CN1016249B - Process for catalytic dewaxing of more than one pefinery-derived lubricating base oil precursor - Google Patents

Abstract

A process for catalytic dewaxing of more than one refinery-derived lubricating base oil precursor which comprises contacting in a first reaction zone in the presence of a hydrogen-containing gas at hydrodewaxing conditions a first feed stream which contains a first wax comprising straight-chain paraffins with a first hydrodewaxing catalyst and contacting in the presence of a hydrogen-containing gas at hydrodewaxing conditions in a parallel-situated second reaction zone a second refinery-derived raffinate lubricating base oil precursor which contains a second wax containing branched and/or cyclic hydrocarbons with a second hydrodewaxing catalyst and optionally contacting in one or more further reaction zones further refinery-derived waxy raffinate lubricating base oil precursor feed streams with a hydrodewaxing catalyst.

Description

Process for catalytic dewaxing of more than one pefinery-derived lubricating base oil precursor

The present invention relates to a kind of refinery and produce the catalytic dewaxing process of more than one lubricant base raw materials.

Aspect different fractions oil or deasphalted oil production lubricant base, occurred one about removing the problem of the content of wax material in the lubricant base raw material.The existence of this class content of wax material is stinking, because it makes final lubricating oil have high pour point, thereby reduces or loses lubricating oil effectiveness at low temperatures fully.

Two kinds of general methods that are used for this type of petroleum fractions oil dewaxing are solvent dewaxing process and catalytic dewaxing method.Therefore the former be out of favour in the recent period because its investment and process cost are all higher.The latter is called the Hydrodewaxing method, has obtained extensive studies.This technology has developed into has brand-new series catalyst, this type of catalyzer is called tectosilicate catalyzer (tectosilicate catalyst) in " hydrothermal chemistry of zeolite " book that RMBarrer showed, comprising aluminosilicate and borosilicate etc.It is inner and stop and do not need the non-content of wax material of Hydrodewaxing to enter to come down to want to adopt a kind of tectosilicate catalyzer, its aperture can make long-chain paraffin material and other content of wax material enter the tectosilicate molecular sieve selectively.

With crude oil is raw material, can produce various lubricant base raw materials in many cases, usually be divided into: lightweight high viscosity index (HVI) raw material (viscosity index is 80～100 or 80～150), middle matter high viscosity index (HVI) raw material (viscosity index is 250～300), raffinating oil (hereinafter being called bright stock) of heavy high viscosity index (HVI) raw material (viscosity index is 500～600) and high viscosity index (HVI) bright stock.All these raw materials at it as lubricant base (component) before all must dewaxing.

In brief, so far do not develop yet and a kind ofly can transform the paraffin material in all adopted petroleums or the tectosilicate or the aluminosilicate catalyst composition of other content of wax material selectively, remove the problem of content of wax material selectively to solve, and satisfy the requirement of market quality index.Causing a reason of this dilemma, is that the difference of content of wax material (being counted as pollutent) between all logistics is very big, and straight-chain paraffin is not singly arranged, and the hydrocarbon of side chain and ring texture is arranged.Therefore, it is impossible removing to handle selectively the content of wax material that is contained in all these class lubricating oil feed of base oil with the consistent especially catalyzer in a kind of aperture.

The United States Patent (USP) of announcing in 1980 once determined that ZSM-23 type or ZSM-35 type catalyzer had more the ability of producing high viscosity index (HVI) pressed oil than ZSM-5 type catalyzer for the 4th, 222, No. 855.But this patent fails to recognize or confirm, the pour point index that ZSM-35 can not dewax to and meet current market demands than the oil plant that lightweight neutral oil weighs.Fail also to recognize or confirm that this specific character is to be caused by the special relationship between the molecular structure of catalyzer aperture and different viscosity scope lubricating oil logistics institute content of wax molecule.United States Patent (USP) the 4th, 372, think for No. 839, depending merely on the ZSM-35 catalyzer can not be with depression of pour point in demand minimum level, but this defective can be resolved by the general Video Streaming that adopts two kinds of pattern zeolites, promptly at first contact, contact with the ZSM-5 aluminosilicate then with the ZSM-35 aluminosilicate.

Original patentee once recognized such fact, that is: the feed stream that drops into the Hydrodewaxing device can be separated, and a part of only getting is wherein handled in the Hydrodewaxing device.For example, the people's such as Chen that announced in 1976 United States Patent (USP) the 3rd, 956, in No. 102, the patentee thinks, petroleum fractions is separated, only in all logistics of the separately back gained of usefulness ZSM-5 type catalyst treatment merges untreated logistics and Hydrodewaxing product then, makes the finished product.

An object of the present invention is to provide a kind of flow process of feasible refinery's dewaxing process, so that more than one refinery's lubricant base raw material of handling selectively and miscarrying, rather than in single reactor with those processing power deficiencies, to another type lubricant base raw material very effective different catalysts mixed packing that then seems to a certain type of lubrication oil feed of base oil.Therefore, this flow process can make multiple dewaxing lubricant base oil with fabulous pour point and viscosity index.

So, the present invention relates to a kind of refinery and produce the catalytic dewaxing process of more than one lubricant base raw materials, this method comprises: hydrogen-containing gas exist and the Hydrodewaxing condition under, first via feed stream (contain the refinery and produce raffinating oil of first kind of lubricant base raw material containing first kind of wax being made up of straight-chain paraffin) is contacted with first kind of catalyst for hydrogenation de-waxing selecting the above-mentioned first kind of wax of conversion in first reaction zone; Under hydrogen-containing gas existence and Hydrodewaxing condition, the raffinating oil of the second road lubricant base raw material of being produced from the refinery the second kind of wax that contains band side chain and/or cyclic hydrocarbon contacts with second kind of catalyst for hydrogenation de-waxing selecting to transform above-mentioned second kind of wax in second reaction zone that be arranged in parallel; Can also be randomly hydrogen-containing gas exist and the Hydrodewaxing condition under, the content of wax that other refinery is produced the lubricant base raw material is raffinated oil and is contacted with catalyst for hydrogenation de-waxing in one or several other reaction zone; Obtain two kinds of refineries and produce the logistics of dewaxing lubricant base oil from above-mentioned all reaction zones are parallel at least.

The catalyzer that is applied in two kinds of patterns of this selectivity parallel channels Hydrodewaxing method is exactly existing those catalyzer that are called dewaxing catalyst in traditional technology.For example, United States Patent (USP) the 3rd, 702, No. 886 are open and the type ZSM 5 molecular sieve of its application in Hydrodewaxing has been described.In addition, also has the disclosed ferrierite that combines at least a metal of from VI B family, VII B family and VIII family, selecting in 692 at United States Patent (USP) the 4th, 343.But do not recognize yet so far: with the proximate molecular sieve in ferrierite aperture, some types of feedstock can not be dewaxed to and conform with the needed specification standards in market, but when the aperture being similar to or be attached in the process greater than the dewaxing catalyst of ZSM-5, then for the parallel dewaxing operation of the selectivity of specific type raw material, surprising unexpected cooperation usefulness will be produced.

Method of the present invention should comprise the catalytic hydrodewaxing zone of three or more parallel runnings.

One embodiment of the invention are the methods that prepared four or more dewaxing lubricant base oil by a kind of crude oil feeding logistics, this method comprises: this crude oil feeding is sent into pressure remain between 1.7 crust and 6.7 crust (definitely), column bottom temperature remains between 232 ℃ and 399 ℃ and tower top temperature remains in the atmospheric distillation tower between 204 ℃ and 316 ℃, so that this crude oil feeding is divided at least a tower base stream (drawing from this fractionation plant) that contains the lightweight overhead stream (drawing from the normal pressure fractionation plant) of heavy gas oil and lighter hydrocarbon and contain the hydrocarbon heavier than heavy gas oil; Other oil refining apparatus is drawn and delivered to above-mentioned heavy gas oil and lighter hydrocarbon with further processing; To draw from this atmospheric fractional tower, the tower base stream that contains the hydrocarbon heavier than heavy gas oil is sent into tower top pressure and is remained on 0.02 crust and 0.09 and cling between (definitely), tower top temperature remains between 38 ℃ to 93 ℃, tower bottom pressure remains on 0.13 and clings between 0.33 crust (definitely) and column bottom temperature remains in the vacuum fractionation tower between 316 ℃ to 399 ℃, to obtain at least four kinds of thick lubricating oil process-streams, contain ⅰ. the effusive light decompression gas oil of cat head, ⅱ. viscosity index is 80～100 or 80～150 high viscosity index (HVI) (below be abbreviated as HVI80～100 or 80～a 150) distillate, ⅲ. viscosity index is 250～300 high viscosity index (HVI) (below be abbreviated as HVI250～a 300) distillate, ⅳ. viscosity index is 500～600 high viscosity index (HVI) (below be abbreviated as HVI500～600) heavy distillate and ⅴ. contain the tower base stream of residual oil; Then, this tower base stream that contains residual oil is delivered to deasphalting unit, this residual oil is contacted with solvent, carry out the residual oil diasphaltene, generate and be rich in pitch logistics and diasphaltene lubricating oil (DAO) logistics; This is rich in the pitch logistics draws from this deasphalting unit; This diasphaltene lubricating oil (DAO) is drawn from this deasphalting unit; This HVI80～100 or 80～150 distillates, HVI250～300 distillates, HVI500～600 distillates and this DAO hydrocarbon stream are passed through the solvent extraction operation respectively, carry out solvent extraction there respectively, and with the HVI80 behind the solvent extraction that obtains respectively～100 or 80～150 content of wax raffinate oil, HVI250～300 content of wax are raffinated oil, HVI500～600 content of wax are raffinated oil and the bright stock content of wax is raffinated oil, and (being transformed by this DAO logistics) is transported to selectivity catalytic dewaxing operation respectively.This operation comprises: described HVI80～100 or 80～150 content of wax are raffinated oil logistics by the first catalytic dewaxing district that contains synthetic ferrierite (having a kind of melts combine of selecting from periodic table of elements VI B family, VII B family and VIII family at least in this zeolite) catalyzer is housed, to obtain pour point and be lower than the H VI 80～100 or 80～150 logistics of H VI of-4 ℃ basic dewaxing; H VI 250～300 content of wax behind the solvent extraction are raffinated oil logistics by the second catalytic dewaxing district of catalyzer is housed, to obtain pour point and be lower than H VI 250～300 lubricating oil of-4 ℃ basic dewaxing, it is 0.9 ± 0.2M at interior synthetic ferrierite and constitutive molar ratio that described catalyzer contains by at least a melts combine of selecting from periodic table of elements VI B family, VII B family and VIII family _2/nO: Al ₂O ₃: 5-100SiO ₂: 0-40H ₂O(wherein M is a positively charged ion, and n is this cationic valence mumber) the mixture formed of crystalline aluminosilicate zeolitic, the aperture of this zeolite is between 0.5 millimicron and 0.9 millimicron; H VI 500～600 content of wax behind the solvent extraction are raffinated oil logistics by the 3rd catalytic dewaxing district of catalyzer is housed, to obtain pour point and be lower than H VI 500～600 lubricating oil of-4 ℃ basic dewaxing, it is 0.9 ± 0.2M at interior synthetic ferrierite and constitutive molar ratio that described catalyzer contains by at least a melts combine of selecting from periodic table of elements VI B family, VII B family and VIII family _2/nO: Al ₂O ₃: 5-100SiO ₂: 0-40H ₂O(wherein M is a positively charged ion, and n is this cationic valence mumber) the mixture formed of crystalline aluminosilicate zeolitic, the aperture of this zeolite is between 0.5 millimicron and 0.9 millimicron; Is 0.9 ± 0.2M with the logistics of raffinating oil of the described bright stock content of wax by constitutive molar ratio is housed _2/nO: Al ₂O ₃: 5-100SiO ₂: 0-40H ₂O(wherein M is a positively charged ion, and n is this cationic valence mumber) the 4th catalytic dewaxing district of aluminosilicate zeolites (aperture is between 0.5 millimicron and 0.9 millimicron), the bright stock that makes pour point and be lower than-4 ℃ the basic dewaxing lubricating oil of raffinating oil.

All above-mentioned four kinds of different lubricant base feed streams all contain different content of wax pollutents, even oil pour point is brought up to the unbearably content of wax component of degree of adoption.The molecular characterization of these logistics is different with viscosity.In general, what must dewax also may have only two kinds of logistics, i.e. (1) H VI 80～100 or lightweight logistics and (2) heavy bright stock logistics of 80～150.Also have three kinds or more, by fractionating system logistics that produce, different viscosity.The present invention handles this type of two or more logistics on parallel working equipment, so that basic dewaxing.

Various tectosilicate catalyzer all can be used for handling arbitrary this type of logistics.A series in this type of tectosilicate is named is that ZSM-5 aluminosilicate composition, its characteristic determined by x-ray diffraction pattern, of the table 1 in No. the 3rd, 852,189, people's such as Chen the United States Patent (USP).

Estimate to also have other catalyzer to use in the present invention as a kind of catalyst component.For example, can also use mordenite, crystalline borosilicate and silicate.Can be upgrading mordenite,, but be not limited to these comprising upgrading mordenite through obtaining with these cationic exchange of H, Be, Mg, Tl, Ce, Nd, Pb, Th, Nb, Rh, Ba, Sr, La and Ca through cationic exchange.Also comprise with as metal chloride, the upgrading mordenite that obtains by vapor deposition techniques, but be not limited to these.

Second kind of tectosilicate series catalyst is that the class of raffinating oil such as H VI 80～100 or 80～150 content of wax is had optionally series catalyst than the light lubricant dewaxing, and its effect has to dewaxing than heavy lubricating oil with above-mentioned that optionally aluminosilicate is opposite.Winquist is at United States Patent (USP) the 4th, 343, and the example of being lifted in 692 is an example of this type of catalyzer.Other this type of catalyzer is, and is that handled or untreated, be with or without ZSM-35, ZSM-23, ZSM-38, ZSM-21 and the natural ferrierite of catalytic metal thereon.

Can also contemplate, this two classes catalyzer can place on the same class carrier, and according to the concentration that is combined in wherein metal, acid sites or guide to cationic difference on the carrier and make wax class reaction in a kind of catalyst selectivity ground and the light lubricant material, make another kind of catalyst selectivity ground and react than the wax class in the heavy lubricating oil material.

Though known above-mentioned two types dewaxing catalyst is suitable for the dewaxing of some charging, but do not recognize, unite the synchronous cooperation of using this catalyzer of two types, can be and face the refiner who whole different oils is dewaxed and get into a difficult position, unexpected, more feasible dewaxing process is provided.Two kinds of catalyzer, a kind of have an aperture close with ferrierite, and another kind has with ZSM-5 and equates or the aperture big than ZSM-5 why can free this predicament, is because the wax class that has in the light lubricant is with different than the wax class that has in the heavy lubricating oil.

Dewaxing step of the present invention or all steps that dewaxes are carried out in the presence of hydrogen, are 350 and 2670 liters of (STP) H at the hydrogen cycling rate preferably ₂/ carry out under rising between the feed oil." STP " expression standard temperature (℃) and standard pressure (1 crust, absolute).Reaction conditions generally be holding temperature between 150 ℃ and 500 ℃, pressure preferably clings between (definitely) 2 and 20 between 2 and 200 crust (definitely).More suitable liquid hourly space velocity (LHSV) is from 0.1 to 10, especially with between 0.5 and 5.0 for the most suitable.

The thick lubricating oil that contemplated herein need parallel working are handled generally contains in 0.1 to 50%(weight) waxy hydrocarbon (referring generally to when the temperature of hanging down 3 ℃ than pour point is solid-state hydrocarbon) in the scope.Pour point is by the ASTM(American Standard of Testing Materials) the D-97 determination of test method.For example, the pour point of H VI 80～100 or 80～150 processed oils is-18 ℃, and the pour point of H VI bright stock processed oil is-7 ℃.Selection is applicable to the special dewaxing catalyst of concrete charging, is the key that the present invention operates.At first must study in the lubricant base raw material, exist, the type of undesired waxy hydrocarbon, because found the type of existing content of wax material in the content of wax of H VI 80～100 or 80～150 lubricant base raw materials is raffinated oil, the type of content of wax material in raffinating oil with H VI 250～300, H VI 500～600 or the bright stock content of wax, both are different.In fact, the wax in overweighting the thick lubricating oil of H VI 80～100 or 80～150 contains the more side chain and the ring texture of vast scale than H VI 80～100 or 80～150 curiously.This in fact discovery relate to do not recognize as yet so far have an aperture catalyzer problem close with ferrierite, be the wax that this type of catalyzer can not remove ring texture, therefore can not dewax to than the lubricating oil logistics that H VI 150 lubricating oil weigh meets the pour point of market demands.

The average carbon number that it is believed that the content of wax thing in the lubricating oil that is present in H VI 80～100 or 80～150 is 23, but known concerning the single composition of this logistics, and its hydrocarbon compositional range comprises 18 carbon atoms and 31 carbon atoms of trace.It is believed that the source difference of based on crude, the average carbon number that is present in the content of wax thing in the lubricating oil of H VI 250～300 is 29 or 31, and the scope of its hydrocarbon component comprises the hydrocarbon of some 24 carbon to 37 carbon.The average carbon number that it is believed that the content of wax hydro carbons in H VI bright stock is 38, and its hydrocarbon compositional range comprises the hydrocarbon of some 22 carbon atom to 52 carbon atoms.First kind of content of wax (H VI 80～100 or 80～150) contained wax of raffinating oil can contain the weight greater than 45%() normal alkane, logistics such as bright stock and other content of wax is raffinated oil, its normal alkane component may be less than 10%(weight).The concentration of this nalka chloroflo structure will be decided on the crude oil of access to plant.Be surprised to find that so a large amount of side chain and ring-type components arranged, in heavy oil promptly greater than 55%(weight), and in light oil contained side chain and ring-type component less than 55%.

In the independent parallel operation that provides, (a kind of aperture is similar to ferrierite to two kinds of dewaxing catalysts, another kind of aperture be similar to or greater than ZSM-5) synchronous cooperation, will reduce the size of dewaxing special purpose reactor, although required reactor may be more.Stop at the handiness of the dewaxing (and another kind of catalyzer continues its synchronous operation) on its a kind of catalyzer, and before entering running temperature rise in latter stage, just select regeneration, can prolong the work-ing life of macroporous catalyst significantly, unlikely owing to its mis-behave loses product.Owing to avoided the full factory that reactivation of catalyst caused to stop work,, can establish storage tank outside the battery limit (BL) less, and the device of each reactor also can design lessly so whole dewaxing device can design lessly.If device has an accident, perhaps pollutent (as sodium) enters in a certain reactor, and other reactor still continues its operation, is not subjected to overslaugh.If the crude oil feeding of refinery has changed, since the handiness of the catalyzer that provides, the original plan target that still can maintain market.

In this parallel circulation operating system, can and preferentially adopt successive dewaxing operation.Because the sealing of the hydro carbons that absorbs, or enclose a spot of catalyzer poison and during active decline when some catalyzer, can carry out the hydrogen reactivate of catalyzer by the simple steps operation that stops to dewax.The hydrogen reactivate is under the temperature between 343 ℃ to 538 ℃, finishes in the presence of hydrogen-containing gas.Can make a kind of dewaxing catalyst reactivate or regeneration, other dewaxing catalyst then continues to finish its catalyst operation separately, exhausts up to their activity and needs reactivate.

Can carry out the oxidation regeneration of catalyzer on the spot, perhaps preferably regenerate in the other regeneration container outside the battery limit (BL), method is to pass through oxygen-containing gas under 371 ℃ to 566 ℃ temperature, and the recovery time will fully be removed sedimentary coke, thus the regeneration dewaxing catalyst.Regenerated catalyzer sent in its separately dewaxing reactor thereafter.Oxygen-containing gas can be air, purity oxygen or oxygen and other mixed gas as the rare gas element of classes such as nitrogen or hydrogen.

In the scope of the invention, plan to handle as previously mentioned at least two kinds even four kinds of lubricant base raw materials from vacuum distillation apparatus.But in the scope of the invention, these logistics are fusion mutually also, as long as in the parallel working reaction zone, for undesired content of wax thing in the conversion base oil raw material adopts at least two kinds of different catalyzer.In addition, also provide the lower procedure of whole catalytic dewaxing process, the technology that is adopted comprises clay treatment and hydrofining, to improve the colourity and the stability of pressed oil.Further propose, downstream at whole catalytic dewaxing process, can adopt conventional mixing process to prepare various lubricant bases or technical oils, for example automotive engine oil, transformer oil, compressor oil, locomotive are with oil, refrigerator oil, hydraulic efficiency oil, gear oil or need arbitrary other lubricant of special pour point quality under specified temperature.

The invention still further relates to the catalysis for preparing by method as mentioned above and take off lubricant base.

Represented process sketch is from crude oil feeding in the accompanying drawing, produces the example of four kinds of different dewaxing lubricant base oils.But this process sketch also can be suitable for to two kinds of different lubricating oil logistics for few.

This schema is not given utility appliance miscellaneous such as finishing the required various pumps of this process, condenser, susceptor.This schema can not be construed as limiting this novel parallel operational method.In the drawings, the crude oil in the pipeline 1 is sent to separation column 3, discharges light product steam by pipeline 5 there, is cat head or side-stream or the two, discharges from process and sends to further processing to reclaim other hydrocarbon ils.Vacuum distillation apparatus 9 is discharged and delivered to the tower base stream of separation column 3 by pipeline 7.This logistics comprises all heavier than heavy gas oil material.In vacuum still, produced nearly five kinds of logistics, overhead stream is discharged by pipeline 11, and its initial boiling point is about 238 ℃, and 50% recovered temperature is about 354 ℃, also will further process according to known common process technology, is worth to improve its oil plant.For instance, from vacuum distillation apparatus, discharge three logistics as side line, be the slightly blue oil not that H VI 80～100 or 80～150, H VI 250～300 and H V 500～600 contain content of wax thing, above-mentioned content of wax thing can make pour point high to the planned target that is an impediment to open lubricating oil market.H VI 80～100 or 80～150 distillate logistics are discharged by pipeline 13, and the distillate logistics of H VI 250～300 is discharged by pipeline 15, and the distillate logistics of H VI 500～600 is discharged by pipeline 17.The 5th logistics discharged by pipeline 19 at the bottom of the tower of vacuum distillation tower 9, wherein contains just like heavier feeds such as pitch and residual oil.This logistics will be delivered to deasphalting unit 21, discharges rich bitumen product by pipeline 23 there, and produced simultaneously deasphalted oil is then discharged through pipeline 25.This logistics generally uses term (DAO) to represent, wherein still contains the undesirable content of wax thing of inherent, and this content of wax thing can be brought up to the pour point of lubricating oil in most of industrial degree that can not be suitable for.

Can choose wantonly in the present invention and whether adopt pre-solvent extraction system to handle content of wax lubricating oil distillate.Solvent is as in the common extraction solvents such as phenol, N-N-methyl-2-2-pyrrolidone N-, furfural any.These solvent streams are joined respectively in intermittent type extraction plant 27,29,31 and 33 by pipeline 35,37,39 and 41.Logistics 43,45,47 and 49 be the discharging a kind of slip shape logistics (slip stream) or tower at the bottom of the foreign material logistics, wherein contain the aromatic hydrocarbon, nitrogen and the sulphur compound that extract, these logistics need (not drawn on the figure) in distillation tower yet and are handled, solvent is turned back to the solvent extraction system.Part or all logistics for 51,53,55 and 57 also will adopt above-mentioned treating method.It must be noted that, this solvent extraction system can multi-region or in a district with the discontinuous method operation, whenever next only carries out solvent extraction to the logistics of raffinating oil of each content of wax that comes from vacuum still respectively in a time.Each logistics from the solvent extraction district is delivered to optional hydrotreatment system 59,61,63 and 65 by pipeline 51,53,55 and 57, and hydrogen inlet pipeline 67,69,71 and 73 is arranged in this system.Though these hydrotreaters are with several expression respectively, in fact they can be an integral device that is used to handle multiple logistics.Also can before solvent extraction, carry out hydrotreatment.In any case, this dewaxing hydrogenation pretreating zone is sheerly chosen wantonly, it exists and the layout arrangement, in the parallel circulation operation process chart of the two-way of lubricant base raw material on different catalyst for hydrogenation de-waxing of current consideration, is not the necessary process feature of whole technological process.

The effect of hydrotreater is exactly to remove impurity aromatic hydroxy compound, sulphur compound, nitrogen compound, and the aromatic hydroxy compound of complexity is changed into better simply aromatic hydroxy compound, so that catalytic dewaxing process is easier to carry out.Hydrotreatment is to carry out under the hydroprocessing condition of gentleness, comprises temperature from 260 ℃ to 454 ℃, and pressure clings to (definitely) to 107 crust (definitely) from 74.In hydrogen, can or use pure hydrogen with rare gas element.Also can consider will be such as refinery logistics such as reformate gas streams as the hydrogen source.But, must point out again that this dewaxing hydrogenation pre-treatment step is chosen wantonly, need not to finish purpose of the present invention by it.That cross through solvent extraction or cross and each logistics (or logistics of only handling) through hydrotreatment more if necessary through single hydrotreater, discharge by pipeline 75,77,79 and 81 from hydrotreater 59,61,63 and 65 respectively.These logistics directly are sent to each corresponding catalytic dewaxing unit 83,85,87 and 89, and having hydrogen to enter pipeline 91,93,95 and 97 there provides hydrogen.Each dewaxing lubricant is discharged by pipeline 99,101,103 and 105 from each catalyzer dewaxing device (perhaps at least 2 devices) 83,85,87 and 89 respectively, goes further blending again.

After producing these logistics, generally to carry out hydrotreatment, with further refining final dewaxed product.A remarkable advantage of the present invention is exactly that the product in the pipeline 99 need not fully again through hydrotreatment after concocting with other feed stream use magnesium alkali zeolite catalyst in dewaxing district 83 after.Save that this is expensive and may be the additional step of trouble, unexpectedly producing one needs any other method of hydrotreatment dewaxing lightweight oil to want effectively and the whole process of saving money compared with those.If necessary, with the interior hydrotreatment that also can comprise lightweight oil dewaxing logistics, however doing is not have what benefit economically in the scope of the invention.In a word, present method adopts relatively effectively catalyzer, and production lightweight H VI 80～100 or 80～150 lubricant base need not carry out the pressed oil that hydrotreatment produces with other heavy pressed oil that may need to dewax in the presence of hydrogen.

Another specific embodiments of the present invention comprises directly delivers to hydrotreater 65 with deasphalted oil (DAO) logistics from deasphalting unit 21 without the solvent extraction step, should pre-dewaxing hydrotreatment be under gentle or harsh hydroprocessing condition, to carry out, be that pressure clings to (definitely) greater than 74, temperature is greater than 260 ℃.The logistics of hydrotreatment is sent to catalyzer dewaxing device 89 by pipeline 81, carries out above-mentioned processing again.

When needs low-down (for example being lower than-18 ℃) lubricating oil pour point, also can choose a pre-solvent dewaxing system in the present invention wantonly and handle content of wax lubricating oil and raffinate oil.Solvent promptly is common dewaxing solvent, and for example propane or the alkyl ketone that mixes with aromatic components are as methylethylketone and toluene.Can these logistics be introduced with the form of periodical operation.Solvent can reclaim and reuse in the solvent dewaxing process by distillation.This pre-solvent dewaxing process can be carried out in several districts, also can carry out in a district, adopts periodical operation, handles a kind of content of wax of vacuum still generation at every turn and raffinates oil.

In Hydrodewaxing device 83, catalyzer is the catalyzer that the aperture is similar to synthetic ferrierite aperture preferably.The catalyzer preferably (being used for the bright stock content of wax raffinates oil) that is used for Hydrodewaxing device 89 is that the aperture is similar to or greater than United States Patent (USP) the 3rd, 702, the catalyzer in the ZSM-5 catalyzer aperture described in No. 886.The latter also can be used for Hydrodewaxing device 85 and 87 altogether with the smaller zeolite in aperture.In addition, owing to used magnesium alkali zeolite catalyst preferably, avoided the dewaxing back end hydrogenation to handle.

Operational condition in separation column 3 or 9, deasphalting unit 21, solvent extraction device 27,29,31,33 and hydrotreater 59,69,71 and 73 is well-known to those those skilled in the art.The condition and the adoptable catalyzer that logistics 101,103,105 or they and 99 logistics that combine are carried out hydrotreatment also are notorious.In the reactor 83,85,87 and 89, the operational condition of Hydrodewaxing step then as previously described.As long as selected charging just can be determined optimal conversion condition at the special-purpose catalyst composition of 83,85,87 and 89 each devices, and without any need for technical skill or undue experimentation.

Claims (10)

1, the refinery produces the catalytic dewaxing process of more than one lubricant base raw materials, this method comprises: in first reaction zone, under hydrogen-containing gas existence and Hydrodewaxing condition, make first via feed stream (contain first kind of refinery and produce raffinating oil of lubricant base raw material, wherein contain the first kind of wax that comprises straight-chain paraffin, the side chain of this first kind of wax and cyclic hydrocarbon content less than 55% (weight) with have optionally to transforming above-mentioned first kind of wax that first kind of catalyst for hydrogenation de-waxing contacts, in second reaction zone that be arranged in parallel, under hydrogen-containing gas existence and Hydrodewaxing condition, make the second tunnel refinery produce the raffinating oil of lubricant base raw material (wherein contain and comprise) and have optionally to transforming above-mentioned second kind of wax that second kind of catalyst for hydrogenation de-waxing contacts greater than the side chain of 55% (weight) and/or second kind of wax of cyclic hydrocarbon, and in optional one or more other reaction zone, under hydrogen-containing gas existence and Hydrodewaxing condition, the content of wax that makes other refinery produce the lubricant base raw material is raffinated oil and is contacted with catalyst for hydrogenation de-waxing, obtains the parallel logistics that two kinds of refineries produce the dewaxing lubricant base oil from above-mentioned reaction zone at least.

2, according to the process of claim 1 wherein the logistics of described lubricant base material feeding, obtain through oil at the bottom of the tower of fractionation hydrocarbon ils feed stream air distillation.

3, according to the method for claim 1 or 2, wherein said Hydrodewaxing condition comprises temperature between 150 ℃ and 500 ℃, and pressure is between 2 and 200 crust (definitely), and hydrogen/oily charge ratio is at 350 and 2670 liters of (under the standard temperature and pressure) H ₂Between/liter oily the charging.

4, according to the method for claim 1 or 2, wherein said first kind of catalyst for hydrogenation de-waxing comprises the synthetic ferrierite, wherein introduces a kind of metal in VII B family, VII B family and the VIII family in the periodic table of elements that is selected from least.

5, according to the method for claim 4, wherein said first kind of feed stream comprises the content of wax lube stock of HVI80～150 or 80～100, and this oil plant is Hydrodewaxing in first reaction zone, handles from then on to obtain lubricant base without follow-up hydrogenation.

6, according to the method for claim 1 or 2, wherein said second kind of catalyst for hydrogenation de-waxing comprises having the aperture from 0.5 millimicron to 0.9 millimicron crystalline aluminosilicate, and the mol ratio of its composition is:

0.9 ± 0.2M ₂/ nO: Al ₂O ₃: 5-100SiO ₂: 0-40H ₂O(wherein M is a positively charged ion, and n is this cationic valence mumber).

7, according to the method for claim 1 or 2, the catalytic hydrodewaxing zone that be arranged in parallel comprising at least 3 (preferably 4 or more).

8,, under the situation that wherein said various catalyst for hydrogenation de-waxing can have nothing to do in the dewaxing operation with other dewaxing reaction zone, be to regenerate under 371 ℃ to the 566 ℃ conditions in oxygen-containing gas existence and temperature according to the method for claim 1 or 2.

9, to carry out reactivate from 343 ℃ to 538 ℃ under the condition in hydrogen-containing gas existence and temperature subsequently with the catalyzer after the rare gas element flushing regeneration after the method according to Claim 8, wherein said regeneration.

10, according to the method for claim 1 or 2, at least two kinds of dewaxing lubricant base oils are wherein made at least a lube product through blending.

Images