CN1158377C - Dewaxing process - Google Patents

Dewaxing process Download PDF

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CN1158377C
CN1158377C CN 98813229 CN98813229A CN1158377C CN 1158377 C CN1158377 C CN 1158377C CN 98813229 CN98813229 CN 98813229 CN 98813229 A CN98813229 A CN 98813229A CN 1158377 C CN1158377 C CN 1158377C
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feed
method according
hydrocarbon oil
catalyst
dewaxing
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CN 98813229
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CN1284115A (en )
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J・M・罗森鲍姆
J·M·罗森鲍姆
豪厄尔
R·L·豪厄尔
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切夫里昂美国公司
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00Cracking of hydrocarbon oils in the presence of hydrogen or hydrogen generating compounds, to obtain lower boiling fractions
    • C10G47/02Cracking of hydrocarbon oils in the presence of hydrogen or hydrogen generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10Cracking of hydrocarbon oils in the presence of hydrogen or hydrogen generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12Inorganic carriers
    • C10G47/16Crystalline alumino-silicate carriers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves

Abstract

用于转化烃油的本发明方法包括下列步骤:(1)在加入的氢气存在下,使烃油进料与催化剂接触,该催化剂选自SAPO-11,SAPO-31或SAPO-41的中等孔径硅铝磷酸盐分子筛和加氢组分,及其混合物,其中至少一部分进料被转化;和(2)将至少一部分转化了的进料通入分馏塔,其中分馏至少一部分转化了的进料,从而产生至少一种塔顶馏分和一种塔底馏分;和(3)将至少一部分塔底馏分与步骤(1)的烃油进料混合。 The method of the present invention for conversion of hydrocarbon oils comprising the steps of: (1) in the presence of hydrogen added to the hydrocarbon oil feedstock with a catalyst, the catalyst is selected from SAPO-11, SAPO-31 or SAPO-41 intermediate pore size of silicoaluminophosphate molecular sieve and a hydrogenation component, and mixtures thereof, wherein at least a portion of the feed is converted; and (2) converting at least part of the feed into the fractionation column, wherein converting at least part of the fractionation of the feed, thereby producing at least one overhead fraction and one bottoms fraction; and (3) at least a portion of the bottoms fraction of step (1) mixing a hydrocarbon oil feed.

Description

脱蜡方法 Dewaxing method

发明领域本发明涉及使润滑油催化脱蜡的方法。 Field of the Invention The present invention relates to a method for catalytic dewaxing the lubricating oil. 更准确地说,该发明涉及使烃油进料脱蜡的方法,其中至少部分分馏塔底产物再循环到进料中。 More specifically, the invention relates to dewaxing of hydrocarbon oil feed, wherein at least a portion of fractionator bottoms recycled to the feed.

发明背景某些石油馏出物脱蜡的方法是公知的。 BACKGROUND OF THE INVENTION Some petroleum distillate dewaxing methods are well known. 当高石蜡油用于在低温下时,它必须是流动的产品例如润滑油,燃料油,和喷气式发动机燃料中时,就需要脱蜡。 When a high paraffin oil at a low temperature, it must be liquid products such as lubricating oil, fuel oil, and jet fuels, it is necessary dewaxing. 存在于这种油中的较高分子量直链正构的、取代的和低支链链烷烃是蜡,该蜡会引起油的高倾点和高浊点。 This oil is present in the higher molecular weight n-linear, substituted and slightly branched paraffins is a wax, the wax will cause high pour points and high cloud points in the oils. 如果要得到足够的低倾点,就必须全部地或部分地除去蜡。 To obtain a sufficiently low pour point, it is necessary to wholly or partially remove the wax. 在过去,使用了各种溶剂除去技术以除去这些蜡,比如丙烷脱蜡和甲乙酮脱蜡;然而,这些技术的操作费用高、严重环境影响和产生质量次于催化-脱蜡油的油。 In the past, various solvent removal techniques to remove these waxes, such as propane dewaxing dewaxed and methyl ethyl ketone; however, the high operating costs of these technologies, a serious environmental impact and produce inferior quality Catalytic - oil dewaxing. 催化脱蜡方法是更经济的,并且通过选择性异构化和裂化链烷烃组分、产生低分子量产物来除去蜡,其中有些低分子量产物可以通过蒸馏除去。 Catalytic dewaxing processes are more economical, and by isomerization and selective cracking chain alkanes, produce low molecular weight products to remove wax, some low molecular weight products can be removed by distillation.

因为它们的选择性,已知的脱蜡催化剂通常包括具有下述孔径的铝硅酸盐沸石,该孔径仅可接纳直链正链烷烃或与其一起的仅仅是低支链的链烷烃,但是排除更多支链的物质、大的环脂族化合物和芳烃。 Because of their selectivity, known dewaxing catalysts generally comprise an aluminosilicate zeolite having a pore diameter below, the aperture may only receive or straight chain n-paraffins together therewith only low branched paraffins, but excluding more branched species, a large cycloaliphatic and aromatic compounds. 已经建议沸石例如ZSM-5,ZSM-11,ZSM-12,ZSM-23,ZSM-35和ZSM-38用于脱蜡方法。 Has been proposed, for example, zeolites ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35 and ZSM-38 for the dewaxing process. 这些沸石的应用描述在美国专利3,700,585;3,894,938;4,176,050;4,181,598;4,222,855;4,229,282和4,247,388中,这些专利公开的内容引入本文作为参考。 Application of these zeolites is described in U.S. Patent No. 3,700,585; 3,894,938; 4,176,050; 4,181,598; 4,222,855; 4,229,282 and 4,247,388 the contents disclosed in these patents incorporated herein by reference.

因为具有这种功能的许多脱蜡方法是通过裂化反应的,因此许多有用的产物降解成低分子量物质。 Since many dewaxing process is the cracking reaction by having such a function, and therefore many useful products degraded into low molecular weight substances. 例如,含蜡的链烷烃可以裂化成丁烷,丙烷、乙烷和甲烷,它们是对油的蜡状性质不起作用的较轻的正链烷烃。 For example, waxy paraffins may be cracked to butane, propane, ethane and methane, which is inactive waxy nature of the oil lighter n-paraffins. 因为这些较轻产物通常比较高分子量的物质具有更低的价值,因此需要限制催化脱蜡方法期间发生的裂化程度。 Because the degree of cracking occurring during these lighter products are generally higher molecular weight material has a lower value, it is necessary to limit the catalytic dewaxing process.

欧洲专利申请225,053公开了一种生产润滑油的方法,该方法包括通过异构化脱蜡来部分脱蜡润滑油基础进料,接着选择脱蜡步骤。 European Patent Application 225,053 discloses a process for producing lubricating oil, the method comprising isomerization dewaxing be dewaxed lubricating base feed section, then select the dewaxing step. 该异构化脱蜡步骤的进行使用了大孔高硅沸石脱蜡催化剂,比如高硅Y沸石或β沸石,这些催化剂使基础进料中的含蜡组分异构化成为低含蜡的支链异链烷烃。 The isomerization dewaxing step performed using a large pore high silica zeolite dewaxing catalyst such as high silica zeolite Y or zeolite β, the base catalyst feed waxy components become isomerized wax containing branched low chain isoparaffins. 选择性脱蜡步骤或者可以是溶剂脱蜡,例如甲乙酮脱蜡操作,或者可以是催化脱蜡,优选使用高选择性沸石比如ZSM-22或ZSM-23。 Selective dewaxing step or solvent dewaxing may be, for example, methyl ethyl ketone dewaxing or catalytic dewaxing may be preferable to use highly selective zeolites such as ZSM-22 or ZSM-23.

美国专利4,437,976公开了二段烃脱蜡加氢处理方法,其中通过在沸石催化剂存在下使进料催化脱蜡,然后在加氢处理催化剂存在下使其至少液体部分经过加氢,来降低沸点为400°F-1050°F的烃进料的倾点,其中所述的加氢处理催化剂含有加氢组分和选自ZSM-5,ZSM-11,ZSM-23和ZSM-35沸石的含硅多孔结晶物质。 U.S. Patent No. 4,437,976 discloses a two-stage hydrocarbon dewaxing hydrotreating process wherein the feed by catalytic dewaxing in the presence of a zeolite catalyst, and then in the presence of a hydrogenation catalyst such that at least part of the liquid after hydrogenation, to lower the boiling point of 400 ° F-1050 ° F the pour point of the hydrocarbon feed, wherein the hydrotreating catalyst comprising a hydrogenation component selected from silicon-containing ZSM-5, ZSM-11, ZSM-23 and ZSM-35 zeolite a porous crystalline material.

Chester等人的美国专利4,575,416公开了一种加氢脱蜡方法,该方法使用了具有约束指数不小于1、具有规定性质的第二催化组分和加氢组分的第一沸石催化剂。 The first zeolite catalyst Chester et al., U.S. Patent No. 4,575,416 discloses a hydrodewaxing process using the method having a Constraint Index not less than 1, having a second predetermined properties of the catalytic component and a hydrogenation component.

美国专利5,149,421提出了一种脱蜡催化剂,该催化剂提供了对脱蜡方法中得到的产物性质的优良选择性。 U.S. Patent No. 5,149,421 proposes a dewaxing catalyst which provides superior selectivity for the product properties obtained in the dewaxing process. 通过在脱蜡方法中使用中等孔径硅铝磷酸盐分子筛催化剂,烃油进料被有效地脱蜡,得到的产物比使用其他铝硅酸盐沸石得到的产物具有更高的分子量。 By using an intermediate pore size silicoaluminophosphate molecular sieve in the catalyst in the dewaxing process, hydrocarbon oil feedstock is effectively dewaxed to obtain products other than the product obtained aluminosilicate zeolites having a higher molecular weight. 与上述使用铝硅酸盐沸石的现有技术相比,由脱蜡方法得到的产物在给定的倾点下具有更好的粘度和粘度指数。 As compared with the prior art aluminosilicate zeolites, the product obtained by the dewaxing process have better viscosities and viscosity index at a given pour point.

然而,有利的是提供这样一种方法,该方法提供了比已知方法更高的收率,或者在相同的收率下使倾点的降低值增大了。 However, it is advantageous to provide such a method, the method provides a higher yield than the known methods, or to reduce the pour point value at the same yield is increased. 本发明就提供了这样的方法。 The present invention provides such a method.

发明概述本发明克服了现有技术中的这些问题和缺点,提供了烃油催化脱蜡的方法,该方法产生了优良的润滑油收率。 SUMMARY The present invention overcomes these problems and disadvantages of the prior art, a catalytic dewaxing of a hydrocarbon oil, the method produces a superior lube yield.

本发明转化烃油的方法包括下面步骤:(1)在加入的氢气存在下,使烃油进料与催化剂接触,该催化剂选自SAPO-11,SAPO-31或SAPO-41的中等孔径硅铝磷酸盐分子筛和一种加氢组分及其混合物,其中转化了至少部分进料;和(2)使至少部分转化的进料通过分馏塔,在分馏塔中分馏至少部分转化了的进料,从而产生至少一种塔顶馏分和一种塔底馏分;和(3)使至少部分塔底馏分与步骤(1)的烃油进料混合。 The method of the present invention into hydrocarbon oils include the following steps: (1) in the presence of hydrogen added to the hydrocarbon oil feedstock with a catalyst, the catalyst is selected from an intermediate pore size silicoaluminophosphate SAPO-11, SAPO-31 or SAPO-41 of the molecular sieves and one hydrogenation component, and mixtures thereof, wherein at least part of the feed conversion; and (2) at least partially converted feed by fractional distillation column, a fractionation is at least partially converted feed fractionation column, thereby producing at least one overhead fraction and one bottoms fraction; and (3) at least part of the bottom fraction of step (1) mixing a hydrocarbon oil feed.

附图简述图1描述了本发明方法的一个实施方案的简化流程图。 DRAWINGS Figure 1 depicts a simplified flow diagram of one embodiment of the method of the present invention.

发明详述A.方法的步骤本发明转化烃油的方法包括下面步骤:(1)在加入的氢气存在下,使烃油原料与催化剂体系接触,该催化剂体系包括选自SAPO-11,SAPO-31或SAPO-41的中等孔径硅铝磷酸盐分子筛和一种加氢组分及其混合物的催化剂,其中转化了至少部分进料;和(2)使至少部分转化了的进料通过分馏塔,在分馏塔中分馏至少部分转化进料,从而产生至少一种塔顶馏分和一种塔底馏分;和(3)使至少部分塔底馏分与步骤(1)的烃油进料混合。 DETAILED DESCRIPTION A. method step of the method of the present invention conversion of hydrocarbon oils include the following steps: (1) in the presence of hydrogen added to the hydrocarbon oil feedstock with the catalyst system, the catalyst system include those selected from SAPO-11, SAPO- intermediate pore size silicoaluminophosphate molecular sieve catalyst and one hydrogenation component, and mixtures of SAPO-41 or 31, wherein at least part of the feed conversion; and (2) contacting the at least partially converted feed by fractional distillation column, fractionating at least partially converted feed fractionation column to produce at least one overhead fraction and one bottoms fraction; and (3) at least part of the bottom fraction of step (1) mixing a hydrocarbon oil feed.

催化剂体系还任选地包括选自中等孔径铝硅酸盐沸石催化剂、无定形催化剂及其混合物的催化剂。 The catalyst system optionally further comprises an aluminosilicate selected from medium pore zeolite catalyst, an amorphous catalyst and the catalyst mixtures. 为进行预处理,该进料可以进行加氢裂解或溶剂抽提和加氢处理。 For pretreatment, the feed may be hydrocracked or solvent extracted and hydrotreated. 这类方法和典型的加氢裂解条件描述在1990年5月1日授权的Miller的美国专利4,921,594中,该专利全部引入本文作为参考。 Such methods and typical hydrocracking conditions are described in U.S. Patent May 1, 1990 to Miller authorized 4,921,594, which patent is fully incorporated herein by reference. 后处理可以包括下述的加氢精制。 Post-processing may include the following hydrorefining.

不受到理论的限制,在一个实施方案中,脱蜡机理是蜡状化合物的异构化和/或裂化。 Not limited by theory, in one embodiment, the dewaxing mechanism is isomerization of waxy compound and / or cracking. 通常,与溶剂脱蜡相比,催化脱蜡例如Chevron的ISODEWAXING催化脱蜡方法改善了进料的倾点和粘度指数。 Typically, compared to solvent dewaxing, catalytic dewaxing of Chevron e.g. ISODEWAXING catalytic dewaxing process improves the pour point of the feed and the viscosity index.

B.进料本发明方法可以用来使各种烃油进料脱蜡,通常分类为任何含蜡烃进料,润滑油进料,或中间馏分油。 B. feed process of the present invention can be used to make a variety of hydrocarbon oil feed dewaxing, generally classified as any waxy hydrocarbon feed, feed lubricating oil, or middle distillates. 进料包括馏分油,例如加氢裂化产物,高沸点润滑油料,比如脱沥青油和溶剂抽提油。 The feed comprises a distillate, e.g. hydrocracked product, a high boiling point lubricating oil stocks, such as deasphalted oil and solvent extraction of oil. 进料通常是沸点高于约350°F的C10+进料,因为轻质油通常不含有大量的含蜡组分。 The feed is usually higher than the boiling point of the C10 + feedstock to about 350 ° F, because light oil generally do not contain large amounts of waxy components. 然而,该方法使用下列原料是特别有用的,这些原料包括馏分油料例如中间馏分油,包括粗柴油,煤油,和喷气式发动机燃料,润滑油料,燃料油和其倾点和粘度需要保持在某种规格限度范围内的其他馏分油。 However, this method using the following starting materials are particularly useful, such materials include, for example, the middle distillate oil fraction, including gas oil, kerosene, and jet fuels, lubricating oil stocks, and the fuel oil viscosity and pour point which needs to be kept a certain other distillates within the specification limits. 通常,润滑油料的沸点高于230℃(450°F),更通常高于315℃(600°F)。 Typically, the lubricating oil feedstock having a boiling point higher than 230 ℃ (450 ° F), more typically greater than 315 ℃ (600 ° F).

氢处理油料是这种油料和其他馏分油的适合来源,因为它们含有比溶剂处理油料更高的氢含量,并且通常相对来说没有杂原子(例如硫和氮化合物),这些杂原子会损害脱蜡和加氢精制催化剂的性能。 Hydrogen treatment of this oil are suitable sources of oil and other distillate oil, because they contain more oil than the hydrogen content of the solvent treatment, and are generally relatively free heteroatoms (such as sulfur and nitrogen compounds), these heteroatoms off damage of the wax and hydrofining catalyst. 本方法的进料通常是C10+进料,含有链烷烃,烯烃,环烷,芳烃和杂环化合物和大量的高分子量正链烷烃和提供给进料含蜡性质的低支链和取代的链烷烃。 The feed of the present process is typically C10 + feedstock containing paraffins, olefins, naphthenes, aromatics and heterocyclic compounds and a large amount of high molecular weight n-paraffins and provided to feed low-branched wax properties and substituted paraffins . 在加工期间,进料分子经过一些裂化或加氢裂解,形成可用于低粘度产物的液体物质。 During processing, feed molecules after some cracking or hydrocracking to form liquid substances may be used for a low viscosity product. 然而,要限制发生裂化的程度,以保持有价值的液体的收率。 However, to limit the extent of cracking occurs, in order to maintain the yield of valuable liquid.

典型的进料包括轻粗柴油,重瓦斯油和沸点高于350°F的常压渣油。 Typical feedstocks include light gas oil, heavy gas oil and atmospheric residue boiling above 350 ° F in. 在一个实施方案中,进料含有主要量的、沸点高于约350°F的烃油进料和含有直链和低支链烃。 In one embodiment, the feed containing a major amount of a hydrocarbon oil feedstock boiling above about 350 ° F and containing straight chain and slightly branched chain hydrocarbons. 术语″主要量″是指超过50重量百分数。 The term "major amount" means more than 50 weight percent.

虽然当进料含有有机氮(含氮杂质)时本发明方法仍可以实际应用,但优选进料中的有机氮含量小于50ppmw,更优选小于10ppmw。 Although the method of the present invention when the feed may actually still contains organic nitrogen applied when (nitrogen containing impurities), but the organic nitrogen content of the feed is preferably less than 50 ppmw, more preferably less than 10 ppmw. 当进料含有小于10ppmw有机氮时,以催化剂的活性和周期长度(连续再生或启动和第一次再生之间的时间)表示时,得到了特别好的效果。 When the feed contains less than 10ppmw organic nitrogen, and the active catalyst cycle length (time between successive reproduction or start and first regeneration) is obtained particularly good results.

C.硅铝磷酸盐分子筛催化剂组合物1.概况:中等孔径硅铝磷酸盐分子筛(SAPO)是用于本发明方法的催化剂。 C. silicoaluminophosphate molecular sieve catalyst composition 1. Overview: intermediate pore size silicoaluminophosphate molecular sieve (of SAPO) catalyst used in the process of the present invention. 适当的SAPO是任何常规的中等孔隙SAPO。 Appropriate SAPO any conventional intermediate pore SAPO. 该SAPO是单独使用,或与沸石和/或无定形催化剂结合使用。 The SAPO used alone, or in combination with zeolite and / or amorphous catalysts. 可用于本发明的硅铝磷酸盐分子筛的例子描述在美国专利4,440,871和5,149,421中,这些专利公开的内容引入本文作为参考。 Examples of the present invention can be used in the silicoaluminophosphate molecular sieves described in U.S. Patent No. 4,440,871 and 5,149,421, the contents of these patents are incorporated herein by reference in the disclosure.

该中等孔径硅铝磷酸盐分子筛催化剂用于本发明方法中,以转化含蜡组分成为不含蜡组分,并将它们的倾点降低约30°F至约60°F。 The intermediate pore size silicoaluminophosphate molecular sieve catalysts used in the process according to the present invention, the conversion of waxy components become wax-free components and reduce their pour point of about 30 ° F to about 60 ° F. 所用的催化剂的量取决于反应条件。 The amount of catalyst used depends on the reaction conditions.

在一个优选实施方案中,最终催化剂将是组合物,其包括中等孔径硅铝磷酸盐分子筛,铂或钯加氢金属组分和无机氧化物基质。 In a preferred embodiment, the final catalyst is a composition comprising intermediate pore size silicoaluminophosphate molecular sieve, platinum or palladium hydrogenation metal component and an inorganic oxide matrix. 适用于本发明方法中的优选中等孔径硅铝磷酸盐分子筛包括SAPO-11,SAPO-31和SAPO-41。 A method suitable for the present invention is preferably an intermediate pore size silicoaluminophosphate molecular sieves include SAPO-11, SAPO-31 and SAPO-41. 最优选的硅铝磷酸盐是SAPO-11,最优选的金属组分是铂,最优选的粘合剂是氧化铝;SAPO-11,SAPO-31和SAPO-41及其制备方法的描述发表在上面引用的专利和R.Szostak的“分子筛手册”(Van NorstrandReinhold 1992),第410-413,415-416,419-420页中,这些文献公开的内容引入本文作为参考。 The most preferred silicoaluminophosphate is SAPO-11, the most preferred metal component is platinum, the most preferred binder is alumina; SAPO-11, SAPO-41 and its preparation process is described and published in the SAPO-31 "Handbook of Molecular Sieves" of the above-cited patents and in R.Szostak (Van NorstrandReinhold 1992), pages 410-413,415-416,419-420, the disclosure content of these documents incorporated herein by reference.

2.特别的制备:分子筛可以与其他对脱蜡方法中使用的温度和其他条件是稳定的材料组合。 2. Special preparation: stable molecular sieve can be combined with other materials used for the dewaxing temperature and other process conditions. 这样的基质材料包括活性的和非活性的的材料和合成的或天然形成的沸石以及无机材料比如粘土,二氧化硅和金属氧化物。 Such matrix materials include active and zeolites, and naturally occurring inorganic materials or synthetic materials and non-activity, such as clays, silica and metal oxides. 无机材料可以是天然形成的或者是以凝胶状沉淀物,溶胶或凝胶、包括二氧化硅和金属氧化物的混合物的形式。 The inorganic material may be natural, or is formed of gelatinous precipitates, sols or gels, including in the form of mixtures of silica and metal oxides. 非活性材料合适作为粘合剂或作为稀释剂,以控制脱蜡方法中的转化数量,以便不需使用其他的控制反应速率的方法就可经济地得到产物。 Inactive material suitable as an adhesive or as a diluent to control the amount of conversion in the dewaxing process so that without the use of other methods of controlling the reaction rate the product can be economically obtained.

硅铝磷酸盐可以与天然形成的粘土例如膨润土和高岭土结合。 Clay silicoaluminophosphates may be formed with a natural binding e.g. bentonite and kaolin. 这些材料即粘土、氧化物等等的作用是部分作为催化剂的粘合剂。 That is the role of these materials, clays, oxides, etc. that the adhesive portion as a catalyst. 希望提供一种具有好的压碎强度的催化剂,因为在石油炼制中,该催化剂经常经受野蛮装卸和反应器中的大的作用应力,这样会将催化剂打成可能堵塞反应器的碎片。 Desirable to provide a catalyst having good crush strength, because in petroleum refining, the catalyst is often subjected to rough handling large and stress acts in the reactor, the catalyst will be labeled so that debris may clog the reactor.

可以与硅铝磷酸盐复合的天然形成的粘土包括蒙脱土和高岭土类,该高岭土类包括亚膨润土,并且该高岭土通常是所说的Dixie,McNamee,Georgia和Florida粘土,或其他的主要矿物成分是多水高岭土,高岭石,地开石,珍珠陶土或富硅高岭石的高岭土。 Phosphate and aluminosilicate clay may be naturally occurring compound include the montmorillonite and kaolin family, which includes the sub-class kaolin, bentonite, and kaolin which is generally called Dixie, McNamee, Georgia and Florida clays, or other main mineral constituent kaolin is halloysite, kaolinite, dickite, pearl or silicon-rich clay kaolinite. 纤维状粘土例如多水高岭土、海泡石和硅镁土也可以用作载体。 The fibrous clays such as halloysite, sepiolite and attapulgite can also be used as carriers. 这样的粘土可以以最初开采的未加工状态使用,或者开始就经过锻烧,酸处理或化学改性。 Such clays can be used in the raw state as originally mined using, or after calcination outset, acid treatment or chemical modification.

除上述的材料之外,该硅铝磷酸盐可以与多孔基质材料组合,例如,无机氧化物基质,和基质材料的混合物,比如二氧化硅,氧化铝,二氧化钛,氧化镁,二氧化硅-氧化铝,二氧化硅-氧化镁,二氧化硅-氧化锆,二氧化硅-氧化钍,二氧化硅-氧化铍,二氧化硅-二氧化钛,二氧化钛-氧化锆和三元组合物比如二氧化硅-氧化铝-氧化钍,二氧化硅-氧化铝-二氧化钛,二氧化硅-氧化铝-氧化镁和二氧化硅-氧化镁-氧化锆。 In addition to the above materials, the silicoaluminophosphate can be a combination of a porous matrix material, e.g., an inorganic oxide matrix, and mixtures of matrix materials such as silica, alumina, titania, magnesia, silica - oxide alumina, silica - magnesia, silica - zirconia, silica - thoria, silica - beryllia, silica - titania, titania - zirconia, and ternary compositions such as silica - alumina - thoria, silica - alumina - titania, silica - alumina - silica and magnesia - magnesium oxide - zirconium oxide. 该基质可以以共凝胶或密切的物理状态混合物的形式存在。 The matrix can be in the form of a cogel or close physical state of the mixture.

用于本发明方法的硅铝磷酸盐催化剂还可以与其他的沸石组合,例如合成的和天然的八面沸石,(例如X和Y型)毛沸石和丝光沸石。 Silicoaluminophosphate catalyst used in the process according to the present invention may also be other combinations zeolite, such as synthetic and natural faujasites, (e.g., X and Y), erionite and mordenite. 它们还可以与纯粹的合成沸石比如ZSM系列的那些沸石组合。 They may also be combined with zeolites such as those of pure synthetic zeolite ZSM series. 沸石的混合物还可以与多孔无机基质组合。 Mixtures of zeolites may also be combined with a porous inorganic matrix.

D.沸石用于本发明方法的适当铝硅酸盐沸石催化剂的例子包括ZSM-22,ZSM-23和ZSM-35。 D. Examples of suitable zeolitic aluminosilicate zeolites used in the process of the present invention catalysts include ZSM-22, ZSM-23 and ZSM-35. 这些教导在R.Szostak的“分子筛手册”(Van NorstrandReinhold 1992),第538-542和545-546页中可见,该专利在本文引入作为参考,和在美国专利4,481,177;4,076,842;和4,016,245中可见,这些专利公开的内容在本文引入作为参考。 These teachings R.Szostak the "Handbook of Molecular Sieves" (Van NorstrandReinhold 1992), pp. 538-542 and 545-546 is visible, which patent is incorporated herein by reference, and in U.S. Patent No. 4,481,177; 4,076,842; and 4,016,245 visible, disclosures of these patents is incorporated herein by reference.

硅铝磷酸盐分子筛催化剂和铝硅酸盐沸石催化剂可以以提高转化进料收率的中等孔径硅铝磷酸盐分子筛与中等孔径铝硅酸盐沸石分子筛的有效重量比用于本发明方法中。 Silicoaluminophosphate molecular sieve catalyst and the aluminosilicate zeolite catalyst may improve the feed conversion yield intermediate pore size silicoaluminophosphate molecular sieve and an intermediate pore size aluminosilicate zeolite molecular sieve effective method of weight ratio for the present invention. 优选的重量比是约1∶5到约20∶1。 Preferred weight ratio is about 20 to about 1:5. 用于该方法的沸石在约400℃-约454℃下测定的约束指数为约4至约12。 Zeolites used in this method is about 400 ℃ - about 454 deg.] C measured at a Constraint Index of from about 4 to about 12.

在本发明的另一个实施方案中,SSZ-48,优选是氢形式的,可用于本发明的脱蜡方法。 In another embodiment of the present invention, SSZ-48, preferably hydrogen form, it can be used in the dewaxing method of the present invention. 不受理论的限制,认为SSZ-48是通过选择除去直链链烷烃来脱蜡的。 Is not limited by theory, SSZ-48 is believed to remove linear paraffins by selecting dewaxing. 通常,当在异构化脱蜡(还称作加氢脱蜡)条件下含蜡进料与SSZ-48接触时,脱蜡产物的粘度指数得到了改善(与溶剂脱蜡进料相比)。 Typically, when the isomerization dewaxing (also referred to as hydrodewaxing) conditions waxy feed contacted with SSZ-48, the viscosity index of the dewaxed product is improved (compared to the solvent dewaxed feed) .

在制备SSZ-48沸石时,十氢喹啉鎓阳离子用作结晶模板。 In preparing SSZ-48 zeolites, decahydroquinoline cation as a crystallization template. 这种十氢喹啉鎓阳离子可以具有下列结构: Such decahydroquinoline cation may have the following structure: 与阳离子有关的阴离子(X-)可以是对沸石的形成无害的任何阴离子。 Anion associated with the cation (X-) may be any anion to form harmless zeolite. 代表性的阴离子包括卤素,例如氟根,氯根、溴根和碘根,氢氧根,乙酸根,硫酸根,四氟硼酸根,羧酸根等等。 Representative anions include halogen, e.g., fluoride, chloride, bromide and iodide, hydroxide, acetate, sulfate, tetrafluoroborate, carboxylate and the like. 氢氧根是最优选的阴离子。 Hydroxide is the most preferred anion.

通常,SSZ-48是一种或多种选自下面的氧化物与十氢喹啉鎓阳离子模板剂接触而制备的,所述氧化物选自单价的元素氧化物,二价元素氧化物,三价元素氧化物,和四价元素氧化物。 Typically, SSZ-48 is selected from one or more oxides of decahydro- quinolinium cation in contact with the prepared template, the oxide of element selected from oxides, divalent element oxides monovalent, tris trivalent element oxides, and tetravalent element oxides.

SSZ-48是由具有下表1所示的组分的反应混合物制备的。 SSZ-48 is prepared from a mixture of reactive components shown in the following Table 1.

表1反应混合物 Table 1 The reaction mixture was

其中Y是硅,锗或其混合物;W是铝,镓,铁,硼,钛,铟,钒或其混合物;c是1或2;当c是1时d是2(即,W是四价的),或当c是2时d是3或5(即,当W是三价时d是3,当W是五价时d是5);M是碱金属阳离子、碱土金属阳离子或其混合物;n是M的化合价(即,1或2);Q是至少一个十氢喹啉鎓阳离子,a是1或2,当a是1时(即,W是四价)b是2,当a是2时(即,W是三价)b是3。 Wherein Y is silicon, germanium or mixtures thereof; W is aluminum, gallium, iron, boron, titanium, indium, vanadium or mixtures thereof; c is 1 or 2; d is 1 when c is 2 (i.e., W is tetravalent ) or when c is 2 and d is 3 or 5 (i.e., when W is trivalent d is 3 when W is pentavalent d is 5); M is an alkali metal cation, alkaline earth metal cation or mixtures thereof ; n is the valence of M (i.e., 1 or 2); Q is at least one decahydroquinoline cation, a is 1 or 2 when a is 1 (i.e., W is tetravalent) b is 2, and when a is 2 (i.e., W is trivalent) b is 3.

在实践中,SSZ-48是由下列方法制备的,该方法包括:(a)制备一种水溶液,该水溶液含有至少一种能够形成结晶分子筛的氧化物源和具有对SSZ-48的形成无害的阴离子平衡离子的十氢喹啉鎓阳离子;(b)保持该水溶液在足以形成SSZ-48晶体的条件下;和(c)回收SSZ-48晶体。 In practice, SSZ-48 is prepared by the following method, the method comprising: (a) preparing an aqueous solution containing at least one oxide capable of forming a crystalline molecular sieve having a form harmless to source and SSZ-48 of the decahydro anionic counterions quinolinium cation; (b) maintaining the aqueous solution under conditions sufficient to SSZ-48 crystal formation; and (c) recovering SSZ-48 crystals.

因此,SSZ-48可以含有该结晶物质和模板剂和结合的金属和非金属氧化物,该金属和非金属氧化物通过共享的氧原子结合成四面体配位,以形成交叉联结的三维空间晶体结构。 Accordingly, SSZ-48 may comprise the crystalline material and the templating agent and the binding metal and non-metal oxides, metal and non-metal oxides by sharing oxygen atoms are bonded to tetrahedrally coordinated, to form a three-dimensional cross-linking of the crystals structure. 该金属和非金属氧化物包括一种第一四价元素的氧化物或其混合物,一种不同于第一四价元素的第二四价元素或其混合物,三价元素,五价元素,或它们的混合物。 The metallic and non-metallic oxides comprise one oxide of a first tetravalent element or mixture thereof, one first tetravalent element, second tetravalent element or mixture thereof is different from, trivalent element, pentavalent element, or mixtures thereof. 该第一四价元素优选选自硅、锗及其混合物。 The first tetravalent element is preferably selected from silicon, germanium and mixtures thereof. 更优选的是,第一四价元素是硅。 More preferably, the first tetravalent element is silicon. 第二四价元素(不同于第一四价元素),三价元素和五价元素优选选自铝,镓,铁,硼,钛,铟、钒和它们的混合物。 The second tetravalent element (different from the first tetravalent element), trivalent element and pentavalent element is preferably selected from aluminum, gallium, iron, boron, titanium, indium, vanadium and mixtures thereof. 更优选的是,第二三价或四价元素是铝或硼。 More preferably, the second trivalent or tetravalent element is aluminum or boron.

用于反应混合物的氧化铝的典型来源包括铝酸盐,氧化铝,铝胶体,涂在氧化硅溶胶上的氧化铝,水合氧化铝凝胶例如Al(OH)3和铝化合物例如AlCl3和Al2(SO4)3。 Typical sources of aluminum oxide for the reaction mixture include aluminates, alumina, aluminum colloids, coated on the alumina silica sol, hydrated alumina gels such as Al (OH) 3 and aluminum compounds such as AlCl3 and Al2 ( SO4) 3. 典型的氧化硅源包括硅酸盐,二氧化硅水凝胶,硅酸,煅制氧化硅,胶态氧化硅,四烷基正硅酸盐,和硅氢氧化物。 Typical sources of silicon oxide include silicates, silica hydrogel, silicic acid, fumed silica, colloidal silica, tetraalkyl orthosilicates, and silica hydroxides. 可以以相应于它们的铝和硅的相应物的形式加入硼,以及镓,锗,钛,铟、钒和铁。 Boron may be added, as well as gallium, germanium, titanium, indium, vanadium and iron in the form corresponding to their aluminum and silicon counterparts of.

沸石试剂来源可以提供铝或硼的来源。 Source zeolite reagent may provide a source of aluminum or boron. 在大多数情况下,沸石来源还提供了二氧化硅的来源。 In most cases, the source zeolite also provides a source of silica. 以其脱铝或脱硼形式的沸石来源也可以用作二氧化硅的来源,附加的硅使用例如上面列出的常规来源。 Source zeolite in its dealuminated or deboronated form may also be used as a source of silica, silicon added using conventional sources such as listed above. 对于本方法使用沸石试剂来源作为氧化铝的来源更完全地描述在1993年2月16日授权的Zones等人的发明名称为″制备硼硅酸盐沸石″的美国专利5,187,132中,该专利公开的内容引入本文作为参考。 For the present process using a zeolite reagent as a source of alumina, a source more fully described in the February 16, 1993 to Zones et al authorized U.S. Patent No. 5,187,132 is entitled "Preparation of borosilicate zeolite", the disclosure of this patent incorporated herein by reference.

通常,在反应混合物中使用碱金属氢氧化物和/或碱土金属氢氧化物,例如钠,钾,锂,铯,铷,钙和镁的氢氧化物;然而,只要保持了相等的碱度,将可以省去该组分。 Typically, an alkali metal hydroxide and / or alkaline earth metal hydroxide in the reaction mixture, e.g., sodium, potassium, lithium, cesium, rubidium, calcium and magnesium hydroxides; however, as long as the equivalent basicity maintained, this component will be omitted. 模板剂可能用来提供氢氧离子。 The templating agent may be used to provide hydroxide ion. 因此,这有益于离子交换,例如,卤根交换氢氧离子,从而减少或消除了碱金属氢氧化物的需求量。 Accordingly, an ion exchange which is beneficial, for example, halide exchange hydroxide ions, thereby reducing or eliminating the alkali metal hydroxide demand. 碱金属阳离子或碱土阳离子可以是合成结晶氧化物的一部分,以便平衡其中的价电子电荷。 An alkali metal cation or alkaline earth cation may be part of the synthesized crystalline oxide, in order to balance valence electron charges therein.

该反应混合物保持在高温下,直到SSZ-48沸石的晶体形成。 The reaction mixture is maintained at an elevated temperature until crystals of the SSZ-48 zeolite are formed. 水热结晶通常在自生压力下,在温度为100℃和200℃之间,优选在135℃和160℃之间下进行。 The hydrothermal crystallization is usually under autogenous pressure, at the temperature of 100 ℃ and 200 ℃ between, preferably carried out at between 135 deg.] C and 160 ℃. 结晶时间通常大于1天,优选约3到约20天。 Crystallization time is typically greater than 1 day, preferably from about 3 to about 20 days.

优选的是,该沸石的制备使用温和搅拌或搅动。 Preferably, the zeolite is prepared using mild stirring or agitation.

在水热结晶步骤期间,允许从反应混合物自然地成核该SSZ-48晶体。 During the hydrothermal crystallization step, the reaction mixture was allowed to naturally from the nucleation SSZ-48 crystals. 使用SSZ-48晶体作为晶种,可以有利于减少完全结晶所必需的时间。 Using SSZ-48 crystals as seed crystals, it may help reduce the time necessary for complete crystallization. 另外,引晶可以提高通过促进SSZ-48的成核和/或生成而得到的产物的纯度,该纯度超过任何所不希望的相。 In addition, seeding can increase the purity of SSZ-48 by promoting the nucleation and / or generation of the product obtained, the purity of more than any undesired phases. 当用作晶种时,SSZ-48晶体的加入量为用于反应混合物中二氧化硅重量的0.1%-10%。 When used as seeds, SSZ-48 crystals added in an amount of 0.1% to 10% for the reaction mixture in the weight of silica.

一旦沸石晶体已经形成,通过标准的机械分离方法,例如过滤法,从反应混合物分离出固体产物。 Once the zeolite crystals have been formed by standard mechanical separation methods such as filtration, the solid product was isolated from the reaction mixture. 水洗该晶体,然后干燥例如在90℃-150℃下干燥8-24小时,得到合成的SSZ-48沸石晶体。 The crystals were washed with water, dried and then dried, for example, for 8-24 hours at 90 ℃ -150 ℃, SSZ-48 zeolite crystals obtained in the synthesis. 该干燥步骤可以在大气压力或在真空下进行。 The drying step may be carried out at atmospheric pressure or under vacuum.

所制备的SSZ-48中的、选自氧化硅,氧化锗和它们的混合物的一种氧化物与选自氧化铝,氧化镓,氧化铁,氧化硼,氧化钛,氧化铟,氧化钒和它们的混合物的一种氧化物的摩尔比大于约40;并具有下表2的X射线衍射线。 Selected from alumina and an oxide of SSZ-48, selected from silicon oxide, germanium oxide and mixtures thereof are prepared, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, vanadium oxide, and their molar ratio of an oxide of the mixture is greater than about 40; and with X-ray diffraction lines in table 2.

表2合成的SSZ-48 Table 2 Synthesis of SSZ-48

(a)±0.3(b)提供的X射线图是基于相对强度等级,其中在X射线图中的最强线的数值为100:W(弱)是小于20;M(中等)是在20和40之间;S(强)是在40和60之间;VS(非常强)是大于60。 (A) ± 0.3 (b) X-ray pattern is provided based on a relative intensity scale where the value of the strongest line in the X-ray pattern of 100: W (weak) is less than 20; M (medium) and in 20 40; S (strong) is between 40 and 60; VS (very strong) is greater than 60.

SSZ-48还具有一种组成,是合成的和无水状态,用摩尔比表示,显示在下表3。 SSZ-48 further has a composition, expressed and synthetic anhydrous state, expressed by the molar ratio, are shown in Table 3.

表3合成的SSZ-48YO2/WcOd40-100M2/n/YO20.01-0.03Q/YO20.02-0.05其中Y是硅,锗或其混合物;W是铝,镓,铁,硼,钛,铟,钒或其混合物;c是1或2;当c是1时d是2(即,W是四价的)或当c是2时d是3或5(即,当W是三价时d是3,当W是五价时d是5);M是碱金属阳离子,碱土金属阳离子或其混合物;n是M的化合价(即,1或2);和Q是至少一种十氢喹啉鎓阳离子。 Table 3 Synthesis of SSZ-48YO2 / WcOd40-100M2 / n / YO20.01-0.03Q / YO20.02-0.05 wherein Y is silicon, germanium or mixtures thereof; W is aluminum, gallium, iron, boron, titanium, indium, vanadium or mixtures thereof; c is 1 or 2; d is 1 when c is 2 (i.e., W is tetravalent) or d is 2 when c is 3 or 5 (i.e., when W is a trivalent d 3, when W is pentavalent. 5 is d); M is an alkali metal cation, alkaline earth metal cation or mixtures thereof; n is the valence of M (i.e., 1 or 2); and Q is at least one onium decahydroquinoline cation.

一种提高二氧化硅与硼的摩尔比的方法是使用标准的酸浸取或螯合处理法。 A method of increasing the silica to boron molar ratio method using standard acid leaching or chelating treatment. 通过使用将铝插入到结晶骨架中的方法,也可得到较低的二氧化硅与氧化铝之比。 By using the method of aluminum is inserted into the crystalline framework, it can be obtained low silica to alumina ratio. 例如,用氧化铝粘合剂或溶解的氧化铝源热处理沸石,就可以插入铝。 For example, heat source zeolite with an alumina binder or dissolved alumina, aluminum can be inserted. 这样的方法描述在Chang等人的1985年12月17日授予的美国专利4,559,315中,该专利公开的内容在本文引入作为参考。 Such methods are described in U.S. Patent No. Chang et al December 17, 1985 granted 4,559,315, the contents of which patents are incorporated herein by reference.

合成的SSZ-48沸石具有如上表2所示的展示其特征线的X射线粉末衍射谱图的晶体结构,从而使其区别于其他的已知沸石。 Synthesis of SSZ-48 zeolite As shown in Table 2 having an X-ray powder diffraction pattern shows the characteristic line of its crystal structure, so that it is different from other known zeolites.

锻烧以后,SSZ-48沸石具有包括表4所示特征线的X射线粉末衍射谱图的晶体结构。 After calcination, SSZ-48 zeolites having a characteristic line includes a X-ray powder diffraction spectrum of the crystal structure shown in Table 4.

表4煅烧的SSZ-482θ(a)d相对强度(b)6.55 13.5 VS8.0 11.0 VS9.4 9.40 S11.3 7.82 M20.05 4.42 M22.7 3.91 M24.1 3.69 M26.5 3.36 M27.9 3.20 W35.85 2.50 W(a)±0.3 TABLE 4 SSZ-482θ (a) d relative intensity (b) calcined 6.55 13.5 VS8.0 11.0 VS9.4 9.40 S11.3 7.82 M20.05 4.42 M22.7 3.91 M24.1 3.69 M26.5 3.36 M27.9 3.20 W35.85 2.50 W (a) ± 0.3

用标准方法测定X射线粉末衍射谱图。 X-ray powder diffraction pattern measured using standard procedures. 辐射是铜的K-α/偶极子(alpha/doublet)。 Radiation of copper K-α / dipole (alpha / doublet). 峰高和位置,作为2θ的函数,其中θ是布喇格角,是从峰值的相对强度读取的,并且可以计算出d,对应于记录线的平面间距(埃)。 The peak heights and the positions, as a function of 2θ, where θ is the Bragg angle, are read from the relative intensities of the peaks, can be calculated and d, corresponding to the recorded lines, the interplanar spacing (Angstroms).

由于仪器误差和个体样品之间的差别,散射角(2θ)尺寸的变化估计有±0.30度。 Due to differences between individual samples and instrument error, the dimensional change of the scattering angle (2 [Theta]) estimated at ± 0.30 degrees.

上述表2的X射线衍射谱图表征了″合成的″或″制备的″SSZ-48沸石。 X-ray diffraction pattern in Table 2 characterizes the "synthetic" or "made" SSZ-48 zeolites. 由于晶格常数的变化,特定样品的二氧化硅比氧化铝或二氧化硅比硼的摩尔比的变化会引起衍射图样的较小变化。 Due to changes in lattice constant than the change ratio of boron or silica alumina molar ratio of silica of a particular sample will cause small variations in the diffraction pattern. 另外,十分小的晶体将影响峰值的形状和强度,导致显著的峰加宽。 In addition, sufficiently small crystals will affect the shape and intensity of peaks, leading to significant peak broadening.

煅烧过的SSZ-48的代表性的峰值显示在表4中。 Representative peaks SSZ-48 calcined shown in Table 4. 与“制备的”材料的谱图相比,锻烧还可以导致峰值的强度变化,以及衍射图样的较小移位。 Compared with the spectrum of materials "prepared", calcined it can also result in changes in the intensity of the peak, and a smaller shift of the diffraction pattern. 用不同的其他阳离子(例如H+或NH4+)交换沸石中存在的金属或其他阳离子而制备的沸石产生了本质上相同的衍射图样,即使再进行一次交换,平面间距的移位和峰值的相对强度的变化也是较小的。 With other cations different (e.g., H + or NH4 +) zeolite prepared exchanged zeolite in the presence of a metal or other cations yielded the same diffraction pattern essentially even then an exchange, the relative intensity shift and peak plane spacing change is also smaller. 尽管有这些较小的波动,但通过这些处理基础晶格仍保持不变。 Despite these minor fluctuations, but it remains unchanged by these treatments base lattice.

晶体SSZ-48可以以合成的形式使用,但优选经过热处理(煅烧)。 SSZ-48 crystals can be used in synthetic form, but is preferably heat treated (calcined). 通常,希望通过离子交换和用氢,铵,或任何所需金属离子替换来除去碱金属阳离子。 Typically, it is desirable, and by ion exchange with hydrogen, ammonium, or any desired metal ion substitution to remove the alkali metal cation. 沸石可用螯合剂例如乙二胺四乙酸或稀酸溶液浸滤,以增加二氧化硅与氧化铝的摩尔比.沸石还可以通入蒸汽;通入蒸汽有助于稳定晶体晶格以免受酸的腐蚀。 Zeolite is available chelating agents such as ethylenediaminetetraacetic acid or dilute acid leaching solution, to increase the silica to alumina mole ratio of zeolites may also be introduced into steam;. Into steam helps to stabilize the crystalline lattice to protect against acid corrosion.

用于本方法的SSZ-48,和任何其他的沸石,可密切地与加氢组分结合,比如钨,钒,钼,铼,镍,钴,铬,锰,或贵金属,比如用钯或铂,以用于要求加氢-脱氢功能的那些应用。 The method of the present SSZ-48, zeolite and any other, may be intimately combined with a hydrogenation component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal, such as palladium or platinum , required for the hydrogenation - dehydrogenation function of those applications. 优选用铂和钯。 Preferably with platinum and palladium.

可通过标准的离子交换技术,用金属阳离子替换沸石中的一些阳离子来将金属引入到沸石中(参见,例如Plank等人的1964年7月7日授予的美国专利3,140,249,Plank等人的1964年7月7日授予的3,140,251和Plank等人的1964年7月7日授予的美国专利3,140,253,这些专利公开的内容在本文引入作为参考)。 Can be switched technology by standard ion, replacing some cations in the zeolite with metal cations to metal is introduced into the zeolite (see, e.g. U.S. Pat Plank et al., July 7, 1964 granted 3,140,249, Plank et al., 1964, July 7 granted 3,140,251 and Plank et al. US Patent July 7, 1964 granted 3,140,253, the disclosures herein incorporated by reference). 典型的替换阳离子包括金属阳离子,例如稀土族,IA族,IIA族和VIII族金属,以及它们的混合物。 Typical replacing cations include metal cations such as rare earth, IA group, IIA and Group VIII metals, and mixtures thereof. 在替换的金属阳离子中,优选例如稀土族,锰,钙,镁,锌,镉,铂,钯,镍,钴,钛,铝,锡,铁的金属阳离子。 In an alternative metal cations, such as rare earth family, manganese, calcium, magnesium, zinc, cadmium, platinum, palladium, nickel, cobalt, titanium, aluminum, tin, iron metal cation.

将催化活性金属引入到分子筛中的技术公开在文献中,现有的金属加入技术和处理分子筛形成活性催化剂的技术比如在分子筛制备过程中离子交换、浸渍或吸收的技术都适用于本方法。 The catalytically active metals into a molecular sieve are disclosed in the technical literature, conventional metal processing techniques and molecular sieves were added to form an active catalyst such as ion exchange techniques during preparation of the molecular sieve, impregnation or absorption techniques are applicable to the present method. 这样的技术公开在美国专利3,236,761;3,226,339;3,236,762;3,620,960;3,373.109;4,202,996;4,440,781和4,710,485中,这些专利公开的内容引入本文作为参考。 Such techniques are disclosed in U.S. Patent No. 3,236,761; 3,226,339; 3,236,762; 3,620,960; 3,373.109; 4,202,996; 4,440,781 and 4,710,485, the disclosures incorporated herein by reference. 金属的量为沸石重量的约0.01%-10%,优选约0.2%-约5%。 The amount of metal ranges from about 0.01% to 10% by weight of zeolite, preferably from about 0.2% - about 5%.

氢,铵,和金属组分可经离子交换进入沸石中。 Hydrogen, ammonium, and metal components can be ion exchanged into the zeolite. 也可以用金属浸渍沸石,或用标准的本领域已知方法将金属和沸石物理地和密切地混合。 Zeolite may be impregnated with a metal, or by standard methods known in the art and will be mixed metal zeolite and intimately physically.

典型的离子交换技术包括使合成沸石与含有需要替换的一种或多种阳离子的溶液接触。 Typical ion exchange techniques include contacting the synthetic zeolite need to replace one or more cations with a solution containing. 虽然可以使用各种各样的盐,但是特别优选使用氯化物和其他的卤化物,乙酸盐,硝酸盐和硫酸盐。 Although a wide variety of salts can be used, but it is particularly preferred to use chlorides and other halides, acetates, nitrates and sulfates. 在离子交换步骤之前通常要煅烧沸石,以除去通道和表面上存在的有机物质,因为这样得到了更有效的离子交换。 Before the ion exchange step typically calcined zeolite channels and to remove the organic matter present on the surface, so as to obtain a more effective ion exchange. 典型的离子交换技术公开在许多专利中,包括Plank等人的1964年7月7日授予的美国专利3,140,249;Plank等人的1964年7月7日授予的美国专利3,140,251;Plank等人的1964年7月7日授予的美国专利3,140,253;这些专利公开的内容在本文引入作为参考。 Typical ion exchange techniques are disclosed in numerous patents, including Plank, et al., US Patent July 7, 1964 granted 3,140,249; US Patent Plank et al, July 7, 1964 granted 3,140,251; Plank, et al., 1964 US Patent July 7 granted 3,140,253; the disclosures herein incorporated by reference.

与需要交换的阳离子的盐溶液接触之后,通常是用水洗涤沸石并在65-约200℃下干燥。 After contacting with the salt solution to be exchanged cation, the zeolite is typically washed with water and dried at 65 to about 200 ℃. 洗涤之后,沸石在空气或惰性气体中、在约200℃-约800℃的温度下煅烧1-48小时或更长时间,以制备在烃类转化过程中尤其有效的催化活性产品。 After washing, the zeolite in air or an inert gas at about 200 ℃ - calcined at a temperature of 1-48 deg.] C to about 800 hours or more to prepare particularly effective in the hydrocarbon conversion process catalytically active product.

与SSZ-48的合成形式中存在的阳离子无关,形成沸石的基础晶格的原子空间排列基本上保持不变。 Present in the synthesized form of SSZ-48 independent of cations, forming the basis of the crystal lattice of the zeolite remains essentially unchanged arrangement of their atoms in space.

加氢组分以优选约0.05-5重量%的适当量存在,以提供有效的加氢脱蜡和临氢异构化催化剂。 The hydrogenation component in suitable amounts of from about 0.05 to 5% by weight is preferably present to provide an effective hydrodewaxing and hydroisomerization catalyst. 催化剂可以以裂化反应为代价的方式运行,以强化异构脱蜡(isodewaxing)。 The catalyst may be at the expense of cracking reactions run to enhance isodewaxing (isodewaxing).

用于本方法的任何二种或多种沸石可以以层状催化剂的形式用作脱蜡催化剂。 Any two or more zeolites used in the present process may be used as a dewaxing catalyst in the form of a layered catalyst. 即,催化剂包括第一层和第二层,第一层含有例如沸石SSZ-48和至少一种VIII族金属,第二层含有另一种铝硅酸盐沸石,例如任意的比沸石SSZ-48具有更多形状选择的一种沸石。 That is, the catalyst comprises a first and second layers, a first layer comprising such as zeolite SSZ-48 and at least one Group VIII metal, a second layer comprising another aluminosilicate zeolite, such as any of the zeolites SSZ-48 more zeolite having a selected shape. 层状催化剂的使用公开在Miller等人的1992年9月22日授予的美国专利5,149,421中,该专利在本文完全引入作为参考。 Using a layered catalyst is disclosed in Miller et al., September 22, 1992 granted US Patent No. 5,149,421, which is incorporated herein fully incorporated by reference. 分层也可包括与为加氢裂化或加氢精制而设计的非沸石组分分层的沸石床,例如,SSZ-48。 Layered bed may also include zeolite and non-zeolitic component is layered hydrocracking or hydrofinishing designed, e.g., SSZ-48. 在这个意义上密切混合的催化剂系统代表了另一种有用的变体,以代替分层。 The catalyst system in the sense of intimate mixing represents another useful variant, instead of hierarchical.

E.无定形催化剂用于本发明的无定形催化剂是对进料具有加氢和/或异构化作用的任何无定形催化剂。 Amorphous amorphous catalyst E. The catalyst used in the present invention are any amorphous catalysts having hydrogenation and / or isomerization of the feed. 这样的无定形催化剂教导在例如美国专利4,383,913中,该专利公开的内容在本文引入作为参考。 Such amorphous catalysts are taught, for example, in U.S. Patent No. 4,383,913, the contents of which patents are incorporated herein by reference.

这些催化剂包括,例如,无定形的催化性无机氧化物,例如,催化活性二氧化硅-氧化铝,粘土,合成的或酸活化的粘土,二氧化硅,氧化铝,二氧化硅-氧化铝,二氧化硅-氧化锆,二氧化硅-氧化镁,氧化铝-氧化硼,氧化铝-二氧化钛,柱状或交联的粘土,等等和它们的混合物。 These catalysts include, for example, amorphous catalytic inorganic oxides, e.g., catalytically active silica - alumina, clays, synthetic or acid activated clays, silica, alumina, silica - alumina, silica - zirconia, silica - magnesia, alumina - boria, alumina - titania, columnar or cross-linked clays, and the like, and mixtures thereof.

F.工艺操作条件该方法在催化脱蜡条件下进行。 F. Process operating conditions of the method carried out under catalytic dewaxing conditions. 这样的条件是已知的并教导在例如下列美国专利5,591,322;5,149,421;和4,181,598中,这些专利公开的内容引入本文作为参考。 Such conditions are known and taught, for example, in the following U.S. Patents 5,591,322; 5,149,421; and 4,181,598, the disclosures incorporated herein by reference. 催化脱蜡条件主要取决于所用的进料和所要求的倾点。 Catalytic dewaxing conditions depending on the feed used and the desired pour point. 在催化脱蜡过程中反应区中优选存在氢。 Hydrogen is preferably present in the reaction zone during the catalytic dewaxing. 氢与进料之比,也就是说氢的循环速率,通常为约500至约30,000SCF/bbl(标准立方英尺/桶),优选约1000-约20,000SCF/bbl。 Ratio of hydrogen to feed ratio, that is to say a hydrogen circulation rate is generally (SCF / Bbl standard) of about 500 to about 30,000SCF / bbl, preferably from about 1000 to about 20,000SCF / bbl. 通常,将氢与产物分开并再循环到反应区。 Typically, the hydrogen product is separated and recycled to the reaction zone.

再循环到进料中的分馏塔底产物的百分比是提高总收率的有效量。 Percentage fractionator bottoms recycled to the feed product is an effective amount to improve the overall yield. 优选的是,再循环的百分比为约1-约100,或更优选约10-约50。 Preferably, the percentage of recycled about 1 to about 100, or more preferably from about 10 to about 50. 分馏塔底产物与新进料的比例是降低倾点不损失收率或提高总收率、同时又维持倾点的有效比例。 Fractionating the bottom product and raw feed ratio to reduce the pour point without loss of yield or total yield increase, while maintaining an effective ratio of pour point. 优选的是,该比例为约1∶100-约60∶100,或更优选约1∶100-约40∶100。 Preferably, the ratio is about from about 1:100- 60:100, or more preferably from about to about 40:100 1:100-.

中等孔径的铝硅酸盐沸石催化剂和/或无定形催化剂,象硅铝磷酸盐分子筛催化剂一样,可任选地用于相同的反应器,或可以用于一个分开的反应器中。 Intermediate pore size aluminosilicate zeolite catalyst and / or amorphous catalysts, such as silicoaluminophosphate molecular sieves as catalysts, may optionally be used in the same reactor, or may be used in a separate reactor. 当二种或多种催化剂用于相同的反应器时,它们可以按顺序分层或混合。 When two or more catalysts used in the same reactor, they may be sequentially layered or mixed. 当按顺序分层时,该SAPO任意地是第一或第二层。 When hierarchical order, the SAPO optionally the first or second layer. 当二种或多种催化剂用于相同的反应器时,它们也可以密切地混合。 When two or more catalysts used in the same reactor, they may be intimately mixed. 任何常规的催化剂床构型可用于本发明方法。 Any conventional catalyst bed configuration can be used in the process of the present invention.

本发明的催化异构化步骤可以按照要求将要脱蜡的进料与催化剂固定床、与固定的流化床、或移动床接触来进行。 Catalytic isomerization step of the present invention may be dewaxed feed with a fixed bed of catalyst, with a fixed fluidized bed, or moving bed contacting is performed as required. 因此,一种简单的和优选的构型是喷淋床操作,其中进料可以喷淋通过固定床,优选的在氢存在下。 Thus, a simple and preferred configuration is a trickle-bed operation in which the spray can feed through a fixed bed, preferably in the presence of hydrogen.

所用的催化脱蜡条件取决于所用的进料和所需倾点。 Catalytic dewaxing conditions employed depend on the feed used and the desired pour point. 对于不同的催化过程,一些普通的工艺操作条件显示在下表5中: For different catalytic processes, some common process conditions shown in Table 5:

1几百个大气压2气相反应3烃分压4液相反应5WHSV 1 2 atm hundreds of gas phase reaction 3 Hydrocarbon partial pressure 4 Liquid reaction 5WHSV

在本发明方法中,通常,温度为约200℃-约475℃,优选为约250℃-约450℃。 In the method of the present invention, in general, a temperature of from about 200 ℃ - about 475 deg.] C, preferably from about 250 ℃ - about 450 ℃. 压力通常为约15磅/平方英寸-约3000磅/平方英寸,优选为约200磅/平方英寸-3000磅/平方英寸。 Pressure is generally from about 15 pounds / square inch - about 3000 pounds / square inch, preferably about 200 pounds / square inch -3000 pounds / square inch. 液时空速(LHSV)优选是0.1-20,优选约0.2-10。 A liquid hourly space velocity (LHSV) is preferably 0.1 to 20, preferably from about 0.2 to 10.

在催化异构化过程中,在反应区中优选存在氢。 In the catalytic isomerization process, preferably in the presence of hydrogen in the reaction zone. 氢与进料之比通常为约500-约30,000SCF/bbl(标准立方英尺/桶),优选为约1000-约20,000SCF/bbl。 Ratio of hydrogen to feed ratio is typically from about 500 to about 30,000SCF / bbl (standard cubic feet / barrel), preferably from about 1000 to about 20,000SCF / bbl. 通常,氢将与产物分开并再循环到反应区。 Typically, the hydrogen will be separated from the product and recycled to the reaction zone.

G.后处理通常希望所用温和的加氢(有时称作加氢精制)。 G. After the desired treatment is typically mild hydrogenation (sometimes referred to as hydrofinishing). 加氢精制步骤有利于制备适合的稳定产物(例如,润滑油),因为不饱和产物倾向于对空气和光不稳定和倾向于降解。 Hydrofinishing step is conducive to the stability of the product of Preparation for (e.g., lubricating oil) since unsaturated products tend to be unstable air and light and tend to degrade. 加氢精制步骤可以在异构化步骤之后进行。 Hydrofinishing step may be performed after the isomerization step. 加氢精制通常在下列条件下进行:温度为约190℃-约340℃,压力为约400磅/平方英寸-约3000左右磅/平方英寸,空速(LHSV)为约0.1-大约20,和氢再循环速率为约400-约1500SCF/bbl。 Hydrofinishing is usually carried out under the following conditions: temperature of about 190 deg.] C - to about 340. deg.] C, a pressure of about 400 lbs / square inch - about 3000 lbs / square inch, a space velocity (LHSV of) from about 0.1 to about 20, and a hydrogen recycle rate of about 400 to about 1500SCF / bbl.

所用的加氢催化剂必须不但对加氢润滑油馏分中的烯烃和二烯烃有足够的活性,而且对还原所存在的任何芳烃有足够的活性。 The hydrogenation catalyst used must not only have a sufficient activity for the hydrogenation of the lubricating oil fraction olefins and diolefins, and there is sufficient activity for the reduction of any aromatics present.

适当的加氢催化剂包括常规金属加氢催化剂,特别是VIII族金属比如钴,镍、钯和铂。 Suitable hydrogenation catalysts include conventional metallic hydrogenation catalysts, particularly the Group VIII metals such as cobalt, nickel, palladium and platinum. 该金属通常与载体比如铝土矿,氧化铝,硅胶,二氧化硅-氧化铝组合物、和结晶型铝硅酸盐沸石和其他的分子筛结合。 The generally metallic such as bauxite, alumina, silica gel, a silica support - binding alumina composition, and crystalline aluminosilicate zeolites and other molecular sieves. 钯是特别优选的加氢金属。 Palladium is a particularly preferred hydrogenation metal. 如果需要的话,非贵金属VIII族金属可以与钼酸盐一起使用。 If desired, non-noble Group VIII metals can be used with molybdates. 可以使用金属氧化物或硫化物。 Metal oxides or sulfides can be used. 合适的催化剂公开在美国专利3,852,207;4,157,294;4,921,594;3,904,513和4,673,487中,这些专利公开的内容在本文引入作为参考。 Suitable catalysts are disclosed in U.S. Patent No. 3,852,207; 4,157,294; 4,921,594; 3,904,513 and 4,673,487, the disclosures incorporated herein by reference.

对附图的详述图1描述了本发明方法的一个实施方案的简化流程图。 DETAILED DESCRIPTION OF THE DRAWINGS FIG 1 depicts a simplified flow diagram of one embodiment of the method of the present invention. 将润滑油进料物流5和氢气流10通入催化脱蜡装置15,例如,异构脱蜡(ISODEWAXING)催化脱蜡装置。 The lubricating oil feed stream 5 and 15, for example, dewaxing (ISODEWAXING) catalytic dewaxing unit 10 through the hydrogen gas stream into the catalytic dewaxing unit. 将催化脱蜡装置15的流出物20通入加氢精制装置25。 The effluent from catalytic dewaxing unit 15 is passed into the hydrotreating apparatus 20 25. 将加氢精制装置25的流出物30通入常压蒸馏塔35进行最初的分馏。 The hydrotreating reactor 25 effluent 30 into an atmospheric distillation column 35 for initial fractionation. 从常压蒸馏塔35取出各种产物物流,例如,轻质气体物流36,石脑油物流37,喷气式发动机燃料物流38,和塔底流出物40。 Various product stream withdrawn from the atmospheric distillation column 35, e.g., light gases stream 36, naphtha stream 37, jet fuel stream 38, and bottoms stream 40. 将常压蒸馏塔35的塔底流出物40通入减压蒸馏塔45进行进一步分馏。 The bottoms of atmospheric distillation column 35 effluent 40 into vacuum distillation column 45 for further fractionation. 从减压蒸馏塔45取出各种产物物流,例如,柴油机燃料物流50,60号中性油物流55,100号中性油物流60,和塔底流出物(或300号中性油)65。 The product stream 45 withdrawn from the various vacuum distillation column, e.g., diesel fuel stream 50,60 neutral oil stream No. No. 55,100 neutral oil stream 60, and bottoms stream (or 300 Neutral Oil) 65. 取出的一部分塔底流出物65作为300号中性油物流70,一部分通过物流75再循环,与新鲜的润滑油进料物流5混合。 Withdrawn bottoms stream 65, as part of a 300 neutral oil stream 70, through a portion of the recycle stream 75 with fresh lubricant mixed feed stream 5.

描述性实施方案通过下列实施例进一步阐明本发明,这些实施例纯粹是为了举例说明本发明。 Description of exemplary embodiments of the present invention is further illustrated by the following examples, these embodiments are merely to illustrate the invention.

·在大规模中试装置测验中已经证明了分馏塔底产物再循环操作的好处。 • In a large-scale pilot plant tests have proven the benefits of fractional distillation bottom product recycling operations. 为了示范开车,异构脱蜡反应器装有约5,000立方厘米的贵金属浸渍的SAPO-11催化剂,加氢精制反应器装有约5,000立方厘米的Chevron专有的加氢精制催化剂。 To demonstrate drive, isomerization dewaxing reactor filled with about 5,000 cc of a precious metal impregnated SAPO-11 catalyst, hydrotreating reactor was loaded with about Chevron proprietary hydrofinishing catalyst 5,000 cubic centimeters. 在线蒸馏产生了3种润滑油馏分和中间馏分。 Three line distillation produced middle distillate fraction and a lubricating oil. 该中试装置配置成模拟图1所示的工艺流程图。 The pilot plant is configured to simulate a process flow diagram shown in FIG.

·试验2个宽沸点加氢裂化进料。 · Test 2 wide boiling hydrocracked feed. 对这些进料的检测值显示在表6。 The detected value of these feeds are shown in Table 6. 异构脱蜡和加氢精制之后,将全部液体产物分馏成3个成品基础油馏分-60号中性油,100号中性油和300号中性油。 After isomerization dewaxing and hydrofinishing, the whole liquid product was fractionated into 3 finished base oil fraction No. -60 neutral oil, 100 neutral oil and 300 neutral oil. 表7概述了再循环一部分分馏塔底产物而得到的性能改善。 Table 7 summarizes the performance improvement of a portion of fractionator bottoms recycle product was obtained.

·对于试验1至4,新鲜原料速率维持大致不变,而分馏塔底产物再循环的百分比和异构脱蜡塔的加权平均床层温度(WAT)是变化的。 · For tests 1-4, the fresh feed rate is maintained substantially constant, while the percentage of fractionator bottoms recycle and a weighted average bed temperature dewaxing column (WAT) is varied. 在运行期间加氢精制塔是在大致恒温下操作。 During operation of the hydrotreating column is operated at a substantially constant temperature.

A.比较试验1和试验2显示了当再循环大量分馏塔底产物时,可以降低异构脱蜡塔的WAT,虽然在二种情况下脱蜡苛刻度稍有不同,但引人注目地提高了总的润滑油收率-从70%提高至80%。 A. Comparison Tests 1 and 2 show a large recirculation when the fractionator bottoms can be reduced WAT column dewaxing, the dewaxing severity although slightly different in either case, but increase dramatically the total lube yield - increased from 70 to 80%. 再循环还将100N和300N的倾点改至彼此非常接近-试验2中的倾点之间的差别为18℃,而试验1中的只有9℃。 Recycling 100N and 300N pour point will be changed to the close proximity to each other - the difference between the pour point of Test 2 was 18 ℃, but only test 1 9 ℃. 这意味着利用再循环,100N没有被过渡脱蜡而成为300N可接受的倾点。 This means that the use of recycled, 100N transition has not been dewaxed 300N become acceptable pour point.

B.试验3达到了与试验2相同的300N倾点。 B. Test 3 and Test achieve the same 300N pour point 2. 利用再循环(试验3),我们能够提高全部润滑油收率3%,和提高低倾点高价值100N的收率4%。 The use of recycled (test 3), we can increase the yield of 3% of the total lubricating oil, low pour point and improve high-value 100N yield of 4%. 另外,利用再循环降低了100N的过度脱蜡程度。 In addition, the use of recycled reduces the excessive degree of dewaxing 100N.

C.试验4是在与试验2相同的异构脱蜡塔加权平均床层温度下运行,而在试验4中,异构脱蜡塔进料含有13分馏塔底产物(再循环)。 C. Test 4 was run under the same test isodewaxing Taga 2 weighted average bed temperature, while in test 4, the isomerization dewaxing fractionating column feed 13 comprising bottom product (recycled). 虽然总的润滑油收率是相同的,但是在试验4中,有2%不到的300N和2%多的60N。 Although the total lube yield is the same, but in Test 4, there are less than 300N 2% and more than 60N 2%. 更重要的是,在试验4中,成品润滑油馏分的倾点实质上是较低的。 More importantly, in Test 4, the pour point of the finished lube fractions are substantially lower. 因此,再循环可以改善成品润滑油的产品性能,而没有改变总收率。 Thus, recycling can improve the product properties of the finished lubricating oil, without changing the overall yield.

对于试验5至7,新鲜原料速率以及分馏回流的百分比是变化的。 For tests 5-7, and the percentage of the fresh feed rate is varied at reflux for fractionation. 另外,加氢精制塔是在大致恒温下操作。 In addition, the hydrotreating column is operated at a substantially constant temperature.

A.对于试验6,新鲜原料速率提高了23%,而没有任何再循环。 A. For Test 6, the fresh feed rate was increased by 23% without any recycling. 为了保持上述接近倾点在300N,异构脱蜡塔的WAT必需提高5°F,但是在这种情况下(没有再循环),总的润滑油收率保持相同,而润滑油馏分的倾点稍微有些提高(变坏)。 In order to maintain the approach pour point WAT 300N, dewaxing tower must be increased 5 ° F, but in this case (without recycling), the total lube yield remains the same pour point lubricating oil fraction slightly increase (deterioration).

B.对于试验7,实质上保持新鲜原料速率,异构脱蜡塔进料含有14%的分馏塔底产物。 B. For Test 7, the fresh feed rate remains substantially, isodewaxing column feed contained 14% fractionator bottoms. 在这种情况下,我们能够稍微降低异构脱蜡塔催化剂温度,同时保持接近上述产物倾点,我们看到总的润滑油收率提高了2%。 In this case, we were able to slightly reduce the temperature of the dewaxing catalyst column, while maintaining a pour point close to the product, we see the total lube yield increased by 2%. 也许更重要的是,100N的收率提高4%,而100N倾点有稍微下降。 Perhaps more importantly, the yield of 4% 100N, 100N and pour point dropped slightly.

上面的比较实施例显示了,当再循环一部分分馏塔底产物时,能得到意外改善的性能。 Comparative Example The above embodiment shows that when recycling a portion of the fractionator bottoms product, unexpectedly improved properties can be obtained. 因为增加残留物的再循环量将最后限制可处理的新鲜原料的数量,经济上的限制通常将指出再循环的最高数量。 Because the increase in the recirculation amount of the final residue to limit the number of fresh feed that can be processed, economic limits will be noted that the maximum number is generally recycled.

表6中试试验进料进料A 进料B蜡质性质API比重 35.9 33.7氮ppm 1.6 1.3硫,ppm 7.3 6.3芳烃 6.04 7.7粘度,cSt@65C 9.110 11.766100C 4.24 5.137蜡的粘度指数 121 118倾点,℃ 39 39蜡含量,重量% 22.96 18.09蒸馏,°F10% 640 67850% 787 81990% 960 970溶剂脱蜡油粘度,cSt@40C 21.418 30.327100C 4.306 5.309粘度指数 107 108倾点,℃ -18 -21 Table 6 Test sample feed Feed A Feed B API Gravity 35.9 33.7 waxy nature Nitrogen ppm 1.6 1.3 Sulfur, ppm 7.3 6.3 Aromatics 6.04 7.7 Viscosity, cSt @ 65C 9.110 11.766100C 4.24 5.137 Viscosity Index 121 118 Pour point wax , ℃ 39 39 wax content, wt% 22.96 18.09 distillation, ° F10% 640 67850% 787 81990% 960 970 solvent dewaxed oil viscosity, cSt @ 40C 21.418 30.327100C 4.306 5.309 viscosity index 107 108 pour point, ℃ -18 -21

表7中试装置概括 Pilot plant are summarized in Table 7

两种进料都有有利于再循环的收率和/倾点。 Two feeds are beneficial to the yield and recycled / pour point.

Claims (39)

  1. 1.一种转化烃油的方法,包括:(a)在加入的氢气存在下,使烃油进料与催化剂体系接触,该催化剂体系含有一种中等孔径硅铝磷酸盐分子筛和一种加氢组分,其中所述的进料为润滑油原料且至少一部分所述的进料被转化;(b)将至少一部分转化了的进料通入分馏塔,其中分馏至少一部分所述的转化了的进料,从而产生至少一种塔顶馏分和一种塔底馏分;和(c)将至少一部分塔底馏分与步骤(a)的烃油进料混合,以提高收率或降低产物的倾点。 A method for the conversion of a hydrocarbon oil, comprising: (a) in the presence of hydrogen added to the hydrocarbon oil feed contacted with the catalyst system, the catalyst system contains a intermediate pore size silicoaluminophosphate molecular sieve and one hydrogenation component, wherein said lubricating oil feed and the feed of the feedstock is converted at least a portion of; (b) converting at least part of the fractionation column the feed inlet, wherein the fractionation of the at least a portion of said transformed feed, to produce at least one overhead fraction and one bottoms; and (c) at least a portion of the bottoms fraction of step (a) mixing a hydrocarbon oil feed, to increase or decrease the yield of the product pour point .
  2. 2.根据权利要求1的方法,其中所述的催化剂是选自SAPO-11,SAPO-31或SAPO-41。 2. The method according to claim 1, wherein said catalyst is selected from SAPO-11, SAPO-31 or SAPO-41.
  3. 3.根据权利要求1的方法,其中所述的催化剂还包括一种选自中等孔径铝硅酸盐沸石催化剂,无定形催化剂,和它们的混合物的催化剂。 3. The method according to claim 1, wherein said catalyst further comprises a medium pore zeolite catalyst is selected from aluminum, an amorphous catalyst, and mixtures thereof catalysts.
  4. 4.根据权利要求2的方法,其中所述的硅铝磷酸盐分子筛包括SAPO-11,所说的加氢组分包括铂。 4. A method according to claim 2, wherein said silicoaluminophosphate molecular sieve comprises SAPO-11, said hydrogenation component comprises platinum.
  5. 5.根据权利要求4的方法,其中所述的催化剂体系主要由SAPO-11组成。 The method according to claim 4, wherein the catalyst system is mainly composed of SAPO-11.
  6. 6.根据权利要求1的方法,其中所述的加氢组分的存在量为0.01%-10%,以分子筛的重量计。 6. The method according to claim 1, wherein said hydrogenation component is present in an amount of 0.01% to 10%, by weight of molecular sieve.
  7. 7.根据权利要求2的方法,其中该催化剂体系还包括一种中等孔径铝硅酸盐沸石催化剂并主要是氢的形式。 7. A method according to claim 2, wherein the catalyst system further comprises a medium pore size aluminosilicate zeolite catalyst and is primarily in the form of hydrogen.
  8. 8.根据权利要求7的方法,其中所述的催化剂还包括一种加氢组分。 8. A method according to claim 7, wherein said catalyst also comprises a hydrogenation component.
  9. 9.根据权利要求8的方法,其中所述的加氢组分包括一种VIII族金属。 9. A method according to claim 8, wherein the hydrogenation component comprises one Group VIII metal.
  10. 10.根据权利要求9的方法,其中所述的加氢组分选自铂,钯,及其混合物。 10. The method of claim 9, wherein said hydrogenation component is selected from platinum, palladium, and mixtures thereof.
  11. 11.根据权利要求7的方法,其中所述的中等孔径铝硅酸盐沸石的约束指数在400℃-454℃下测得为4-12。 11. The method according to claim 7, wherein the constraint index of intermediate pore size aluminosilicate zeolites at 400 ℃ -454 ℃ measured to 4-12.
  12. 12.根据权利要求7的方法,其中所述的中等孔径铝硅酸盐沸石选自ZSM-5,ZSM-11,ZSM-12,ZSM-22,ZSM-23,ZSM-35,SSZ-48,和它们的混合物。 12. The method according to claim 7, wherein said intermediate pore size aluminosilicate zeolite is selected from ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, SSZ-48, and mixtures thereof.
  13. 13.根据权利要求7的方法,其中所述的中等孔径铝硅酸盐沸石催化剂还含有选自包括铂,钯和镍及其混合物的VIII族金属,或包括钼,铬,钨,和它们的混合物的VIB族金属。 13. The method according to claim 7, wherein said intermediate pore size aluminosilicate zeolite catalyst further comprises a Group VIII metal selected from the group comprising platinum, palladium and nickel and mixtures thereof, or include molybdenum, chromium, tungsten, and their group VIB metal of the mixture.
  14. 14.根据权利要求7的方法,其中所述中等孔径硅铝磷酸盐分子筛与所述中等孔径硅铝磷酸盐沸石分子筛的重量比为1∶5-20∶1。 14. The method according to claim 7, wherein said intermediate pore size silicoaluminophosphate molecular sieve and the weight of the intermediate pore size silicoaluminophosphate molecular sieve zeolite ratio 1:5-20:1.
  15. 15.根据权利要求1的方法,其中所述的方法是脱蜡方法,其中所述的接触是在脱蜡条件下进行的。 15. The method according to claim 1, wherein said method is a dewaxing process, wherein said contacting is conducted under dewaxing conditions.
  16. 16.根据权利要求15的方法,其中所述的接触是在下列条件下进行的:温度为200℃-475℃,压力为15磅/平方英寸-3000磅/平方英寸,液时空速为0.1小时-1-20小时-1和氢循环速率为500-30,000 SCF/bbl。 16. The method according to claim 15, wherein said contacting is carried out under the following conditions: temperature of 200 ℃ -475 ℃, a pressure of 15 pounds / square inch -3000 pounds / square inch, a liquid hourly space velocity of 0.1 hours -1-20 hr -1 and a hydrogen circulation rate of 500-30,000 SCF / bbl.
  17. 17.根据权利要求15的方法,其中与所述的烃油进料混合的分馏塔底产物的量是提高转化进料的收率或降低了转化进料的倾点的有效量。 17. The method according to claim 15, wherein the hydrocarbon oil feed is mixed in an amount of bottom product is fractionated to increase the yield or conversion of the feed reduced the pour point of an effective amount of conversion of the feed.
  18. 18.根据权利要求17的方法,其中1重量%-80重量%的分馏塔底产物与烃油进料混合。 18. The method of claim 17, wherein 1% to 80 wt% by weight of the product fractionator bottoms mixed with the hydrocarbon oil feedstock.
  19. 19.根据权利要求15的方法,其中与烃油进料混合的分馏塔底产物与烃油进料的重量比是提高转化进料的收率或降低转化进料的倾点的有效重量比。 19. The method of claim 15, wherein the hydrocarbon oil feed and fractionating the bottom product and the mixed ratio by weight of the hydrocarbon oil feed is to improve the yield or conversion of the feed to reduce the effective weight of the pour point of the feed conversion ratio.
  20. 20.根据权利要求19的方法,其中与烃油进料混合的分馏塔底产物与烃油进料的重量比为1∶100-60∶100。 20. The method of claim 19, wherein the weight of the hydrocarbon oil feed to the fractionator bottoms mixed with the hydrocarbon oil feed ratio 1:100-60:100.
  21. 21.根据权利要求1的方法,其中所述的烃油进料含有小于50ppmw的有机氮。 21. The method according to claim 1, wherein said hydrocarbon oil feedstock contains less than 50ppmw organic nitrogen.
  22. 22.根据权利要求21的方法,其中所述的烃油进料含有小于10ppmw的有机氮。 22. The method according to claim 21, wherein said hydrocarbon oil feedstock contains less than 10ppmw organic nitrogen.
  23. 23.根据权利要求1的方法,其中所述的烃油进料是含蜡重质高粘度润滑油料。 23. The method according to claim 1, wherein said hydrocarbon oil feedstock is a heavy waxy bright stock.
  24. 24.根据权利要求1的方法,其中所述的烃油进料包括润滑油范围的提余油,其中该方法是一种使提余油加氢脱蜡的方法,包括在加入的氢存在下、在加氢脱蜡条件下使提余油与催化剂体系接触。 24. The method according to claim 1, wherein said hydrocarbon oil feed comprising a lubricating oil range raffinate, wherein the method is a method that the raffinate hydrodewaxing, comprising the addition of hydrogen in the presence of under hydrodewaxing conditions for the raffinate contacted with the catalyst system.
  25. 25.根据权利要求1的方法,其中所述的烃油进料包括含蜡烃进料,其中该方法是,相对于常规溶剂脱蜡法而言,改善了含蜡烃进料的脱蜡产物的粘度指数的方法,包括在异构脱蜡条件下使催化剂与含蜡烃进料接触。 25. The method according to claim 1, wherein said hydrocarbon oil feedstock comprises a waxy hydrocarbon feed, wherein the process is, relative to conventional solvent dewaxing process, improving the dewaxed product of waxy hydrocarbon feeds the method of viscosity index, comprising contacting the catalyst under isomerization dewaxing conditions with a waxy hydrocarbon feed.
  26. 26.根据权利要求1的方法,其中至少主要部分的烃油进料的沸点高于350°F,并含有直链和轻度支链烃,其中该方法是使沸点高于350°F、并含有直链和轻度支链烃的烃油进料催化脱蜡的方法,包括在加入的氢气存在下、在氢压为15-3000磅/平方英寸和脱蜡条件下,使烃油进料与催化剂体系接触。 26. The method of claim 1, wherein at least a major portion of a hydrocarbon oil having a boiling point of the feed is above 350 ° F, and containing straight chain and slightly branched chain hydrocarbons, wherein the process is a boiling point above 350 ° F, and a hydrocarbon oil feed containing straight catalytic dewaxing chain and slightly branched chain hydrocarbons, including in the presence of added hydrogen, at a hydrogen pressure of 15-3000 pounds / square inch and dewaxing conditions, the hydrocarbon oil feed contacted with the catalyst system.
  27. 27.根据权利要求1的方法,其中该方法是一种制备润滑油的方法:(a)其中所述的烃油进料是在加氢裂化区使烃质进料加氢裂化、以得到一种含有加氢裂化油的流出物;和(b)其中所述的接触步骤包括,在温度为至少200℃、压力为15磅/平方英寸一3000磅/平方英寸、和在加入的氢气存在下,用所说催化剂使所述的流出物催化脱蜡。 27. The method according to claim 1, wherein the process is a process for preparing a lubricating oil: (a) wherein said hydrocarbon oil feedstock is a hydrocarbon feedstocks hydrocracking in a hydrocracking zone to obtain a species effluent comprising hydrocracked oil; and the contacting step (b) wherein said comprises, at a temperature of at least 200 ℃, a pressure of 15 lbs / inch to 3000 lbs / square inch, and in the presence of added hydrogen , with said catalyst in said catalytic dewaxing the effluent.
  28. 28.一种对烃油进行脱蜡的方法,包括:(a)在加入的氢气存在下,使润滑油进料与催化剂体系接触,该催化剂体系含有一种中等孔径硅铝磷酸盐分子筛和一种加氢组分,其中以硅铝磷酸盐分子筛的重量计,所述的加氢组分的存在量为0.01%-10%,并含有一种选自沸石,无定形催化剂,及其混合物的催化剂,其中至少一部分进料被脱蜡;(b)将至少一部分脱蜡进料通入一个分馏塔,其中分馏至少一部分所述的脱蜡进料,从而产生至少一种塔顶馏分和一种塔底馏分;和(c)使有效量的塔底馏分与步骤(a)的烃油进料混合,以提高脱蜡进料的收率或降低其倾点。 28. A method for dewaxing a hydrocarbon oil, comprising: (a) in the presence of hydrogen added, the lubricating oil feed contacted with the catalyst system, the catalyst system contains a intermediate pore size silicoaluminophosphate molecular sieve and a species hydrogenation component, wherein the silicoaluminophosphate molecular sieve by weight of the hydrogenation component is present in an amount of 0.01% to 10%, and comprising one selected from zeolite, an amorphous catalyst, and mixtures thereof the catalyst, wherein at least a portion of the feed is dewaxed; (b) at least a portion of the dewaxed fed into a fractionation column, wherein said fractionation dewaxing least a portion of the feed to produce at least one overhead fraction and one bottoms fraction; and (c) an effective amount of the bottoms fraction of step (a) mixing a hydrocarbon oil feed, to increase the yield of dewaxed feedstock or reduce the pour point.
  29. 29.根据权利要求28的方法,其中所述的硅铝磷酸盐分子筛包括SAPO-11,加氢组分包括铂。 29. The method of claim 28, wherein said silicoaluminophosphate molecular sieve comprises SAPO-11, the hydrogenation component comprises platinum.
  30. 30.根据权利要求29的方法,其中所述的硅铝磷酸盐分子筛主要由SAPO-11组成。 30. The method of claim 29, wherein the silicoaluminophosphate molecular sieve SAPO-11 is mainly composed of.
  31. 31.根据权利要求28的方法,其中所述的铝硅酸盐沸石催化剂还包括一种VIII族金属加氢组分。 31. The method according to claim 28, wherein said aluminosilicate zeolite catalyst further comprises one Group VIII metal hydrogenation component.
  32. 32.根据权利要求31的方法,其中所述的中等孔径硅铝酸盐沸石选自ZSM-5,ZSM-11,ZSM-12,ZSM-22,ZSM-23,ZSM-35,SSZ-48,和它们的混合物。 32. The method according to claim 31, wherein said intermediate pore size aluminosilicate zeolite is selected from ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, SSZ-48, and mixtures thereof.
  33. 33.根据权利要求28的方法,其中所述中等孔径硅铝磷酸盐分子筛与所述中等孔径硅铝磷酸盐沸石分子筛的重量比为1∶5-20∶1。 33. The method according to claim 28, wherein said intermediate pore size silicoaluminophosphate molecular sieve and the weight of the intermediate pore size silicoaluminophosphate molecular sieve zeolite ratio 1:5-20:1.
  34. 34.根据权利要求28的方法,其中所述的方法是脱蜡方法,其中所述的接触是在脱蜡条件下进行的。 34. The method according to claim 28, wherein said method is a dewaxing process, wherein said contacting is conducted under dewaxing conditions.
  35. 35.根据权利要求34的方法,其中所述的接触是在下列条件下进行:温度为200℃-475℃,压力为15磅/平方英寸-3000磅/平方英寸,液时空速为0.1小时-1-20小时-1和氢循环速率为500-30,000SCF/bbl。 35. The method according to claim 34, wherein said contacting is carried out under the following conditions: temperature of 200 ℃ -475 ℃, a pressure of 15 pounds / square inch -3000 pounds / square inch, a liquid hourly space velocity of 0.1 hr - 1-20 h -1 and a hydrogen circulation rate of 500-30,000SCF / bbl.
  36. 36.根据权利要求28的方法,其中1重量%-80重量%的分馏塔底产物与烃油进料混合。 36. The method according to claim 28, wherein 1% to 80 wt% by weight of the product fractionator bottoms mixed with the hydrocarbon oil feedstock.
  37. 37.根据权利要求36的方法,其中与烃油进料混合的分馏塔底产物与烃油进料的重量比为1∶100-60∶100。 37. The method according to claim 36, wherein the weight of the hydrocarbon oil feed to the fractionator bottoms mixed with the hydrocarbon oil feed ratio 1:100-60:100.
  38. 38.根据权利要求28的方法,其中所述的烃油进料含有小于50ppmw的有机氮。 38. The method according to claim 28, wherein said hydrocarbon oil feedstock contains less than 50ppmw organic nitrogen.
  39. 39.一种对烃油进行脱蜡的方法,包括:(a)在温度为200℃-475℃温度、压力为15磅/平方英寸-3000磅/平方英寸、液时空速为0.1小时-1-20小时-1和氢循环速率为500-30,000SCF/bbl的条件下,在加入的氢气存在下,使含有小于50ppmw有机氮的润滑油进料与催化剂接触,该催化剂主要由一种SAPO-11中等孔径硅铝磷酸盐分子筛和一种加氢组分和一种含有VIII族金属加氢组分的SSZ-32沸石催化剂组成,其中,以硅铝磷酸盐分子筛的重量计,该加氢组分存在量为0.01%-10%,其中SAPO-11与SSZ-32的重量比为1∶5-20∶1,其中至少一部分所述的进料被脱蜡;(b)将至少一部分脱蜡了的进料通入分馏塔,其中分馏至少一部分所述的脱蜡进料,从而产生至少一种塔顶馏分和一种塔底馏分;和(c)将1重量%-80重量%的塔底馏分的脱蜡进料与步骤(a)的烃油进料接触。 39. A method for dewaxing a hydrocarbon oil, comprising: (a) at a temperature of temperature 200 ℃ -475 ℃, a pressure of 15 pounds / square inch -3000 pounds / square inch, a liquid hourly space velocity is from 0.1 h -1 -20 hr -1 and a hydrogen circulation rate of 500-30,000SCF / bbl under conditions, in the presence of hydrogen added, the lubricating oil is less than 50ppmw organic nitrogen containing feed contacted with the catalyst, the catalyst consisting essentially of one SAPO- 11 intermediate pore size silicoaluminophosphate molecular sieve and one hydrogenation component and SSZ-32 zeolite catalysts containing a group VIII metal hydrogenation component composition, wherein the silicoaluminophosphate molecular sieve to the weight of the hydrogenation component partial amount from 0.01% to 10%, wherein the weight ratio of SAPO-11 SSZ-32 is 1:5-20:1, wherein at least a portion of the feed to be dewaxed; (b) at least a portion of the dewaxed feed into the fractionation column, wherein said fractionation dewaxing least a portion of the feed to produce at least one overhead fraction and one bottoms fraction; and (c) 1 wt% to 80 wt% of the column dewaxed feed with the bottom fraction in step (a) contacting the hydrocarbon oil feed.
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