about 14.1% (weight).Because dewaxing reduces hydrogen richness, so the hydrogen richness of waxy oil must be than the about 0.2-0.5% (weight) of hydrogen richness height of the oil that dewaxes.Therefore, the feature of key of the present invention is that hydroeracking unit provides the underpressure distillation product with at least 14.3% (weight) hydrogen.In Fig. 5, the PONA of the lube stock of these hydrocracking analyzes explanation, and they have very big variation aspect composition, and some has very high paraffinicity, and some has very high cycloalkanes content, and some other is between the two.Therefore, be possible in any unlimited variation of the composition of VI value, this variation can be described by the scope for the VI hydrogen richness of arbitrary value.For carbonatoms is C ₁₇-C ₅₅The hydrogen richness of 150 isoparaffins be respectively 15.1%-14.6%.For alkyl cyclohexane, it is constant, 14.37%; For alkylbenzene, it is 12.4-13.69%.Thus, the consequent is that the pressed oil product must be a lot of in high hydrogen richness isoparaffin and alkyl cyclohexane.The Gas Oil Isomax device, promptly surpass 40% change into 345 ℃-the situation of light product under the hydroeracking unit operated, can produce 345 ℃+the product with suitable hydrogen richness be 115 pressed oil so that viscosity index is provided.

Embodiment 3

Fig. 6 (a, b and c part) is for the lube oil hydrogenation cracking of the heavy vacuum gas oil that obtains from Statfjord crude oil and the explanation of Gas Oil Isomax.This weight vacuum gas oil carries out hydrocracking under the situation of various transformation efficiencys in pilot plant, distills isocrackate, removes the material of all 345 ℃ (653).Then, 345 ℃+waxy oil carry out solvent dewaxing to-18 ℃ of (0) pour points, and measure viscosity and VI.Transformation efficiency be 10-about 30% be called lube oil hydrogenation cracking scope, transformation efficiency be 30% and Geng Gao be called the Gas Oil Isomax scope.Obviously, in order to obtain having the product that VI is 115 dewaxing, need the transformation efficiency of hydrocracking to be about 35%.The degree of needed conversion depends on the viscosity of the charging that enters hydroeracking unit.Fig. 6 also illustrates how to reduce viscosity when hydrocracking begins.Why Here it is limits the product of Gas Oil Isomax device production low viscosity scope, for example is 60-250SSU or is 3-6cSt at 100 ℃ at 100 °F).Fig. 6 be also illustrated in the Gas Oil Isomax device 345 ℃+yield be low.

Data in embodiment 4-12 obtain from catalytic dewaxing and two reactor process of hydrotreatment.(embodiment 5 is seen in detailed discussion).First reactor contains a kind of patent catalyst for hydrogenation de-waxing HZSM-5.

For high pressure with low voltage operatedly all use same catalyst for hydrogenation de-waxing.In second reactor, use the Hydrobon catalyst of industry.In low pressure (2.86 * 10 ³-4.2 * 10 ³Kpa) operation, only designing Hydrobon catalyst, to be used for alkene saturated.But,, need aromatic hydrocarbons to a certain degree saturated for good oxidative stability and UV light stability.Use is at high pressure (1.73 * 10 ⁴Kpa) to be used for aromatic hydrocarbons saturated for Cao Zuo Hydrobon catalyst.For a comparison is provided, 1.53 * 10 ⁴Kpa estimates the Hydrobon catalyst that uses in low pressure.

Embodiment is as 4

Using NOACK evaporation test machine purified (not adding agent) base oil to be carried out NOACK volatility test (seeing Fig. 7 and 8) according to CECL-40-T-87 " lubricating oil evaporation loss " test.In general, this method is determined at the vaporization losses % (weight) that remains on 250 ℃ of (482) time samples of 60 minutes under the logistics of fixed air.

Fig. 7 represents to be followed by high pressure and low pressure catalytic dewaxing the NOACK volatility of the oil base stock that hydrofining produces.General, NOACK volatility and the per-cent relevant (seeing Fig. 7 and table 5) that in the D2887 simulation distil, steams in 399 ℃ of steamings (750).For these products, between NOACK and the good (see figure 8) that concerns is also arranged at 10%.

When relating separately to 5% or 10% boiling point, flash-point and NOACK show in opposite mode.Fig. 9 provides the relation of flash-point and 5% boiling point.

Table 5

The comparison of the product that use high pressure HDF and standard HDF obtain

The HDF catalyst type Aromatic hydrocarbon saturation catalyst Standard alkene is saturated Hydrobon catalystCondition pressure, Kpa (psig) 1.73 * 10 ⁴KPa 1.73 * 10 ⁴KPa 1.73 * 10 ⁴KPa 1.73 * 10 ⁴KPa 2.86 * 10 ³KPa 2.86 * 10 ³KPa 1.86 * 10 ³Pa 1.53 * 10 ⁴KPa (100%H ₂) (2500) (2500) (2500) (2500) (400) (400) (2500) (2200) HDT temperature, °F 329 (625) 302 (575) 274 (525) 232 (450) 241 (465) 260 (500) 288 (550) 260 (500) Non-impurity-doped (not adding agent) oilThe NOACK volatility; Wt% 23.8 18.8 17.9 20.3 18.6 17.7 19.5 18.0SAB colors 28 28 29 29 1.0 1.5-16 9 light stabilities are to the %UV trap that 42+ 42+ 42+ 42+＜4＜4＜4＜4 fates distill out in 399 ℃ (750 °F) 26.3 21.0 20.8 20.7 22.3 21.6 24.6 24.6 simulations of muddy/precipitation, L/g-cm226nm 0.0113 0.00415 0.00255 0.0281 0.923 0.766 0.726 0.324254nm 0.000740 0.000379 0.000219 0.00119 0.133 0.122 0.129 0.0223275nm 0.00120 0.000461 0.000283 0.00250 0.161 0.142 0.158 0.0372325nm 0.000460 0.000063＜0.000100＜0.000100 0.0287 0.0341 0.0467 0.00336400nm 0.000006 0.000003＜0.000100＜0.000100 0.00275 0.00386 0.00513＜0.000100Oil+0.3%Irganox ML820The RBOT oxidation test reduces the number of minutes 580 500 565 565 472 510 640 560 of 25psi

Embodiment 5

With the low aromatic hydrocarbons of hydrocracking and the raw material of low nitrogen content, two kinds of catalyst system (high pressure catalytic dewaxings+Arosat HDF catalyzer (fluorizated NiW/Al ₂O ₃) and low pressure catalytic dewaxing+HDF catalyzer (Mo/Al ₂O ₃)) can meet the requirement of pour point easily and obtain similar yield of lubricating oil and viscosity.General characteristic is summarized as follows.

1.73 * 10 ⁴Kpa is (with 2.86 * 10 ³Kpa is relatively) [(2500psig and 400psig are relatively)] operation, reduce dewaxing catalyst and wear out from 2.3-0.2 °F/day, prolong the potential length of the cycle greatly, and improved the logistics factor of device.Under high pressure in response to the depression of pour point twice of catalytic dewaxing temperature variation, if desired, it impels produces the very oil base stock (see figure 10) of low pour point.

Yield of lubricating oil and VI are comparison sensitivity (seeing Figure 11) for pressure, the yield of producing 121VI, the 116SUS oil base stock of-15 ℃ of pour points is that (and be benchmark with dried wax, the yield of solvent dewaxing production 129VI, 107SUS oil base stock is 82% (weight) to 67-72% (weight).

The low pressure catalytic dewaxing of standard allows to adjust total aromaticity content (Figure 12) of being determined by the UV specific absorption by at 226nm hardly.1.73 * 10 ⁴Kpa (2500psig) uses aromatic hydrocarbon saturation catalyst to allow to reduce the aromaticity content determined by the UV specific absorption to equilibrium value 274 ℃ of (525) HDF temperature.

Pilot plant at two reactors that have online nitrogen stripping ability carries out the low pressure program.Reactor 1 is equipped with 225cc dewaxing catalyst HZSM-5, and reactor 2 is equipped with 225cc Hydrobon catalyst (Mo/Al ₂O ₃), its design is used for the saturated and low desulfurization of alkene (key is to keep the oxidative stability of conventional bright stock oil base stock).Two kinds of catalyzer all are 1/16 " cylindrical extrusion and be industrial.

Using pure hydrogen 2.9 * 10 ³The 400psig stagnation pressure of kpa (415psi hydrogen dividing potential drop) and have 1.73 * 10 ⁴Carry out low voltage operated under the situation of the 1LHSV (each reactor) of kpa (2500scf/B) hydrogen recycle.For producing the stabile oil base stock of UV light, in order to find out (bracket) processing severity, in pour point (15 ℃) research three kinds of HDF temperature (241 ℃, 274 ℃ and 288 ℃) of regulation in the best.

In the pilot plant of two reactors, carry out the high pressure catalytic dewaxing.Reactor 1 is equipped with the 262cc dewaxing catalyst, and this catalyzer is a used same dewaxing catalyst under operating under standard pressure.Reactor 2 is equipped with the industrial Hydrobon catalyst (Arosat) that 62cc has excellent aromatic hydrocarbons saturability.It is commercial can buy 1/16 " the quatrefoil extrusion.

1.73 * 10 ⁴(the 2500psig stagnation pressure uses pure hydrogen 1.74 * 10 to kpa ⁴Kpa (hydrogen dividing potential drop)) and have under the situation of 1LHSV (each reactor) of 445n.l.l. (2500scf/B hydrogen recycle) and carry out the high pressure catalytic dewaxing.For producing the stabile oil base stock of UV light, in order to find out processing severity, in pour point (15 ℃) research four kinds of hydrofining temperature (329 ℃, 302 ℃, 274 ℃ and 232 ℃) of regulation in the best.The data of Figure 12 clearly show the good aromatic hydrocarbon saturation catalyst of hydrofining reactor needs after dewaxing reactor.

Embodiment 6

Sunlight stability

Method is introduced

In this test, purified (not additivated) oil base stock that is placed in the bottle is exposed under the nature sunlight, and periodic muddiness, precipitation and the colour-change of observing.All samples all are to carry out simultaneously in same position.

The result

When using aromatic hydrocarbon saturation catalyst, the light stability with oil base stock hydrotreatment the high pressure catalytic dewaxing is fabulous, does not precipitate after 42 days (seeing Figure 13).Have very poor light stability by low pressure catalytic dewaxing and hydrofining and the product that also obtains, just degenerate in 2-3 days being equivalent to by solvent dewaxing.This just shows, photo-labile is not the result who produces at catalytic dewaxing step, but the result of unstable component in the oil at the bottom of the hydrocracking tower.Such unstable is usually relevant with the 3+ Polycyclic aromatic hydrocarbons, and it can be by detecting in the UV of 325nm absorptivity.After the absorb light, these compound oxidations produce the chain initiation thing of radical, then it and other hydrocarbon reaction, generation carboxylic acid.In low aroamtic hydrocarbon raw material as these, the solubleness of these oxidation productss is very low, and they are precipitated out.The high pressure catalytic dewaxing have the UV absorptivity of 325nm with hydrorefined oil base stock, it is the several magnitude (seeing Figure 12 and table 5) that is lower than other sample.It should be noted that for removing these unsettledization compounds, standard catalytic dewaxing hydrotreating catalyst, even 1.53 * 10 ⁴Kpa (2200psig) neither be well suited for.The result of the light stability of Figure 13 is associated with the UV result of Figure 14.

Embodiment 7

Carry out the RBOT test (the rotary oxygen bomb oxidation of turbine oil) of oxidative stability according to ASTM method D2272.It is made of base oil+0.3% (weight) Irganox ML820, and Irganox ML820 is the commercial turbine oil additive integral formula that can buy.In this test, sample is placed in the pressure oxygen bomb with water and copper catalyst circle.This oxygen bomb is pressurized to 620kpa (90psi) with oxygen, be placed in the bath of 150 ℃ (302), and tilting axis is to rotation.Record pressure is reduced to the needed the number of minutes of 172kpa (25psi); Therefore, higher result represents good oxidative stability (see Table 5 and Figure 15).

The result

The RBOT performance of the oil base stock of high pressure catalytic dewaxing and low pressure catalytic dewaxing is similarly, and is good (seeing Figure 15).Also fine from the solvent dewaxed oil that same industrial raw material obtains, but mean value is more or less low.With respect to the catalytic dewaxing raw material, the sample of the hydrocracking of solvent dewaxing is suitable poor, and show a kind of general tendency that RBOT stability reduces along with the increase of boiling spread (oil compares with the full range isocrackate at the bottom of 25% tower), running finishes (EOR) and begins (SOR) relatively, the aging increase of the catalyzer of hydrocracking tower with running.

Embodiment 8

Table 5 is by absorbing explanation at the extremely low UV of 400nm, and polycyclic aromatic hydrocarbons is not exist basically in the lubricating oil of following the hydrofining processing with the high pressure catalytic dewaxing.This sunlight stability result with Figure 13 is relevant.

Embodiment 9

1.73 * 10 ⁴Kpa (2500psig) ratio is 2.8 * 10 ³Kpa (400psig) compares, and the aging of dewaxing catalyst reduces significantly.In addition, the lubricating oil pour point is 2.3 times, to more responsive in the temperature variation of higher pressure dewaxing.These difference belong to coke formation speed reduction under higher pressure.

In Figure 10, drawn the situation of catalyst aging.The relation of expression Hydrodewaxing reactor (reactor 1) temperature (actual and be converted to 5 pour points) and pour point and days of operation.As general situation, for the raw material of low nitrogen, aging speed is lower than conventional solvent treatment raw material.

High pressure catalytic dewaxing operation

1.73 * 10 ⁴Under kpa (2500psig) condition, in first two days of running, mark catalyzer at 285 ℃ (545 °F).36 days aging speeds of whole running are negligible.Therefore, 1.73 * 10 ⁴Kpa (2500psig) expection has extremely long length of the cycle.

The low pressure catalytic dewaxing

2.8 * 10 ³Kpa (400psig), the temperature of circulation beginning is about 530 °F.Initial aging speed is-14 ℃ (6.5 °F/day), carries out the transition to lower aging speed-15 ℃ (5.65/day).The pour point conversion relation of 1.3 pour point/1 variations is for pour point scope-30 ℃-4 ℃ (22 °F-+39 °F) in the HDW temperature of reactor, and it is effective eliminating HDW temperature of reactor characteristic.

After turning round 29 days, pressure is increased to 2200psi.In 4 days, the fundamental quantity of the activity of such catalysts of recovery and aging speed are reduced near zero.This just proposes 2.8 * 10 ³Kpa (400psig) causes increasing aging speed by higher coking speed, and some such Jiao is easy to hydrogenation or desorption when pressure increases.

Embodiment 10

General, the working pressure that increases catalytic dewaxing often reduces the distillate yield and correspondingly increases the C5-yield.Yield of lubricating oil is responsive for pressure ratio.With solvent dewaxing (SDW) relatively, the yield of lubricating oil of-15 ℃ of (5) pour points differs about 10% (weight), be 70-72% (weight) with the catalytic dewaxing of ZSM-5 catalyzer, and solvent dewaxing (dried cerul) is 82% (weight).But, should be realized that the wax of most solvent dewaxing unit production always all contains 10-30% oil.So actual solvent dewaxing yield is 74-80%.

Product yield distributes and shows, produces nonselective cracking at 329 ℃ (625 °F) on high reactivity high pressure aromatic hydrocarbon saturation catalyst.Yield of lubricating oil reduces by 6% (weight), shown in Figure 16 (relation of yield of lubricating oil and temperature) and Figure 17 (relation of viscosity and hydrofining severity under the fixed pour point).Most this loss increases along with the increase of distillate yield.Under 329 ℃ of (625) hydrotreatment temperature, the unexpected variation of lubricants performance aspect has also indicated non-selective cracking.

In most of hydrofining operating restraints of whole test, the viscosity of low pressure and high pressure catalytic dewaxing lube products is similar (Figure 18).At-15 ℃ of (5) pour points, are 4.6cSt (116SUS@100) 100 ℃ of viscosity, VI is 121.The oil viscosity of solvent dewaxing is lower, and VI is higher, and the difference of mode aspect that two kinds of methods of this and this reach their target is consistent.

Can find out significantly from lubricants performance discussed above and yield, on the Arosat Hydrobon catalyst, produce non-selective cracking at 329 ℃ (625 °F).Lubricating oil viscosity reduces significantly, and corresponding VI reduces 3-5 numerical value.

(seeing Figure 18)

Main difference between the performance of the lubricating oil that obtains with low pressure and high pressure catalytic dewaxing is the result-in the type of (1) used Hydrobon catalyst and the result of the difference aspect (2) hydrogen pressure of aromatic hydrocarbons degree of saturation in the hydrofining reactor.For the aromatic feed for example darker cut or the product of loop ends hydrocracking at the bottom of the hydrocracking tower, these difference even bigger.

The wax of heavier higher pour point is preferentially removed in solvent dewaxing, and with the catalytic dewaxing of the ZSM-5 less normal paraffin of cracking preferentially, and it also is the component of the highest VI.Therefore, neutral yield of lubricating oil of the light industry of catalytic dewaxing and VI are lower.But the low temperature viscid characteristic of the product of the catalytic dewaxing of production is better than the oil of the solvent dewaxing of suitable viscosity.

Embodiment 11

For the hydrofining reactor condition of the screening in the research of pilot plant, UV specific absorption and product state are believable.5 kinds of wavelength-226,254,275,325 and the specific absorption of 400nm-as the quality indicator of aromatic hydrocarbons amount, at 226nm corresponding to total aromatic hydrocarbons.By represent to have 3 or more rings and 4 or polycyclic aromatic hydrocarbons more respectively in the specific absorption of 325nm and 400nm.

Be used for the noticeable amount that reduces lubricating oil aromatic hydrocarbons of Arosat HDF catalyzer.Standard catalytic dewaxing HDF catalyzer, it is saturated that it is designed for alkene, even 1.53 * 10 ⁴Kpa (2200psi), poor efficiency many (seeing Figure 12 and 21).As seeing from Figure 12, in high pressure catalytic dewaxing near 274 ℃ (525), in the UV of 226nm specific absorption (it is relevant with total aromatic hydrocarbons) by a minimum value-the indicate leap that is restricted to the equilibrium-limited scope from kinetics.Along with the increase of raw material aromatic hydrocarbons, this minimum value will be shifted to higher H DF temperature (with higher UV specific absorption).In the temperature range of research, saturated for aromatic hydrocarbons, the catalytic dewaxing HDF catalyzer of standard is a kinetic limitation.

General, the saturation ratio of polycyclic aromatic hydrocarbons (400nm) is easier to, and in the normal hydrofining temperature range of high pressure, reaction is subjected to the equilibrated restriction, promptly increases along with hydrofining variation of temperature polycyclic aromatic hydrocarbons reduces then.Higher hydrogen pressure is shifted to than low value balance.

Figure 19 represents for the two kinds of different isocrackate UV specific absorptioies and the relation of aromaticity content with 20.A kind of have low aromaticity content, and another kind has high aromaticity content.These data illustrate that clearly high pressure and Arofining catalyzer refine than the high-pressure hydrogenation with the standard Hydrobon catalyst.(seeing Table 6).[table 6]

Product property relatively

HDW temperature ℃ (°F)	HDF temperature ℃ (°F)	Pressure KPa	Aromatic hydrocarbons in the wt.% lubricating oil (CHg=14.3)	Lubricating oil pour point ℃ (°F)	Lubricated yield wt.%	The fractionation yield of aromatic hydrocarbons (lubricating oil aromatic hydrocarbons * yield of lubricating oil)/(aromatic hydrocarbons variation)
							(316)	218	2.8×10 3 KPa(400)	15.3	-15(5)	86	0.9
(335)	218	2.8×10 3 KPa(400)	20.7	-46 (-50)	76	1.1
							(327)	218	1.53×10 4 KPa(2200)	1.7	-15(5)	88	0.1

Embodiment 13

Though as dewaxing catalyst, top other catalyzer of being introduced also can be used as dewaxing catalyst to above-mentioned a lot of embodiment with HZSM-5.This is described at Figure 20, and its dewaxing catalyst is Pt/ZSM-23.The VI that Figure 18 represents the lubricating oil that obtains with Pt/ZSM-23 and yield approximately are that the VI of the lubricating oil that obtains with solvent dewaxing is identical with yield or better.

Embodiment 14

Test the ability that some mesoporous molecular sieves transform normal paraffin (it is the representative of wax in the content of wax light lubricating oil base oil).This normal paraffin is a n-hexadecane.With the molecular sieve of this compound test be ZSM-5, ZSM-23, ZSM-48 and SAPO-11.As by " ALPHA " test determination, for molecular sieve, perhaps in molecular sieve synthetic or change the acidity of catalyzer by steam treatment (known this be the active method of reduction molecular sieve).Is precious metal that platinum is added in the every kind of catalyzer that is prepared by molecular sieve.The concentration of platinum changes with some molecular sieve.Following tabular has gone out molecular sieve, their platinum content and their " ALPHA " activity.

Table 7

The character of molecular sieve

Molecular sieve	Pt，wt.％	" ALPHA " activity	At 0.4LHSV, the temperature of 95% transformation efficiency
				ZSM-23	0.5	30	547
ZSM-23	0.2	30	570
				ZSM-23	0.5	1	603
ZSM-48	0.83	5	619
				SAPO-11	0.7	9	600
ZSM-5	1.1	8	554
				ZSM-5	0.4	1	603
ZSM-5	0.5	280	445at3.0 LHSV

These all mesoporous molecular sieves can both make the wax compound for example n-Hexadecane very high transformation efficiency is arranged.By the activity of such catalysts of every kind of molecular sieve preparation according to the tangible difference of the activity of molecular sieve in the catalyzer.The content of platinum also influences activity.Selectivity of product is subjected to type, platinum content and " ALPHA " active influence of molecular sieve.Figure 21 is the transformation efficiency of n-hexadecane and the graphic representation of temperature condition.Figure 22 has the n-hexadecane of the isomery of 16 carbon atoms to transform the graphic representation of the transformation efficiency of the yield of compound and n-hexadecane.The figure shows, what ZSM-48 and SAPO-11 were general has best choice to isoparaffin.If use high α ZSM-5, selectivity is very low.But Figure 23 shows that ZSM-23 has good selectivity to single branched chain isomer of n-hexadecane.In the VI of decision lube products, such selectivity may be very important.So clearly, normal paraffin or wax change into the isomeric compound of same molecular amount,, need the best bullion content and the acidity and the pore structure of molecular sieve for each used molecular sieve in making finished catalyst.

Claims (33)

1. method of producing the dewaxing lubricant product, this method comprises at least one hydrocracking zone, at least one Hydrodewaxing zone and at least one hydrofining zone, the pour point of this product is less than or equal to that-4 ℃, hydrogen richness at least 13.7 weight %, at least 200 ℃ of flash-points, NOACK number are not more than 20, Saybolt color at least 25, total aromatic hydrocarbons less than 10 weight %, 100 ℃ viscosity at least 3.0cS, viscosity index (VI) be 115 or higher and fabulous oxidative stability, UV light stability and thermostability are arranged, this method comprises the steps:

(a) under the condition of hydrocracking inlet, boiling point is higher than the hydrocracking raw material that 340 ℃ and hydrogen richness be lower than 13.5 weight % and carries out hydrocracking, and the feedstock conversion that makes at least 30 weight % is the product that boiling point is lower than the hydrocarbon of raw material initial boiling point;

(b) at pressure at least 10,000kPa, in the presence of the common hydrogen that adds, be up under 425 ℃ the elevated temperature, at 100 ℃ kinematic viscosity 3.0cS at least, viscosity index VI at least 125, the NOACK number is 20 or lower, hydrogen richness at least 14 weight %, at least 10 ℃ of pour points and nitrogen content are not more than the unconverted material of part of (a) step of 30ppm by distributing equably and contacting Hydrodewaxing with catalyzer, catalyzer comprises selects shape, the constraint mesoporous molecular sieve, wherein divide in sieve to have at least one by containing by the passage in the annular hole of silicon or displaced 10 Sauerstoffatoms of phosphorus atom, this molecular sieve has acid function;

(c) under the saturated condition of aromatic hydrocarbons, the outflow logistics of step (b) contacts with the Arofining catalyzer that effectively has the metal hydrogenation function with the hydrogen that adds together carries out hydrofining, temperature of reaction is about 230-343 ℃, reaction pressure at least 10,000kPa is so that the lube products that obtains dewaxing;

(d) separating by-products from the lube products of step (c) by flash distillation and distillation.

2. according to the process of claim 1 wherein that the boiling point of in step (b) hydrodewaxed unconverted material is at 315 ℃ or higher.

3. according to the process of claim 1 wherein that step 1 (a) also comprises the steps:

(a) in the hydrotreatment zone that the catalyzer with hydrodenitrification and hydrodesulfurization activity is housed, hydrotreatment is carried out in the hydrocarbon charging of step 1 (a);

(b) effluent of the hydrotreatment of step 2 (a) leads to placed in-line hydrocracking zone, contact with hydrocracking catalyst at this zone raw material and to carry out hydrocracking, this catalyzer contains the molecular sieve of the unformed material of macropore or macropore and contains the hydrogenation/dehydrogenation component, in the presence of hydrogen, the effluent that transforms hydrotreatment under elevated temperature and pressure is more lower boiling product, the condition of hydrocracking is hydrogen dividing potential drop 3448-17238kPa, temperature 315-455 ℃, air speed 0.5-10LHSV and hydrogen: oil ratio is 1000-5000SCF/BBI, once by transforming at least 30 weight %, form the logistics of hydrocracking, removed at least 90% nitrogen thus;

(c) effluent of the hydrocracking of step (b) is passed to separated region to remove product, unconverted part is led to the underpressure distillation zone, the operational condition in underpressure distillation zone is the about 300-380 of column bottom temperature ℃, and the about 20-300mmHg of tower bottom pressure produces product cut and tower bottom distillate thus;

(d) product of step 3 (c) is led to the dewaxing zone of step 1 (b).

4. the method for step 3 (c) wherein is recycled to the hydrocracking zone of step 2 (b) to the small part tower bottom distillate.

5. according to the method for claim 1 or 2, wherein the shape mesoporous molecular sieve material of selecting of step 1 (b) is selected from ZSM-5, ZSM-23, ZSM-35, ZSM-11, SAPO-11 or their mixture, and wherein each catalyzer all is loaded with precious metal.

6. according to the method for claim 1 or 2, wherein the shape mesoporous molecular sieve of selecting of step 1 (b) is HZSM-5.

7. according to the method for claim 5, select wherein that shape mesoporous molecular sieve material has the restricted index of 0.5-12 and less than 300 α value.

8. according to the method for claim 7, wherein the α value is less than 30.

9. method according to Claim 8, wherein the α value is less than 10.

10. according to the method for claim 5, wherein molecular sieve material is loaded with 0.2-1.2 weight % precious metal.

11. according to the method for claim 1 or 2, wherein the Hydrobon catalyst of step 1 (c) contains at least a VIIIA family's metal and at least a VIA family metal on porous solid carrier.

12. according to the process of claim 1 wherein that the Hydrobon catalyst of step 1 (c) contains nickel and the tungsten metal on the fluorizated porous alumina carrier of the mixture that comprises aluminum oxide or silicon oxide and aluminum oxide.

13. according to the process of claim 1 wherein that dewaxing zone is to operate with the hydrofining zone basically under identical pressure, and all pressed oil logistics in the stage that wherein dewaxes directly enter the hydrofining zone.

14. according to the method for claim 10, wherein at pressure greater than 10, the aging speed of dewaxing catalyst is not more than about 0.1 ℃/day under the situation of 000kPa.

15. according to the process of claim 1 wherein 1 (b) step be hydrodewaxing at least two the dewaxing zones carry out.

16. according to the process of claim 1 wherein 1 (c) step be hydrodewaxing at least two the dewaxing zones carry out.

17. according to the process of claim 1 wherein that the boiling point of dewaxing lubricant product is higher than about 370 ℃, be 4-10cSt at 100 ℃ KV, in the UV of 315nm optical density less than 0.001L/g-cm.

18. according to the method for claim 17, wherein the dewaxing lubricant product in the UV of 315nm optical density less than 0.001.L/g-cm.

19. according to the method for claim 1 or 2, wherein heavy hydrocarbon feedstocks comprises vacuum gas oil, diasphaltene raffinate oil or both mixtures.

20. according to the method for claim 1 or 2, wherein the Hydrodewaxing zone of 1 (b) step comprises the fixed bed catalytic reactor of many vertical arrangements, wherein chilling logistics hydrogen is used to reduce temperature between bed.

21. according to the method for claim 1 or 2, wherein the hydrofining zone of 1 (c) step comprises the fixed bed catalytic reactor of many vertical arrangements, wherein chilling logistics hydrogen is used to reduce temperature between bed.

22. according to the process of claim 1 wherein that the NOACK number is not more than 10.

23. according to the method for claim 22, wherein the NOACK number is not more than 5.

24. according to the method for claim 2 (c), wherein the NOACK number of the residual oil in underpressure distillation zone is not more than 20.

25. according to the method for claim 24, wherein the NOACK number of the residual oil in underpressure distillation zone is not more than 10.

26. according to the method for claim 25, wherein the NOACK number of the residual oil in underpressure distillation zone is not more than 5.

27. according to the process of claim 1 wherein that the aromaticity content of dewaxing lubricant and product is not more than 2 weight %.

28. show color stability the dewaxing lubricant product exposes 10 days in sunlight and atmosphere after according to the process of claim 1 wherein.

29. according to the process of claim 1 wherein that the 10% distillation point of dewaxing lubricant product is 357 ℃ or higher.

30. according to the method for claim 29, wherein 10% of dewaxing lubricant product distillation point is 413 ℃ or higher.

31. according to the method for claim 30, wherein the distillation of dewaxing lubricant product point is 432 ℃ or higher.

32. according to the process of claim 1 wherein that the pour point of dewaxing lubricant product is-50 to-4 ℃.

33. according to the process of claim 1 wherein that the hydrogen richness of dewaxing lubricant product is at least 14.3 weight %, VI is 120 or bigger.

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