CN101433817A - Desulphurization sorbent - Google Patents

Desulphurization sorbent Download PDF

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CN101433817A
CN101433817A CN 200710177415 CN200710177415A CN101433817A CN 101433817 A CN101433817 A CN 101433817A CN 200710177415 CN200710177415 CN 200710177415 CN 200710177415 A CN200710177415 A CN 200710177415A CN 101433817 A CN101433817 A CN 101433817A
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zeolite
mixture
adsorbent
rare earth
weight
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CN101433817B (en
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唐津莲
张久顺
莉 徐
汪燮卿
许友好
谢朝钢
达志坚
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中国石油化工股份有限公司;中国石油化工股份有限公司石油化工科学研究院
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Abstract

The invention discloses a desulfurization adsorbent, which comprises 1 to 30 weight percent of rare earth-zeolite mixture, 5 to 40 weight percent of active metal oxide and 30 to 94 weight percent of carrier, wherein the carrier comprises alumina and zinc oxide; the rare earth-zeolite mixture and a carrier mixture are preformed into porous heat-resistant solid particles, and then active metal ingredients are introduced on the solid particles to obtain the adsorbent; and a light hydrocarbon oil raw material containing sulfur and a hydrogen donor enter a reactor filled with the adsorbent, materials remained after the reaction are separated, a reaction product is sent into a subsequent separation system for product separation, a spent adsorbent after the reaction is steam-stripped and then is subject to coke-burning regeneration, and the regenerated adsorbent is reduced by the hydrogen donor and is returned to the reactor for cyclic use. The adsorbent realizes the deep removal of sulfide in light hydrocarbon oil, and the produced gasoline has higher octane number, lower benzene content, and higher strength at the same time.

Description

一种脱》克吸附剂技术领域 One desugared "g-adsorbent Field

本发明属于在一种降低轻质石油烃中硫含量的吸附剂及其制备、应用。 The present invention resides in a method of reducing the adsorbent and the production of light hydrocarbon oil sulfur content, applications.

背景技术 Background technique

随着人们对环境保护的日益重视,对作为燃料的轻质烃油中的硫含量 With increasing emphasis on environmental protection, the sulfur content of light hydrocarbon oil as a fuel in the

限制越来越严格。 More stringent restrictions. 以汽油为例,美国环保局(EPA)规定疏限值为30照/g (TierII);欧洲要求汽油硫含量低于50照/g (欧IV排放标准);中国对汽油硫含量的限制也将逐步与国际接轨。 In gasoline, for example, the United States Environmental Protection Agency (EPA) 30 according to a predetermined limit of hydrophobic / g (TierII); European requirements as gasoline sulfur content of less than 50 / g (Euro IV emission standards); Chinese restrictions on the sulfur content of the gasoline also the step by step with international practice. 因而,必须使烃油深度脱硫才能合乎要求。 Accordingly, it is necessary to make the deep desulfurization of a hydrocarbon oil desirable.

目前,油品的深度脱疏方法除加氳技术外,吸附法脱除燃油中的含硫化合物也是近年来非常吸引人的一项技术。 Currently, the depth of de-repellent oil addition method adding Yun technology, adsorption removal of sulfur compounds in the fuel is a very attractive technology in recent years. 如US6350422、 US6955752、 US6482314、 US6428685、 US63461卯所述,采用吸附剂对轻质油进4亍临氬反应吸附,氢耗较低,脱硫效率高,可以生产硫含量在30jig/g以下汽油或柴油,其吸附剂由还原态钴、镍、铁、锰、铜、钼、鴒、银、锡、钒金属中的一种或两种载于载体上构成,所述载体釆用氧化锌氧化物、硅石和氧化铝的混合物,载体中氧化锌占10~90重%、硅石占5~85重%、 氧化铝占5~30重%。 As US6350422, US6955752, US6482314, US6428685, US63461 the sockets using light oil adsorbent right foot 4 into the reaction Pro argon adsorption, low hydrogen consumption, high desulfurization efficiency, the sulfur content of gasoline can be produced in 30jig / g or less diesel its reduced state by the adsorbent of cobalt, nickel, iron, manganese, copper, molybdenum, alba, silver, tin, vanadium contained in one or both constituting the carrier, which preclude the use of a zinc oxide oxide, a mixture of silica and alumina, zinc oxide, the carrier accounts for 10 to 90 wt%, the silica accounts for 5 to 85 wt%, alumina 5-30 wt%. 载体组分与金属组分经混合、成粒、干燥、煅烧制成双金属结构型脱硫吸附剂,在0.7〜2.1MPa、 343〜413'C和临氬的操作条件下捕捉汽油中的硫,生成金属硫化物或利用硫化物极性脱除硫,含疏催化剂循环再生。 Carrier component to the metal component by mixing, granulating, drying, calcination bimetal structure formed desulfurization sorbent to capture sulfur in gasoline at 0.7~2.1MPa, 343~413'C Pro argon and operating conditions, generating polar metal sulfide or sulfide removal using sulfur-containing hydrophobic catalyst regeneration cycle. 上述专利虽然在低氢耗下实现了烃油的深度脱硫,然而其汽油产物辛烷值仍然略有损失。 Although the above patent achieve deep desulfurization of hydrocarbon oil at low hydrogen consumption, however, it is still a slight loss of octane gasoline product.

CN1261218C、 CN1583973A、 CN1583972A均采用沸石脱石克剂对轻质 CN1261218C, CN1583973A, CN1583972A zeolites are used for the light nontronite g agent

油品在非临氬条件下裂化脱硫,选择性裂化硫化物将其转化成烃和无才;u充 Desulfurized cracked oil in a non-clinical atmosphere of argon, selective cracking of hydrocarbons converted to sulfides and without it; U charge

化物,无氢耗,无辛烷值损失,但是,与重质油催化裂化脱硫一样,其脱硫率受原料硫含量、催化剂性质以及转化深度等影响,不足以实现深度脱硫,脱硫率一般在50-80%,只能用于生产低硫成品油,辛烷值损失低。 Compound, no hydrogen consumption, without loss of octane number, however, with the heavy oil FCC as desulfurization, the desulfurization rate is affected by the sulfur content in the raw material, the nature of the catalyst and the conversion depth, enough to achieve deep desulfurization, the desulfurization rate is generally 50 -80%, refined oil only for producing low sulfur, low octane loss.

发明内容本发明的目的之一是在现有技术的基础上提供一种降低轻质燃料油中硫含量的吸附剂。 One object of the present invention is to provide a light fuel oil sulfur content of the adsorbent is reduced on the basis of the prior art.

本发明的目的之二是提供所述吸附剂的制备方法。 Another object of the present invention is to provide a method of the two adsorbents.

本发明的目的之三是提供一种应用所述吸附剂降低石油烃硫含量的方法。 Another object of the present invention is to provide a three-applying the petroleum hydrocarbon adsorbent to reduce the sulfur content of the method.

本发明提供的脱硫吸附剂包括:1-30重%的稀土沸石混合物,5~40 重%的活性金属氧化物和30~94重。 Desulfurization sorbents of the present invention comprises: 1-30% by weight of a mixture of rare earth zeolite, 5 to 40% by weight of active metal oxide and 30 to 94 weight. /。 /. 的含锌硅铝基质载体,均以吸附剂总重量为计算基准。 Zinc-containing alumina matrix carrier, are calculated on the basis of the total weight of the adsorbent.

所述稀土沸石混合物占吸附剂组合物总重量的1-30重%,优选5~25 重%。 The zeolite is a mixture of rare accounting for 1-30 wt% of the total weight of the sorbent composition, preferably 5 to 25 wt%. 以稀土沸石混合物的重量为计算基准,稀土沸石混合物的组成如下: 稀土以RE203计,占1-35重%;沸石混合物占65-99重%。 By weight of zeolite calculated on the basis of a mixture of rare earth, rare earth zeolite mixture composed as follows: In the rare earth RE203 basis, accounting for 1-35 wt%; accounting for 65-99 wt% zeolite mixture.

所述稀土均选自La、 Ce、 Pr、 Nd、 Sm中的一种或两种以上元素。 Are selected from the rare earths La, Ce, Pr, Nd, Sm, one kind or two or more elements.

所述稀土沸石混合物指稀土择形沸石与稀土八面沸石按照重量比例10: 1至1: 10优选1: 1.1至1: 5混合的混合物。 The rare earth refers to a mixture of rare earth shape selective zeolite with rare earth faujasite zeolite in a weight ratio of 10: the mixture is mixed 5: 1 to 1: 10 preferably 1: 1.1 to 1.

其中所述稀土择形选自含稀土的五元环高硅沸石、含稀土的ZRP沸石、含稀土的Beta沸石中一种或几种,其硅铝比为20-500。 Wherein said rare earth is selected from shape-selective high silica zeolite five-membered ring containing rare earth, ZRP zeolites containing rare earth, rare earth-containing zeolite Beta of one or several of its silica to alumina ratio is 20-500. 其中所述五元环高珪沸石选自ZSM-5沸石、ZSM-8沸石、ZSM-ll沸石、ZSM-22 沸石、ZSM-23沸石、ZSM-48沸石、ZSM-57沸石中的一种或几种;Beta 沸石包括NaP型、Hp型、USP型沸石中的一种或几种。 Wherein said five-membered ring zeolite is selected from high-gui ZSM-5 zeolite, ZSM-8 zeolite, ZSM-ll zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-48 zeolite, ZSM-57 zeolite or a several; NaP type zeolites include Beta, Hp type, USP-type zeolite is one or more.

所述八面沸石为X型系列沸石或/和Y型系列沸石。 The faujasite zeolite is type X zeolite series or / and Y series zeolites. 稀土八面沸石优选稀土Y型系列沸石,包括REY型、REHY型、REUSY型沸石中的一种或两种以上的混合物。 Preferably rare earth rare earth faujasite type Y zeolite series, including type REY, REHY type A REUSY type zeolites or a mixture of two or more.

所述活性金属氧化物占吸附剂组合物总量的5~40重%,优选15-30 重%。 The active metal oxide occupies 5 to 40% of the total weight of the sorbent composition, preferably 15-30 weight%. 所述活性金属选自钴、镍、铁、锰、铜、钼、鴒、银、锡、钒等过渡金属中的一种或两种以上金属,优选钴或/和镍。 The active metal selected from cobalt, nickel, iron, manganese, copper, molybdenum, alba, silver, tin, vanadium and other transition metals, one or two or more metals, preferably cobalt and / or nickel.

所述含锌硅铝基质载体含粘土5~85重%,优选35-80重%。 The zinc-containing clay-containing alumina matrix carrier 5 to 85 weight%, preferably 35-80 weight%. 以载体的重量为计算基准,载体的组成如下:氧化铝5~30重%,优选5~15重%; 氧化锌10~65重%,优选15-50重%;余量为粘土。 To calculate the weight of the carrier base, a carrier composition as follows: 5 to 30 weight% alumina, preferably 5 to 15 wt%; zinc oxide, 10 to 65 weight%, preferably 15-50 weight%; the balance being clay. 所述氧化锌可以采用氧化锌,也可以采用其前驱体,包括氬氧化锌及含锌金属盐如硫酸锌、硝酸锌、醋酸锌、卣化锌及含锌铵盐、含锌钠盐等。 The zinc oxide may be zinc oxide, precursors thereof may be used, including argon and zinc salts such as zinc oxide, zinc sulfate, zinc nitrate, zinc acetate, and zinc ammonium wine container, zinc, zinc salt and the like. 所述粘土选自氧化硅、 无定形硅铝、天然多孔载体材料如高呤土、多水高岭土、蒙脱土、膨润土、 硅藻土、海泡石、累脱土等无机氧化物中的一种或两种以上混合物,优选氧化硅、高岭土、累脱土中两种或两种以上的混合物,其中任意两种粘土 The clay inorganic oxide selected from silicon oxide, amorphous silica-alumina, porous support material such as high natural soil methotrexate, halloysite, montmorillonite, bentonite, diatomaceous earth, sepiolite, bentonite and the like accumulated in a or two or more kinds of mixtures, preferably silicon oxide, kaolin, clay mixtures of two or more kinds of tired off, any two clay

组分之间的重量比为0.1〜100:1,优选0.5〜50:1。 The weight ratio between the components is 0.1~100: 1, preferably 0.5~50: 1.

本发明提供的吸附剂制备方法是,将上述稀土择形沸石和稀土八面沸石的混合物与含锌硅铝基质载体混合物预先成形为多孔耐热固体颗粒,再在此固体颗粒上引入金属活性组分的方法。 The method of preparing an adsorbent of the present invention provided that the shape-selective zeolite and the rare rare earth faujasite zinc alumina matrix carrier mixture with the mixture previously formed porous heat-resistant solid particles, reintroduction of the active metal on the solid particles methods minute.

匀的混合物,;干燥i形、J烧。 Uniform mixture; dried i-shaped, J burning. '稀土沸L与载体ki;勿优选的;备方i 是溶胶-凝胶法。 'Rare earth zeolite L and Ki carrier; do not preferred; Preparation entity i sol - gel method.

本发明在固体颗粒上引入金属活性组分的方法,可以釆用现有的各种负载金属氧化物的方法,如浸渍的方法,即采用上述一种或几种金属盐溶 The method of the present invention introduces metal active component in the solid particles, can preclude the use of the conventional method of supporting a variety of metal oxides, such as impregnation method, i.e., one or more of the above-described metal salt solution

液浸渍已成型的载体;或者沉淀的方法,即采用上述一种或几种金属盐溶液或其氧化物、氢氧化物沉积到多孔耐热载体上;或者固体氧化物和/或其前身物-金属盐或其氢氧化物与载体机械混合,研磨或是不研磨的方法; 或者溶胶处理法、胶凝法以及水热法等。 Impregnating the formed carrier liquid; or a method of precipitation, i.e., one or more of the above-described metal salt solution or an oxide, hydroxide deposited onto the porous refractory support; or a solid oxide and / or precursor thereof - metal salt or hydroxide of mechanical mixing with a carrier, or polishing without polishing method; processing method or a sol, gel method and hydrothermal method. 所述金属盐主要是上述金属的疏酸盐、硝酸盐、醋酸盐、卣化物及金属铵盐、金属钠盐等。 The metal salt of the metal salt is mainly hydrophobic, nitrates, acetates, wine container and metal salts thereof, metal sodium salt. 本发明所述吸附剂的金属活性组分在制备过程中采用金属盐的形式,因而引入金属活性组分的优选方法是沉淀的方法或浸渍的方法。 The adsorbent of the present invention in the form of metal salts of the active ingredient during the manufacturing process, and therefore preferred method of introducing the active metal components are precipitated or impregnation method.

金属活性组分及其载体混合物可以采用造粒、挤条或喷雾干燥等方法成型;成型后干燥、焙烧等。 Metal active component and carrier mixture may be employed granulation, spray drying or extruding molding method; after forming and drying, calcining and the like. 其干燥温度可以是室温至400°C,优选为100~200°C,也可以采用孩支波干燥。 Drying temperature may be from room temperature to 400 ° C, preferably 100 ~ 200 ° C, may be employed children branched wave drying. 焙烧温度可以是400-1200°C,优选为500-800°C;焙烧时间0.5-100小时,优选为1~10小时。 Calcination temperature may be 400-1200 ° C, preferably 500-800 ° C; baking time of 0.5 to 100 hours, preferably 1 to 10 hours.

按照本发明所提供的方法,吸附剂优选的制备方法如下: (1)稀土沸石混合物溶胶制备 The method provided by the invention, the adsorbent is preferably prepared as follows: (1) preparing a mixture of rare earth zeolite sol

将市售稀土择形沸石与稀土八面沸石按照一定比例机械混合均匀配制成沸石混合物,按照沸石混合物:铵盐:去离子水=1: 0~1: 3~40(优选1: 1: 20)的重量比在50〜100。 Commercially available shape selective zeolite with rare earth rare earth faujasite mixed in a certain proportion of the mechanical mixture of zeolites formulated according zeolite mixture: ammonium salt: Deionized water = 1: 0 to 1: 3 to 40 (preferably 1: 1:20 ) 50~100 weight ratio. C下离子交换0.1~5小时,过滤、水洗后重复交换一次得到铵型沸石,其Na2O含量不大于0.15重。 Ion exchange C 0.1 ~ 5 hours, filtered, washed with water was repeated once to give the ammonium exchanged zeolite having a Na2O content of not greater than 0.15 weight. /。 /. . 在室温下将上述铵型沸石与计量氯化稀土的水溶液搅拌浸渍2小时,120~200°C 烘干,450~850°〇焙烧0.5~4小时,得到以11£203计的稀土含量为1.0-35 重%的沸石混合物。 At room temperature the aqueous solution of the ammonium form zeolite with rare earth chloride is stirred metering immersed 2 hours, 120 ~ 200 ° C drying, 450 ~ 850 ° square calcined 0.5 to 4 hours, to obtain a rare earth content of 11 £ 203 1.0 meter -35% weight of mixture of zeolites. 将制得的稀土沸石混合物与脱阳离子水按照固液重量比1:1〜1:10混合,打浆,搅拌均匀制得稀土沸石溶胶; (2 )载体溶胶制备将预订重的粉禾状栽体材秤或孰体的固体沉淀物与去离于水混合打 The zeolite mixture was prepared with a rare earth cation removing water at a solid to liquid weight ratio of 1: 1~1: 10 mixing, beating, stirring uniformly to prepare a rare earth zeolite sol; (2) Preparation of sol reservation carrier powder weight Wo-like plant body the solid precipitate material body in what scale or mixed with deionized water to play

浆,得到固含量为5~30重量%的浆液,在搅拌下加入盐酸或硝酸的水溶 Pulp, a solids content of 5 to 30 wt% of the slurry, nitric acid or hydrochloric acid was added with stirring under water-soluble

液,使浆液? Liquid, the slurry? 11=2~4,搅拌均匀,在30〜100。 11 = 2-4, stir, at 30~100. C下静置老化至少0.5小时制得载体溶胶; C and aged by standing at least 0.5 hours to prepare a sol carrier;

(3)固体颗粒制备将步骤(1)与步骤(2)制得的老化后的载体溶胶混合,并加入适量铝溶胶,吸附剂固含量与铝溶胶固含量(以氧化铝计)重量比为10~50, 继续搅拌直到形成均匀的溶胶;将此溶胶在控制尾气温度为250-300。 (3) preparing solid particles of step (1) and Step (2) mixing the sol obtained after the vector aging, and adding an appropriate amount of alumina sol, and the sol solids content of the solid adsorbent is the content of aluminum (in terms of aluminum oxide) weight ratio of 10 to 50, and stirring was continued until a homogeneous sol; sol was controlled at a temperature of exhaust gas 250-300. C, 喷雾压力为50〜60个大气压,喷雾干燥成型,制得微球状的固体载体颗粒。 C, spray pressure of 50 to 60 atmospheres, spray drying and pressing, to obtain microspheroidal particles of a solid support. 将得到的微球状固体颗粒洗涤除去游离Na+,在100〜200。 The resulting solid particles are removed by washing the microspheroidal free Na +, at 100 ~ 200. C下烘干至少2 小时后,再在500〜800。 After drying for at least 2 hours at C, and then at 500~800. C条件下焙烧至少2小时,得到微球状稀土沸石混合物与载体混合物的颗粒; C at least 2 hours under calcination conditions, to give a mixture of microspheroidal particulate zeolite support with a rare earth mixture;

(4 )金属氧化物活性组分引入 (4) the metal oxide active components are introduced

将预订量的含金属活性组分一种或多种的金属盐配成金属离子浓度为l~10mol/L的水溶液,在室温下按照金属氧化物与载体的比例加入步骤(3)制得的微球状稀土沸石混合物与载体混合物的颗粒,边搅拌边加入浓度为0.5~5mol/L的氨水,维持pH为7~10,不断搅拌至沉淀完全后, 升温至60〜10(TC并^L置老化至少0.5小时,过滤,洗涤滤饼至无酸根离子制得金属氢氧化物稀土沸石混合物与载体材料的混合物,在100~200°C 下烘干至少2小时后,再在500〜800'C条件下焙烧至少2小时,粉碎、过筛得到孩t球状吸附剂颗粒。 The amount of the metal-containing active ingredient reservation of one or more salts formulated metal ion concentration of l ~ 10mol L aqueous solution / was added in proportion to the step of the metal oxide support and at room temperature (3) prepared the mixture of rare earth zeolite microspheroidal particulate carrier mixture with stirring was added at a concentration of 0.5 ~ 5mol / L aqueous ammonia, maintaining a pH of 7 to 10, stirring constantly until the precipitation was complete, warmed to 60~10 (TC ^ L and opposing after aging at least 0.5 hours, filtered, the filter cake washed until no ion mixture obtained mixture of zeolites and rare earth metal hydroxide support material, drying at 100 ~ 200 ° C for at least 2 hours and at 500~800'C calcination under conditions at least 2 hours, pulverized, sieved child t spherical adsorbent particles.

上述制得的氧化态活性金属吸附剂在使用前采用特定的方法活化处理,使氧化态活性金属转化为零价态活性金属。 Prepared above was employed oxidation state of the active metal prior to the adsorbent using a particular activation process, the oxidation state of the active metal to zero valent state of the active metal. 本发明提供的处理方法是采用适合的还原剂如氢气等使上述吸附剂活性金属前驱物在200-400 °C的温度,氢气分压0.5-2.5MPa条件下还原至少30分钟,从而产生含有基本上零价态活性金属的吸附剂组合物。 Processing method provided by the invention is the use of a suitable reducing agent such as hydrogen or the like so that the active metal precursor adsorbent at a temperature of 200-400 ° C, a hydrogen partial pressure of 0.5-2.5MPa under reducing conditions at least 30 minutes, to produce a substantially comprising the zero valence state of the active metal sorbent composition.

本发明所使用的吸附剂为便于流化,最好为微球状,其平均粒径在40-200nm,其磨损指数最好小于2.5%.h"。 The adsorbent used in the present invention is to facilitate fluidization, preferably microspheroidal an average particle size of 40-200 nm, preferably wear index of less than 2.5% .h ".

本发明提供的降低轻质烃油硫含量的方法为: Method of reducing the sulfur content light hydrocarbon oil of the present invention provides:

预热后的含硫轻质烃油原料和供氢体,进入装有吸附剂的反应器内, 在温度350-450°C ,压力0.5-2.5MPa,原料油重时空速0.5-10 h",优选4-8 h-1;吸附剂总量与烃油原料的重量比1-20,优选5-15的条件下反应,分禺反应后物肝,反应广物逸入后续分禺舉统近仃严品分禺,反应后的待生吸附剂经汽提后烧焦再生,再生后的吸附剂经供氬体还原后返回反应器循环使用。 After preheating within the sulfur-containing light hydrocarbon oil feedstock and a hydrogen donor, into the reactor containing the sorbent, at a temperature of 350-450 ° C, pressure 0.5-2.5 MPa, a weight hourly space velocity feedstock oil 0.5-10 h " , preferably 4-8 h-1; by weight of the total amount of hydrocarbon oil feedstock with the adsorbent the reaction ratio 1-20, preferably 5-15 conditions after partial liver Yu reaction, the reaction product from escaping into the wide Yu subsequent partial lift system near points Ding Yan Yu products, spent adsorbent after the reaction was stripped burning regeneration, returns the sorbent body after regeneration argon supply reduction reactor recycle.

所述含^i的烃油原料选自汽油、煤油、柴油、瓦斯油馏分中的一种或两种以上的混合物,优选汽油或/和柴油。 A hydrocarbon oil feedstock containing a mixture of ^ i is selected from gasoline, kerosene, diesel oil, gas oil fractions of one or two or more, preferably gasoline and / or diesel fuel. 上述汽油、煤油、柴油、瓦斯油馏分为其全馏分或/和其部分窄馏分。 Above gasoline, kerosene, diesel, gas oil fractions for which the whole fraction or / and a cut portion is narrower. 所述含硫的烃油原料硫含量在 The sulfur-containing hydrocarbon oil feedstock sulfur content

100jLig/g以上,最好在500^ig/g以上。 100jLig / g or more, preferably 500 ^ ig / g or more.

所述供氢体选自氬气、含氩气体、供氬剂中的一种或一种以上的混合物,其中氢气为各种纯度的氢气,含氢气体优选本方法所产干气、催化裂化(FCC)干气、焦化干气、热裂化干气中的一种或一种以上的混合物, 含氢最好30体积%以上,供氢剂选自四氢萘、十氢萘、二氢茚中的一种或一种以上的混合物。 Said hydrogen donor is selected from argon, argon-containing gas, a mixture of argon agent for one or more of various wherein the hydrogen purity hydrogen gas, a hydrogen-containing gas is preferably produced by the process of dry gas, catalytic cracking (FCC) dry gas, dry gas coking, thermal cracking dry gas mixture in one or more, preferably 30 vol% hydrogen, the hydrogen donor is selected from tetrahydronaphthalene, decahydronaphthalene, indan a mixture of one or more than one.

所述反应器可以采用流化床反应器、固定床反应器、移动床反应器或其它类型的反应器及其复合,优选流化床反应器,包括固定流化床、散式流化床、鼓泡床、湍动床、快速床、输送床、密相流化床中的一种或几种。 The reactor may be a fluidized bed reactor, a fixed bed reactor, a moving bed reactor or other type of reactor and its compound, preferably a fluidized bed reactor, comprising a fixed fluidized bed, fluidized bed bulk, bubbling bed, turbulent bed, fast bed, transport bed, one or more dense phase fluidized bed.

本发明与现有技术相比具有下列预料不到的技术效果: The present invention and the prior art having the following unexpected technical effects as compared:

1、 本发明提供的吸附剂由还原态钴、镍等金属、稀土沸石混合物、 氧化锌及氧化硅、氧化铝、高岭土等无机氧化物组成,采用溶胶-凝胶法制得,具有脱^it活性好,吸附剂分布均勻,强度好等特点; 1, the adsorbent of the present invention is provided by the reduced state of cobalt, nickel and other metals, rare earth zeolite mixture, zinc oxide and silicon oxide, aluminum oxide, kaolin and other inorganic oxides by sol - gel method, having removal activity ^ it good, uniform distribution of adsorbent, good strength characteristics;

2、 本发明提供的吸附剂优选钴、镍中的一种或两种金属的还原态为活性组分,优选氧化硅、氧化铝、高呤土中的两种或三种以上的混合物为载体,添加一定量的稀土沸石混合物,通过这些组分之间的协同效应,使得该吸附剂实现深度脱除轻质烃油中硫化物的同时,保持了较高的液收, 尤其是用于汽油脱硫时,与现有技术相比,产物汽油辛烷值较高,而其苯含量较低,本发明提供的吸附剂适于生产超低硫清洁汽油。 2, the adsorbent of the present invention provides preferably cobalt, nickel or two metal reduced state as the active component, preferably silica, alumina, two or three or more high soil mixture whisper carrier adding a quantity of a mixture of rare zeolite, by the synergistic effect between the components, so that the adsorbent is achieved while the depth of removal of the light hydrocarbon oil sulfide, to maintain a high liquid yield, in particular for gasoline desulfurization, as compared with the prior art, high octane gasoline product, and its benzene content is low, the present invention provides an adsorbent suitable for the production of ultra-low sulfur clean gasoline.

3、 釆用本发明所提供的方法处理汽油原料时,可以在低氢耗甚至无氢耗的条件下实现深度脱硫,硫的脱除率可以达到97重%以上,并且降低了汽油烯烃的同时提高了汽油辛烷值,汽油的收率为98重%以上,产物汽油苯含量低,可以用于生产硫含量低于lO^ig/g的高辛烷值清洁汽油。 3 Meanwhile, when the gasoline feedstock Bian treated by the method provided by the invention may be achieved under conditions of low hydrogen consumption or no hydrogen consumption deep desulfurization, the sulfur removal efficiency can be higher than 97 weight%, and reduced the gasoline olefin increased gasoline octane, gasoline yield of 98 weight% or more, the product of low benzene content of gasoline, can be used to produce a sulfur content of less than lO ^ ig / g clean high octane gasoline.

4、 采用本发明所提供的方法处理柴油原料时,在临氢的条件下,柴油原料有较好的脱硫效果,脱硫率达99重。 4, when the method of the present invention provides a process oil feedstock in the presence of hydrogen under conditions of a diesel feedstock better desulfurization effect, the desulfurization rate of 99 wt. /。 /. 以上。 the above. 所生产柴油芳烃含量十六烷值略有提高。 Aromatics content of the cetane number of diesel produced increased slightly. 附闺讥明 Fuguijiming

附图为本发明提供的烃油在流化床反应器内临氬吸附催化转化脱硫的方法流程示意图。 BRIEF present invention provides a hydrocarbon oil in a fluidized bed reactor Pro argon adsorption desulfurization catalytic conversion process flow schematic.

具体实施方式 Detailed ways

下面结合附图对本发明提供的方法予以进一步的说明,但并不因此而使本发明受到任何限制。 The following be further illustrated in conjunction with the method of the present invention provides the drawings, but the present invention is therefore not limited in any way.

附图为本发明提供的烃油在流化床反应器内临氢吸附催化转化脱硫的方法流程示意图。 BRIEF method of the present invention provides a hydrocarbon oil in the presence of hydrogen within the catalytic conversion of a fluidized bed reactor adsorption desulfurization process schematic. 附图采用一个流化床反应器、 一个再生器和一个再生剂还原器。 BRIEF using a fluidized bed reactor, a regenerator and a regenerated catalyst reducer. 所述再生器、再生剂还原器均为流化床。 Said regenerator, regenerated catalyst are fluidized bed reducer.

预热后的汽油馏分原料和供氢体经管线1进入输送管2底部,与来自再生斜管17的再生后的吸附剂接触,在温度350-450。 The preheated naphtha fraction and hydrogen donor via line 1 into the bottom feed pipe 2, the adsorbent from the regeneration inclined pipe 17 is regenerated at a temperature of 350-450. C,压力0.5-2.5MPa, 原料油重时空速0.5-10 h—1,优选4-8h";吸附剂总量与烃油原料的重量比1-20,优选3-15的条件下反应,反应物流进入带有密相流化床反应器的沉降器7,反应油气经管线8送入后续的产品分离系统。待生吸附剂进入汽提器3,由来自管线4的蒸汽汽提待生吸附剂所携带的反应油气,汽提后的待生剂经待生斜管5进入再生器13,含氧气体经管线14引入再生器13,待生脱硫剂在含氧气体的作用下烧焦再生,再生烟气经管线12引出再生器,高温的再生吸附剂经管线15进入再生剂还原器16,采用氮气汽提、冷却后,以氢气还原,还原后的脱硫剂由再生斜管17返回输送管2 底部循环使用,松动风氮气经管线18进入再生剂还原器16。 C, pressure 0.5-2.5 MPa, a weight hourly space velocity of the feedstock oil 0.5-10 h-1, preferably 4-8h "; the total adsorbent weight ratio of the hydrocarbon oil feedstock 1-20, 3-15 preferable reaction conditions, the reaction stream entering settler with a dense phase fluidized bed reactor 7, the reaction of oil and gas via line 8 into the subsequent product separation system. spent adsorbent 3 into the stripper, to mention a steam line 4 from the spent the reaction carried hydrocarbon adsorbent, the stripped spent catalyst to be regenerated by the inclined pipe 5 into the regenerator 13, the oxygen-containing gas introduced into the regenerator 14 via line 13, the spent sorbent burnt under the action of an oxygen-containing gas , and the regeneration flue gas line 12 leads via the regenerator, the high-temperature regenerated sorbent into the regenerator 15 via line 16, reducing agents, stripping with nitrogen, cooled to hydrogen reduction, the reduced sorbent from the regeneration inclined pipe 17 returns recycling the bottom feed pipe 2, a nitrogen gas through line 18 loose air into the regenerator 16 reducer agent.

下面的实施例将对本发明提供的方法予以进一步的说明,但并不因此而使本发明受到任何限制。 The following examples will be provided by the method of the present invention is further illustrated, but the present invention is therefore not limited in any way.

实施例中所使用的原料性质列于表1。 Example embodiments properties of raw materials used are listed in Table 1. 沸石与载体混合物固体颗粒采用溶胶-凝胶法制取。 Zeolite mixture of solid particles with a carrier sol - gel Preparation.

吸附剂的组成釆用X射线焚光光谱法(RIPP 134-卯,见科学出版社《石油化工分析方法(RIPP试验方法)》)。 Preclude the use of sorbent compositions X-ray burning ray spectroscopy (RIPP 134- d, see Science Press "Petrochemical Analysis (the RIPP Test Method)"). 其中吸附剂磨损率的测定采用RIPP29-卯方法,以压缩空气作为流化介质,压力0.6MPa,流量20升/ 分,测出吸附剂小时平均磨损指数。 Wherein the wear rate of the sorbent was measured using the method RIPP29- d, compressed air as the fluidizing medium, 0.6MPa pressure, flow rate of 20 l / min, the adsorbent was measured hourly average wear index.

本实施例所采用吸附剂固体颗粒的制备如下: Preparation of solid sorbent particles employed in this embodiment as follows:

本实施例所采用载体的主要原料如下:C^载体:IO千克拟薄水铝石(固含量为64重%,山东淄博铝厂工业产品,下同)+1.0千克硅溶胶(固含量为25重量%,青岛立帆化工厂出品,下同)+13.1千克氧化锌(纯度99.7。/。,沧州杰威化工有限公司产品); The main raw material using a carrier according to the present embodiment example is as follows: C ^ vectors: IO quasi boehmite kg (solid content of 64 weight%, aluminum Zibo industrial products, the same below) +1.0 kg silica sol (solid content 25 wt% Li-fan Chemical Plant, Qingdao, the same below) +13.1 kg of zinc oxide (purity 99.7./, Morrison Changzhou Chemical Co., Ltd.).;

C2"载体:4千克拟薄水铝石+1.0千克硅溶胶+6千克高岭土(固含量为73重量%,苏州瓷土公司工业出品)+10千克氢氧化锌(氧化锌含量71.5%,沛县氧化锌厂产品); C2 "carrier: 4 kg quasi boehmite sol +6 +1.0 kg kg kaolin (solids content 73% by weight, produced by Suzhou Industrial Corporation clay) zinc hydroxide + 10 kg (71.5% of zinc oxide, oxide Pei zinc plant products);

C3〃载体:5千克拟薄水铝石+4千克高岭土+2千克累脱土(固含量为68重量%,湖北名流累托石科技股份有限公司产品)+3.5千克石克酸锌(纯度98%,济南大海化工有限公司产品); C3〃 carrier: 5 kg quasi boehmite +2 +4 kg kaolin tired kg bentonite (68 wt% solids content, Hubei celebrity rectorite Technology Co. product) +3.5 kg stone g of zinc (purity 98 % Jinan sea Chemical Co., Ltd);

分别将混合好的上述栽体原料与去离子水混合打浆,得到固含量为15 重量%的浆液,在搅拌下加入1.6千克的盐酸水溶液(体积浓度30% ), 继续搅拌,直到形成均匀的溶胶,分别制得"、2#、 3#载体溶胶,待用。 Above, respectively, the mixed raw material plant with deionized water beating, a solids content of 15 wt% slurry was added aqueous hydrochloric acid (30% concentration by volume) under stirring 1.6 kg, stirring was continued until a homogeneous sol were prepared ", # 2, # 3 carrier sol stand.

本实施例所采用稀土沸石溶胶的制备如下: Producing a rare earth zeolite sols of the present embodiment is as follows:

本实施例所采用稀土沸石的原料如下: Rare earth zeolite material according to the present embodiment is as follows:

Sf稀土沸石混合物:7.2公斤ZSM-5沸石(硅铝比25,齐鲁石化公司催化剂厂出品)+0.8公斤NaY沸石(硅铝比3.5,齐鲁石化公司催化剂厂出品)+0.36公斤氯化稀土(内蒙古包头稀土厂出品,干基重48重。/。, 其中各组分的干基含量为La2O325.0%、 Ce203 6.0%、 Pr203 5.0%、 Nd203 10.0%,下同); The mixture of rare earth zeolite Sf: 7.2 kg ZSM-5 zeolite (silica-alumina ratio of 25, produced by Catalyst Plant of Qilu Petrochemical Company) +0.8 kg of NaY zeolite (silica to alumina ratio 3.5, produced by Catalyst Plant of Qilu Petrochemical Company) 0.36 kg of rare earth chloride (Inner Mongolia of rare Earth factory produced, dry basis weight ./ 48, wherein the dry content of each component is La2O325.0%, Ce203 6.0%, Pr203 5.0%, Nd203 10.0%, hereinafter the same).;

S2〃稀土沸石混合物:0.5公斤ZRP沸石(硅铝比50,齐鲁石化公司催化剂厂出品)+2.5公斤HY沸石(硅铝比3.8,齐鲁石化公司催化剂厂出品)+2.31 />斤氯化稀土; S2〃 rare earth zeolite mixture: 0.5 kg ZRP zeolite (silica-alumina ratio of 50, produced by Catalyst Plant of Qilu Petrochemical Company) +2.5 kg HY zeolite (silica to alumina ratio 3.8, produced by Qilu Petrochemical Company Catalyst Factory) +2.31 /> kg of rare earth chloride;

S3"稀土沸石混合物:0.5公斤Nap沸石(珪铝比50,齐鲁石化公司催化剂厂出品)+5.5公斤13X沸石(硅铝比2.3,齐鲁石化公司催化剂厂出品)+7.95公斤氯化稀土; S3 "rare earth zeolite mixture: 0.5 kg of zeolite Nap (Gui aluminum ratio 50, produced by Qilu Petrochemical Company Catalyst Factory) +5.5 kg of 13X zeolite (silica-alumina ratio of 2.3 produced, Qilu Petrochemical Company Catalyst Factory) +7.95 kg of rare earth chloride;

分别将上述沸石混合物按照沸石混合物:硝酸铵:去离子水-l: 1: 20的重量比在卯。 The above mixture of zeolites are zeolite mixture in accordance with: ammonium nitrate: de-ionized water -l: 1: 20 weight ratio d. C下离子交换2小时,过滤、水洗后重复交换一次得到铵型择形沸石,其Na2O含量不大于0.15重。 The C ion exchange 2 hours, filtered, washed with water was repeated once to give the ammonium exchanged type shape selective zeolite weight Na2O content not greater than 0.15. /。 /. . 在室温下将上述铵型沸石分别与按照配比计量的氯化稀土配制成水溶液,搅拌浸渍2小时,在120°C 烘干,550。 At room temperature with the above-described ammonium type zeolite were measured according to the composition formulated as an aqueous solution of rare earth chloride, impregnated stirred for 2 hours, dried at 120 ° C, 550. C焙烧2小时,制得Sf、 S2#、 S3〃稀土择形沸石。 C and calcined for 2 hours to obtain Sf, S2 #, S3〃 rare shape selective zeolite. 将制得的稀土沸石与脱阳离子水按照固液重量比1:1〜1:10混合,打浆,搅拌均匀制得稀土沸石溶胶。 The resulting rare earth zeolite cation removing water at a solid to liquid weight ratio of 1: 1~1: 10 mixing, beating, stirring uniformly to prepare a rare earth zeolite sols. 上述制得的S^ 、 S2#、 S3〃稀土沸石溶胶分别与上述Cf、 C2#、 C3# 载体溶胶混合,并加入适量铝溶胶,吸附剂固含量与铝溶胶固含量(以氧化铝计)重量比为15,继续搅拌直到形成均匀的溶胶;将此溶胶在控制尾气温度为250~300°C,喷雾压力为50-60个大气压,喷雾干燥成型,制得微球状固体颗粒。 The above-obtained S ^, S2 #, respectively S3〃 rare earth zeolite sol, C2 #, C3 # of Cf carrier mixed with the above sol, alumina sol and an appropriate amount was added, the solid adsorbent solids content and the content of aluminum sol (in terms of aluminum oxide) a weight ratio of 15, and stirring was continued until a homogeneous sol; sol was controlled at a temperature of exhaust gas 250 ~ 300 ° C, a spray pressure of 50-60 atmospheres, spray drying and pressing, to obtain microspheroidal solid particles. 将得到的微球状固体颗粒洗涤除去游离Na+,在100〜200。 The resulting solid particles are removed by washing the microspheroidal free Na +, at 100 ~ 200. C下烘干至少2小时后,再在500〜800。 After drying for at least 2 hours at C, and then at 500~800. C条件下焙烧至少2小时, 得到微球状Sl#-Cl#、 S2#-C2#、 S3、C3-稀土固体颗粒。 C under calcination conditions for at least 2 hours to obtain microspheroidal Sl # -Cl #, S2 # -C2 #, S3, C3- rare earth solid particles.

实施例1-3 Example 1-3

实施例l-3说明含稀土沸石混合物的吸附剂组成、制备方法。 Example l-3 described adsorbents zeolite containing rare earth mixture composition, method of preparation. 分别将张家港市华义化工有P艮公司产氯化镍7.5公斤,及硝酸钴与硝 Italian respectively Zhangjiagang Chemical Company have produced P gen 7.5 kg of nickel chloride, and cobalt nitrate and nitrate

酸镍各8.5公斤的金属盐混合物配成金属离子浓度为l~10mol/L的水溶 Metal, nickel formulated mixture of 8.5 kg of the metal ion concentration of l ~ 10mol / L aqueous

液,待用。 It was set aside.

在室温下将氯化镍水溶液与S1"-C1"固体颗粒混合,边搅拌边加入浓度为3mol/L的氨水,维持pH为7〜10,不断搅拌至沉淀完全后,升温至卯。 The "-C1" solid particles are mixed with an aqueous solution of nickel chloride Sl, stirred at room temperature while adding a concentration of 3mol / L of ammonia water, maintained at a pH 7 to 10, stirring constantly until the precipitation was complete, the temperature was raised to d. C并放置老化至少0.5小时,过滤,洗涤滤饼至无酸根离子制得氢氧化镍与P-RE-ZSM5、 P-REY及氧化铝载体材料的混合物,水洗至无氯离子。 C and left for aging for at least 0.5 hours, filtered, the filter cake washed until no ions prepared nickel hydroxide and P-RE-ZSM5, and a mixture of P-REY alumina support material is washed with water until free from chloride ions. 在100〜200'C下烘干至少2小时后,再在500〜800'C条件下焙烧至少2小时,粉碎、过篩得到微球状吸附剂Ni-Zn/Sl#-Cl#,命名为ZYS-1。 After drying 100~200'C at least 2 hours, and then calcined at 500~800'C conditions for at least 2 hours, pulverized, sieved microspheres adsorbent Ni-Zn / Sl # -Cl #, named ZYS -1.

在室温下将硝酸钴与硝酸镍的水溶液饱和法浸渍S2#- C2"载体,不断搅拌浸渍至少4小时后,在100〜200。C下烘干至少2小时,再在500-800 。C条件下焙烧至少2小时,粉碎、过筛得到微球状吸附剂Co-Ni-Zn/S2#-C2#,命名为ZYS-2。 S2 # impregnated cobalt nitrate and nickel nitrate aqueous solution at room temperature, saturated Method - after C2 "carrier, stirring constantly immersed at least 4 hours, at least 2 hours and drying under 100~200.C, then the conditions 500-800 .C calcined at least 2 hours, pulverized, sieved microspheres adsorbent Co-Ni-Zn / S2 # -C2 #, named ZYS-2.

将7.3公斤氧化钴(张家港市华义化工有限公司产品)与S3^C3"固体颗粒加入60公斤水打浆;或者将氧化钴单独打浆后直接与与S3"弗石溶胶与C3"栽体溶胶混合,搅拌均匀后,加入适量铝溶胶,吸附剂固含量与铝溶胶固含量(以氧化铝计)重量比为15,继续搅拌直到形成均匀的溶胶; 将此溶胶在控制尾气温度为250〜300°C,喷雾压力为50-60个大气压,喷雾干燥成型,制得微球状的固体颗粒。洗涤其固体颗粒除去游离Na+后, 在100-200。C下烘干至少2小时,再在500-800。C条件下焙烧至少2小时, 得到微球状吸附剂Co-Zn/S3#-C3#,命名为ZYS-3。 The 7.3 kg cobalt oxide (Zhangjiagang HuaYi Chemical Co., Ltd.) and S3 ^ C3 "solids was added 60 kg of water beating; and S3 are directly or with cobalt oxide alone after beating" Eph stone sol C3 "mixed sols plant body , stir, add appropriate amount of alumina sol, alumina sol with a solid content of adsorbent solids (in terms of aluminum oxide) weight ratio of 15, and stirring was continued until a homogeneous sol; sol was controlled at a temperature of 250~300 ° off-gas C, spray pressure of 50-60 atmospheres, spray drying and pressing, to obtain microspheroidal particles of solid. the solid particles were washed to remove free Na +, in dry 100-200.C at least 2 hours and then at 500-800 baking at .C conditions for at least 2 hours to obtain microspheroidal adsorbent Co-Zn / S3 # -C3 #, designated ZYS-3.

吸附剂ZYS-1、 ZYS-2、 ZYS-3的组成(各组分均以吸附剂的总重量为计算基准)和磨损性能见表2。 (The total weight of the components are calculated on the basis of the adsorbent) adsorbents ZYS-1, ZYS-2, ZYS-3 composition of Table 2 and wear properties. 对比例1-3 Comparative Examples 1-3

与实施例1-3的吸附剂组成相比,本对比例说明不含稀土沸石混合物的双金属氧化物吸附剂的组成、常规制备方法及性能。 Compared with the adsorbent compositions of Examples 1-3, Comparative Example of the present description does not contain a rare earth metal oxide bis zeolite adsorbent mixture composition, and properties of a conventional production method.

按照C1"、 C2#、 C3'载体组成湿混,研磨,干燥成形,焙烧(干燥、 焙烧方法同实施例l-3),再分别浸渍金属离子浓度为1〜10moI/L的硫酸镍水溶液,硝酸钴-硝酸镍混合水溶液及醋酸钴水溶液。再次烘干、焙烧, 粉碎、过筛得到不含稀土沸石混合物的微球状吸附剂Ni-Zn/Cl#、 Co-Ni-Zn/C2#、 Co-Zn/C3#,分别命名为S-4、 S-5、 S-6。其组成和磨损性能列于表2。 According to C1 ", C2 #, C3 'wet mixing the carrier composition, grinding, drying, molding and sintering (drying, calcination method described in Example l-3), and then were immersed metal ion concentration 1~10moI / L of nickel sulfate aqueous solution, cobalt nitrate - mixed aqueous solution of nickel nitrate and cobalt acetate aqueous solution again dried, calcined, pulverized, sieved microspheres adsorbent Ni-Zn rare earth-containing zeolite mixture / Cl #, Co-Ni-Zn / C2 #, Co. -Zn / C3 #, named S-4, S-5, S-6. its composition and wear properties are shown in table 2.

从表2可以看出,吸附剂ZYS-1、 ZYS-2、 ZYS-3强度均较好,其磨损率均小于1.0。 As can be seen from Table 2, the adsorbent ZYS-1, ZYS-2, ZYS-3 are good strength, wear rate of less than 1.0. /。 /. .h"以上,均大于采用常规方法制备的不含稀土沸石混合物的吸附剂S-4、 S-5、 S画6。 .h "or more, greater than the mixture using a zeolite prepared by a conventional method non-rare earth adsorbent S-4, S-5, S 6 Videos.

实施例4-5 Example 4-5

实施例4-5说明稀土沸石混合物的吸附剂在汽油脱斩u方面应用。 Examples 4-5 illustrate the mixture of rare earth zeolite adsorbent in terms of u gasoline cut off applications. 以表1中的原料汽油A、 B为原料,考察原料汽油原料在小型流化床反应器内分别与吸附剂ZYS-1、 ZYS-2充分接触进行吸附与催化转化情况。 Table 1 raw material gas A, B as the raw material, raw gasoline feedstock investigate the adsorption catalytic converter in the case of a fluidized bed reactor are ZYS-1, ZYS-2 full contact with the adsorbent. 吸附剂装填量500克,在使用前采用氢气在360。 500 g loading level of adsorbent using hydrogen at 360 before use. C的温度,氢气流量1.5升/小时的条件下还原60分钟。 Temperature, hydrogen flow rate of 1.5 l C under reducing conditions / hr for 60 minutes. 反应产物、蒸汽和待生吸附剂混合物在沉降器内分离,分离反应产物得到气体产物和液体产物,而待生吸附剂由水蒸汽汽提出待生吸附剂混合物上吸附的烃类产物。 The reaction product vapors and the spent adsorbent mixture separated in settler reaction product is isolated to give gaseous products and liquid products, and spent sorbent made hydrocarbon products adsorbed on the spent adsorbent is a mixture of water steam. 汽提后的吸附剂与加热过的空气"l妄触进行再生,再生后的催化剂混合物经冷却、氬气还原后循环使用。试验条件、试验结果和产物汽油性质及其硫含量均列于表3。 Adsorbent heated air stripped "l jump touch regeneration, the regenerated catalyst mixture was cooled, argon-reduction cycle after use. The test conditions, test results and a sulfur content of product gasoline property and are listed in Table 3.

对比例4-5 Comparative Examples 4-5

与实施例4-5的吸附剂应用试验相比,本对比例说明不含稀土沸石混合物的双金属氧化物吸附剂S-4、 S-5用于汽油脱硫的情况。 Application of Test Example as compared with the adsorbent of the embodiment 4-5, the present description does not contain bimetallic Comparative S-4 of rare earth oxide sorbents zeolite mixture, S-5 for the case of a gasoline desulfurization.

原料汽油A、 B在小型流化床反应器内分别与氬气还原后的吸附剂S-4、 S-5接触进行反应。 Adsorbent S-4, S-5 after contacting the feed gas A, B and argon are restored in a small fluidized bed reactor for reaction. 其他试验工艺条件与试验方法同实施例4~5。 Other test conditions and test methods as in Example 4-5. 试验条件、试验结果和产物汽油性质及其硫含量均列于表3。 Test conditions, test results and product properties of the gasoline and sulfur content are set forth in Table 3. 从表3可以看出,与不加入游石混合物吸附剂的汽油脱硫产品油相对比,加入含磷沸石混合物吸附剂的汽油脱硫率高,均在97.19重%以上; 汽油辛烷值较高,均高于原料油;而其苯含量较低,均低于原料油。 As can be seen from Table 3, the mixture of the adsorbent was not added Stone-desulfurized gasoline product as opposed to oil, gasoline desulfurization rate of addition of the phosphorus-containing zeolite adsorbent mixtures, were more than 97.19 weight%; higher gasoline octane number, higher than the oil feedstock; and its low benzene content, lower than the oil feedstock.

实施例6-7 Examples 6-7

实施例6-7说明稀土沸石混合物的双金属氧化物吸附剂用于柴油脱硫的情况。 Examples 6-7 illustrate mixture of double oxides of rare earth zeolite adsorbent for the case of desulfurization of diesel.

以表1中的原料柴油C、 D为原料,考察柴油原料在小型流化床反应器内分别与吸附剂ZYS-2、 ZYS-3充分接触进行吸附与催化转化情况。 Table 1 diesel feed C, D as raw materials, a diesel feedstock investigate the adsorption catalytic converter in the case of a fluidized bed reactor are ZYS-2, ZYS-3 sufficient contact with the adsorbent. 吸附剂装填量500克,在使用前采用氢气在360。 500 g loading level of adsorbent using hydrogen at 360 before use. C的温度,氢气流量1.5升/ 小时的条件下还原60分钟。 Temperature, hydrogen flow rate of 1.5 l C under reducing conditions / hr for 60 minutes. 反应产物、蒸汽和待生吸附剂混合物在沉降器内分离,分离反应产物得到气体产物和液体产物,而待生吸附剂由水蒸汽汽提出待生吸附剂混合物上吸附的烃类产物。 The reaction product vapors and the spent adsorbent mixture separated in settler reaction product is isolated to give gaseous products and liquid products, and spent sorbent made hydrocarbon products adsorbed on the spent adsorbent is a mixture of water steam. 汽提后的吸附剂与加热过的空气接触进行再生,再生后的催化剂混合物经冷却、氲气还原后循环使用。 The stripped sorbent after regeneration contacted with the heated air, a mixture of regenerated catalyst is cooled, the recycle reducing gas Yun. 试验条件、试验结果和产物柴油性质及其硫含量均列于表4。 Test conditions, test results and the properties of diesel and sulfur content of the product are listed in Table 4.

对比例6-7 Comparative Examples 6-7

与实施例6-7的吸附剂应用试验相比,本对比例说明不含稀土沸石混合物的双金属氧化物吸附剂S-5、 S-6用于柴油脱硫的情况。 Application of Test Example as compared with the adsorbent of the embodiment 6-7, description of the present comparative metal oxide sorbents contain double S-5 zeolite mixture of rare earth, S-6 for the case of desulfurization of diesel.

原料柴油C、 D在小型流化床反应器内分别与氢气还原后的吸附剂S-5、 S-6接触进行反应。 Diesel feed C, D reacted adsorbent S-5 S-6 after reduction with hydrogen in contact with a fluidized bed reactor in a small, respectively. 其他试验工艺条件与试验方法同实施例4~5。 Other test conditions and test methods as in Example 4-5. 试验条件、试验结果和产物柴油性质及其硫含量均列于表4。 Test conditions, test results and the properties of diesel and sulfur content of the product are listed in Table 4.

从表4可以看出,与不加入沸石混合物吸附剂的柴油脱A1L产品油相对比,加入含磷沸石混合物的吸附剂的柴油脱硫率较高,均在99.04重%以上;柴油十六烷值较高,均高于原料油。 Higher apparent from Table 4, without the addition of a mixture of zeolite adsorbent the product diesel oil de A1L contrast, was added a mixture of phosphorus-containing zeolite adsorbents diesel desulfurization rate, the average weight of 99.04% or more; Cetane Number high, higher than the feedstock.

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Claims (16)

1、一种脱硫吸附剂,其特征在于,以吸附剂总重量为计算基准,该吸附剂包括:1-30重%的稀土沸石混合物,5~40重%的活性金属氧化物和30~94重%的载体,其中载体包括氧化铝和氧化锌。 1, a desulfurization adsorbent, wherein the adsorbent is calculated based on the total weight of the base, the adsorbent comprising: a mixture of rare earth zeolite 1-30% by weight, 5 to 40% by weight of active metal oxide and 30 to 94 weight percent of a carrier, wherein the carrier comprises alumina and zinc oxide.
2、 按照权利要求l的吸附剂,其特征在于,以稀土沸石混合物的重量为计算基准,稀土沸石混合物的组成如下:稀土以RE20"+,占1-35重%;沸石混合物占65-99重% 。 2, the adsorbent according to claim l, characterized in that the zeolite weight calculated on the basis of a mixture of rare earth, rare earth zeolite mixture composed as follows: In the rare earth RE20 "+, accounting for 1-35 wt%; mixture of zeolites accounted 65-99 weight%.
3、 按照权利要求1或2的吸附剂,其特征在于所述稀土沸石混合物指稀土择形沸石与稀土八面沸石按照重量比例10: l至l: 10优选1: 1.1至1: 5混合的混合物。 3, the adsorbent according to claim 1 or 2, wherein said rare earth refers to a mixture of rare earth shape selective zeolite with rare earth faujasite zeolite in a weight ratio of 10: l to l: 10 preferably 1: 1.1 to 1: 5 mixture mixture.
4、 按照权利要求3的吸附剂,其特征在于所述稀土择形沸石选自含稀土的五元环高硅沸石、含稀土的ZRP沸石、含稀土的Beta沸石中一种或几种,其珪铝比为20-500。 4, the adsorbent according to claim 3, wherein the shape selective zeolite is selected from rare earth rare earth-containing pentasil high silica zeolite, ZRP zeolites containing rare earth, rare earth-containing zeolite Beta in one or more of which Gui aluminum ratio from 20 to 500.
5、 按照权利要求4的吸附剂组合物,其特征在于所述五元环高硅沸石选自ZSM-5沸石、ZSM-8沸石、ZSM-ll沸石、ZSM-22沸石、ZSM-23 沸石、ZSM-48沸石、ZSM-57沸石中的一种或几种;Beta沸石选自Na卩型、H卩型、USP型沸石中的一种或几种。 5. The sorbent composition of claim 4, wherein the five-membered ring high silica zeolite is selected from ZSM-5 zeolite, ZSM-8 zeolite, ZSM-ll zeolite, ZSM-22 zeolite, ZSM-23 zeolite, zeolite ZSM-48, ZSM-57 zeolite is one or more; Jie Beta zeolite is selected from Na type, H type Jie, USP-type zeolite is one or more.
6、 按照权利要求3的吸附剂,其特征在于所述稀土八面沸石为X型系列沸石或/和Y型系列沸石。 6, the adsorbent according to claim 3, wherein said rare earth faujasite zeolite is type X zeolite series or / and Y series zeolites.
7、 按照权利要求6的吸附剂,其特征在于所述稀土Y型沸石选自REY 型、REHY型、REUSY型沸石中的一种或几种。 7, the adsorbent according to claim 6, wherein said rare earth Y zeolite is selected from one or more type REY, REHY type, REUSY type zeolites.
8、 按照权利要求l的吸附剂,其特征在于所述活性金属选自钴、镍、 铁、锰、铜、钼、鴒、银、锡、钒中的一种或两种以上金属。 8, the adsorbent according to claim l, wherein said active metal is selected from cobalt, nickel, iron, manganese, copper, molybdenum, alba, silver, tin, vanadium, one or two or more metals.
9、 按照权利要求l的吸附剂,其特征在于所述活性金属为钴或/和镍。 9, the adsorbent according to claim l, characterized in that the active metal is cobalt and / or nickel.
10、 按照权利要求l的吸附剂,其特征在于,以载体的重量为计算基准,所述载体包括5~30重%的氧化铝,10-65重。 10, according to claim l of adsorbent, characterized in that, in order to calculate a reference weight of the carrier, the carrier comprises 5 to 30% by weight alumina, 10-65 weight. /。 /. 的氧化锌,余量的粘土。 Zinc oxide, the balance clay.
11、 按照权利要求l的吸附剂,其特征在于所述粘土选自氧化硅、无定形硅铝、高岭土、多水高呤土、蒙脱土、膨润土、硅藻土、海泡石、累脱土中的一种或两种以上混合物。 11. The adsorbent as claimed in claim l, wherein the clay is selected from silicon oxide, amorphous silica-alumina, kaolinite, high water methotrexate, montmorillonite, bentonite, diatomaceous earth, sepiolite, tired off soil mixture of one or two or more.
12、 一种制备权利要求1所述吸附剂的方法,其特征在于该方法包括下列步骤:(1)稀土彿石混合物溶胶制备将市售稀土择形沸石与稀土八面沸石按照一定比例机械混合均匀配制成沸石混合物,按照沸石混合物:铵盐:去离子水=1: 0~1: 3~40的重量比在50〜100。 12. The method of claim 1 for the preparation of adsorbent as claimed in claim, characterized in that the method comprises the steps of: (1) preparing a mixture of rare earth stone Buddha sol commercially available mixed rare mechanical shape selective zeolite with rare earth faujasite certain percentage formulated as a uniform mixture of zeolites, a zeolite in accordance with the mixture: ammonium salt: deionized water = 1: 0 to 1: 3 to 40 by weight ratio of 50~100. C下离子交换0.1-5小时,过滤、水洗后重复交换一次得到铵型沸石,其〜320含量不大于0.15重%。 The C ion exchange 0.1-5 h, filtered, washed with water was repeated once to give the ammonium exchanged zeolite, which ~320 content not greater than 0.15 weight%. 在室温下将上述铵型沸石与计量氯化稀土的水溶液搅拌浸渍2小时,120〜200。 At room temperature the aqueous solution of the ammonium form zeolite with rare earth chloride is stirred metering immersed for 2 hours 120~200. C烘干,450~850°。 Drying C, 450 ~ 850 °. 焙烧0.5-4小时,得到以RE203计的稀土含量为1.0-35重%的沸石混合物。 Calcined 0.5-4 hours, to obtain a rare earth content of RE203 is a mixture of 1.0-35 weight% of a zeolite. 将制得的稀土沸石混合物与脱阳离子水按照固液重量比1:1-1:10混合, 打浆,搅拌均匀制得稀土沸石溶胶; (2 )载体溶胶制备将预订量的粉末状载体材料或载体的固体沉淀物与去离子水混合打浆,得到固含量为5~30重量%的浆液,在搅拌下加入盐酸或硝酸的水溶液,使浆液? The zeolite mixture was prepared with a rare earth cation removing water at a solid to liquid weight ratio of 1: 1-1: 10 mixing, beating, stirring uniformly to prepare a rare earth zeolite sol; (2) Preparation of vector bookings sol powdered carrier material, or the solid precipitate was slurried with deionized water carrier, a solids content of 5 to 30 wt% slurry was added with stirring an aqueous solution of hydrochloric acid or nitric acid, the slurry? 11=2~4,搅拌均匀,在30〜100'C下静置老化至少0.5小时制得载体溶胶;(3)固体颗粒制备将步骤(1)与步骤(2)制得的老化后的载体溶胶混合,并加入适量铝溶胶,吸附剂固含量与铝溶胶固含量重量比为10~50,继续搅拌直到形成均匀的溶胶;将此溶胶在控制尾气温度为250~300°C,喷雾压力为50-60 个大气压,喷雾干燥成型,制得微球状的固体载体颗粒。 11 = 2 to 4, mix well, standing at 30~100'C aged for at least 0.5 hours to prepare a sol carrier; (3) preparing solid particles of step (1) and the step (2) the carrier obtained after aging sol were mixed and added an appropriate amount of alumina sol, alumina sol with a solid content of the adsorbent solid content weight ratio of 10 to 50, and stirring was continued until a homogeneous sol; sol was controlled at a temperature of exhaust gas 250 ~ 300 ° C, spraying pressure 50-60 atmospheres, spray drying and pressing, to obtain microspheroidal particles of a solid support. 将得到的微球状固体颗粒洗涤除去游离Na+,在100〜200。 The resulting solid particles are removed by washing the microspheroidal free Na +, at 100 ~ 200. C下烘干至少2小时后,再在500〜800。 After drying for at least 2 hours at C, and then at 500~800. C条件下焙烧至少2小时,得到微球状稀土沸石混合物与载体混合物的颗粒;(4 )金属氧化物活性组分引入将预订量的含金属活性组分一种或多种的金属盐配成金属离子浓度为l~10mol/L的水溶液,在室温下按照金属氧化物与载体的比例加入步骤(3)制得的微球状稀土沸石混合物与载体混合物的颗粒,边搅拌边加入浓度为0.5~5mol/L的氨水,维持pH为7~10,不断搅拌至沉淀完全后, 升温至60〜10(TC并放置老化至少0.5小时,过滤,洗涤滤饼至无酸根离子制得金属氢氧化物稀土沸石混合物与载体材料的混合物,在100~200°C 下烘干至少2小时后,再在500〜80(TC条件下焙烧至少2小时,粉碎、过筛得到微球状吸附剂颗粒。 C at least 2 hours under calcination conditions, to give a mixture of microspheroidal particulate zeolite support with a rare earth mixture; (4) a metal oxide active component into an active metal-containing component comprising one or more of bookings metal salts dubbed ion concentration of l ~ 10mol L aqueous solution / was added at room temperature, the step ratio of the metal oxide according to the carrier (3) a mixture of a rare earth zeolite microspheres with a carrier obtained by granulating the mixture with stirring was added at a concentration of 0.5 ~ 5mol / L aqueous ammonia, maintaining a pH of 7 to 10, stirring constantly until the precipitation was complete, warmed to 60~10 (TC placed and aged for at least 0.5 hours, filtered, the filter cake washed until no ions of rare earth metal hydroxide prepared zeolite after a mixture with the carrier material dried at 100 ~ 200 ° C at least 2 hours, and then calcined under conditions 500~80 TC (at least 2 hours, pulverized, and sieved to obtain microspheroidal particles of adsorbent.
13、 一种应用权利要求l所述吸附剂降低轻质烃油硫含量的方法,其特征在于预热后的含硫轻质烃油原料和供氩体,进入装有吸附剂的反应器内,在温度350-450。 13, l the adsorbent to reduce an application method of claim sulfur content light hydrocarbon oil, characterized in that the preheated sulfur-containing light hydrocarbon oil feedstock body and the supply of argon, into the reactor containing the sorbent , at a temperature of 350-450. C,压力0.5-2.5MPa,原料油重时空速0.5-10 h",吸附剂总量与烃油原料的重量比1-20的条件下反应,分离反应后物料,反应产物送入后续分离系统进行产品分离,反应后的待生吸附剂经汽提后烧焦再生,再生后的吸附剂经供氢体还原后返回反应器循环使用。 C, pressure 0.5-2.5 MPa, a weight hourly space velocity feedstock oil 0.5-10 h ", the total adsorbent weight ratio of the hydrocarbon oil feedstock under the reaction conditions to 20, after separation of the reaction mass, the reaction product is fed to the subsequent separation system product separation, spent adsorbent after the reaction was stripped burning regeneration, returns the sorbent regenerated hydrogen donor recycling reduction reactor.
14、 按照权利要求13的方法,其特征在于所述含硫的烃油原料选自汽油、煤油、柴油、瓦斯油馏分中的一种或两种以上的混合物。 14. The method according to claim 13, wherein the sulfur-containing hydrocarbon oil feedstock is selected from the above gasoline, kerosene, diesel, gas oil fraction or a mixture of two.
15、 按照权利要求13的方法,其特征在于所述供氢体选自氢气、含氢气体、供氢剂中的一种或一种以上的混合物,其中氢气为各种纯度的氬气,含氢气体为本方法所产干气、催化裂化干气、焦化干气、热裂化干气中的一种或一种以上的混合物,供氢剂选自四氬萘、十氬萘、二氬茚中的一种或一种以上的混合物。 15. The method according to claim 13, wherein said hydrogen donor is selected from hydrogen, a hydrogen-containing gas, a mixture of hydrogen donor agent is one or more, wherein the hydrogen purity for a variety of argon, containing the present method of producing hydrogen gas dry gas, cracking dry gas, dry gas coking, thermal cracking dry gas mixture in one or more of the hydrogen donor is selected from naphthalene argon four, ten argon naphthalene, indene argon a mixture of one or more than one.
16、 按照权利要求13的方法,其特征在于所述反应器选自流化床反应器、固定床反应器、移动床反应器或其它类型的反应器及其复合。 16. The method as claimed in claim 13, characterized in that said reactor is selected from fluidized bed reactors, fixed bed reactors, moving bed reactors or other types of reactors and their compound.
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CN104689785A (en) * 2013-12-05 2015-06-10 无锡市锡源锅炉有限公司 Desulphurization adsorbent for drying furnace
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