CN102548939A - 从烃料流中除去含氮化合物的方法 - Google Patents
从烃料流中除去含氮化合物的方法 Download PDFInfo
- Publication number
- CN102548939A CN102548939A CN201080042430XA CN201080042430A CN102548939A CN 102548939 A CN102548939 A CN 102548939A CN 201080042430X A CN201080042430X A CN 201080042430XA CN 201080042430 A CN201080042430 A CN 201080042430A CN 102548939 A CN102548939 A CN 102548939A
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- CN
- China
- Prior art keywords
- nitrogen
- hydrocarbon feed
- feed steam
- hydrocarbon
- sorbent material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims abstract description 49
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- 229910017464 nitrogen compound Inorganic materials 0.000 title claims description 3
- 150000002830 nitrogen compounds Chemical class 0.000 title claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 144
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
- C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
- C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
- C10G25/05—Removal of non-hydrocarbon compounds, e.g. sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
- C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
-
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Abstract
本发明公开了一种通过使烃进料料流与吸附剂在氮除去条件下接触以产生相对于烃进料料流具有较低氮含量的烃流出物料流而从烃进料料流中除去氮的方法。该烃进料料流包含芳族化合物、有机含氮化合物和二烯烃化合物。
Description
技术领域
本发明涉及一种从烃料流中除去含氮化合物的方法。更特别地,本发明涉及选择性吸附方法在从烃料流中除去含氮化合物的用途。
发明背景
在化学加工和精制工业中熟知分子筛在芳族化合物转化工艺中作为催化剂的用途。具有巨大的工业重要性的芳族化合物转化反应包括芳族化合物如在乙基甲苯、二甲苯、乙基苯、枯烯或高级烷基芳族化合物的生产中和在歧化反应如甲苯歧化、二甲苯异构化中的烷基化或多烷基苯至单烷基苯的烷基转移。该芳族化合物转化工艺的原料通常包括芳族化合物组分或烷基化基质如苯以及C2-C20烯烃烷基化剂或多烷基芳族烃烷基转移剂。在烷基化区域中,芳族化合物进料料流和烯烃进料料流可以在烷基化催化剂上反应以产生烷基化芳族化合物,例如枯烯或乙基苯。烷基化基质中的一部分或所有可以由其他工艺单元(包括苯乙烯工艺单元的分离部分)提供。使多烷基化苯由单烷基化苯产物分离并再循环至烷基转移区域,并与苯在烷基转移催化剂上接触而得到单烷基化苯和苯。
用于芳族化合物转化工艺的催化剂通常包含沸石分子筛。实例包括沸石β(US 4,891,458);沸石Y、沸石ω和沸石β(US 5,030,786);X、Y、L、B、ZSM-5和ω晶型(US 4,185,040);X、Y、超稳定Y、L、ω和丝光沸石(US 4,774,377);和UZM-8沸石(US 6,756,030和US 7,091,390)。本领域已知芳族化合物转化工艺的芳族化合物进料料流通常含有含氮化合物,包括弱碱性有机含氮化合物如腈类,其可以(甚至以ppm和ppb水平)累积作用使下游芳族化合物转化催化剂如芳族化合物烷基化催化剂中毒并显著缩短它们的使用寿命。本领域已知使用各种沸石或分子筛防护床以在芳族化合物转化工艺上游从芳族烃料流中除去一种或多种类型的含氮化合物。实例包括:US 7,205,448;US 5,220,099;WO 00/35836;WO 01/07383;US 4,846,962;US 6,019,887;和US 6,107,535。US 7,205,448公开了酸性分子筛吸附剂在较低温度下相对于弱碱性有机含氮化合物如亚硝酸盐优先吸附水和碱性有机含氮化合物并在增加的温度下在水存在下改善酸性分子筛吸附剂吸附亚硝酸盐的能力。
近年来已发现不饱和脂族烃如烯烃化合物和特别是二烯烃可缩短用于适用于各种工艺料流(包括在芳族化合物转化工艺如烷基化上游的芳族烃进料)的氮防护床的吸附剂(如氮吸附性沸石或分子筛)的有效寿命。这些不饱和脂族如烯烃化合物存在于被含氮化合物污染的芳族化合物工艺料流(包括在苯乙烯工艺分离部分产生的苯料流和在与催化剂或易受到氮中毒影响的其他材料接触之前需要除去含氮化合物的其他料流)中。具有含氮化合物污染物的芳族料流中存在,尤其是存在高度不饱和烯烃化合物(如C4-C6二烯烃)不利地影响氮吸附性材料的性能。不受理论约束,认为烯烃化合物和/或其他不饱和脂族化合物可通过与含氮化合物竞争吸附点和/或通过反应(例如与芳族化合物如苯反应)形成沉积在氮防护床吸附剂上的重质反应产物而缩短氮吸附剂的寿命。
发明概述
本发明涉及从烃料流中除去含氮化合物,同时使存在于烃料流中的不饱和脂族化合物(如烯烃和二烯烃)的吸附和/或反应最小的方法。本发明能够延长吸附剂寿命,这使再生或替换吸附剂的需求最小。本发明还可以用于现有防护床系统而无需额外的设备。
在一个实施方案中,本发明为从包含芳族化合物、有机含氮化合物和二烯烃化合物的烃进料料流中除去氮的方法,该方法包括:使该烃进料料流与吸附剂在氮除去条件下接触以产生相对于烃进料料流具有较低氮含量的烃流出物料流。
在一个实施方案中,吸附剂包含沸石组分、氧化铝组分和金属组分(Madd);其中氧化铝组分为吸附剂的40-90重量%且金属组分为每100g吸附剂0.015-0.08摩尔呈氧化物状态的金属。
在一个实施方案中,该方法的除去的氮与二烯烃之比以相对质量百分数为基础大于1。在另外的实施方案中,烃流出物料流的二烯烃含量为烃进料料流的二烯烃含量的至少30%。在再一实施方案中,烃流出物料流的氮含量不超过烃进料料流的氮含量的50%且烃流出物料流的二烯烃含量为烃进料料流的二烯烃含量的至少30%。
发明详述
本发明涉及从烃进料料流中除去氮的方法,该方法包括使烃进料料流与吸附剂在氮除去条件下接触以产生相对于烃进料料流具有较低氮含量的烃流出物料流。本发明的烃进料料流包含芳族化合物、有机含氮化合物和二烯烃化合物。在实施方案中,芳族烃可以选自苯、萘、蒽、菲及其取代的衍生物,其中苯及其衍生物为优选的芳族化合物。芳族化合物可以具有一个或多个选自具有1-20个碳原子的烷基、羟基和其烷基也具有1-20个碳原子的烷氧基的取代基。当取代基为烷基或烷氧基时,苯基还可以取代在烷基链上。
尽管未取代和单取代的苯、萘、蒽和菲通常最常用于本发明的实践中,但还可以使用多取代的芳族化合物。除了以上所述那些以外,合适的可烷基化芳族化合物的实例还包括联苯、甲苯、二甲苯、乙基苯、丙基苯、丁基苯、戊基苯、己基苯、庚基苯、辛基苯等;苯酚,甲酚,茴香醚,乙氧基-、丙氧基-、丁氧基-、戊氧基-、己氧基苯等。苯、甲苯、二甲苯和或其他进料芳族化合物的来源包括来自石脑油重整单元、芳族化合物提取单元的产物料流,来自苯乙烯单体生产单元的再循环料流和用于生产对二甲苯和其他芳族化合物的石油化学配合物。烃进料料流可以含有另外的一种或多种芳族烃化合物。在实施方案中,芳族烃在烃进料料流中的浓度为烃进料的5-99.9质量%。烃进料料流可以包含50-99.9质量%苯。
烃进料料流包含一种或多种有机含氮化合物。有机含氮化合物通常包括较大比例的碱性含氮化合物如吲哚,吡啶,喹啉,二乙醇胺(DEA),吗啉,包括N-甲酰基吗啉(NFM)和N-甲基吡咯烷酮(NMP)。有机含氮化合物还可以包括弱碱性腈类,如乙腈、丙腈、丙烯腈及其混合物。碱性有机含氮化合物良好吸附在常规粘土或树脂吸附剂防护床上。因此,本发明不要求但包括使用任选的现有技术已知的含有吸附剂以从烃料流中除去碱性有机含氮化合物的碱性氮吸附区域。
在一个实施方案中,有机含氮化合物在烃进料中的浓度为烃进料的30ppb-wt(重量份/十亿份)至1摩尔%;有机含氮化合物的浓度可以为烃进料的100ppb-wt至100ppm-wt(重量份/百万份)。在实施方案中,弱碱性有机含氮化合物如腈类在烃进料中的浓度为烃进料的30ppb-wt至100ppm-wt;
烃进料料流包含一种或多种二烯烃化合物,包括例如每分子具有4-6个碳原子的二烯烃,即C4-C6二烯烃。在实施方案中,二烯烃化合物在烃进料中的浓度为烃进料的30ppb-wt至3000ppm-wt;和二烯烃化合物的浓度可以为烃进料的50ppb-wt至2000ppm-wt。烃进料料流可以包含其他烯烃如单烯烃。通常,所有烯烃在烃进料料流中的总浓度不大于1.0重量%烯烃。烃料流可以含有高达和超过饱和条件的水。
本发明中所用吸附剂和制备吸附剂的方法公开于US 6,632,766中,将其全部内容引入本文作为参考。总之吸附剂包含沸石组分、氧化铝组分和金属组分,其中氧化铝组分以吸附剂的40-90重量%的量存在且金属组分以每100g吸附剂呈氧化物状态的金属为0.015-0.08摩尔的量存在,并且可以称为氮选择性吸附剂。
M2/nO:Al2O3:bSiO2,
其中M为具有“n”价的阳离子且“b”的值为2-500。在实施方案中,沸石为SiO2/Al2O3的摩尔比为2∶1-6∶1的那些和/或具有沸石X、八面沸石、沸石Y、沸石A、丝光沸石、β沸石和镁碱沸石(ferrierite)的晶体结构的那些。优选的沸石为沸石X、Y和A。在一个实施方案中,沸石为13X沸石。
氧化铝组分为活化氧化铝,其可以通过铝的氢氧化物(如三水合氧化铝、三水铝石或水铝氧)在热气体料流或固态热载体中快速脱水而得到。脱水可以使用热气体料流或固态热载体在任何合适的设备中进行。通常,用热气体加热或与热气体接触的时间通常为几分之1秒至4或5秒。气体的温度通常在400-1000℃之间变化。该方法通常称为快速锻烧并例如公开于US 2,915,365。然而,可以使用锻烧的其他方法。活化氧化铝的一个来源为三水铝石,其为由铝土矿使用Bayer方法得到的水合氧化铝的一种形式。然而,如果充分锻烧,则可以使用单水合α-氧化铝、假勃姆石(pseudoboehmite)或三水合氧化铝。可以使用的氧化铝的其他来源包括粘土和氧化铝醇盐。活化氧化铝包括表面积通常大于100m2/g,通常为100-400m2/g的氧化铝。
金属组分(Madd)选自由碱金属、碱土金属和其混合物组成的群组。除了金属阳离子(M)以外,金属组分(Madd)也存在于沸石的交换位置。额外的,金属组分可以与M金属相同或不同。例如,沸石中的M金属可以为钾,而金属组分(Madd)可以为钠。金属组分(Madd)实例包括但不限于钠、钾、锂、铷、铯、钙、锶、镁、钡、锌和铜。在一个实施方案中,金属组分(Madd)选自由钠、钾、锂、铷、铯及其混合物组成的群组。金属组分的来源可以为任何化合物,其在活化条件下分解为金属氧化物。金属组分来源的实例为金属的硝酸盐、氢氧化物、羧酸盐、碳酸盐和氧化物。成型吸附剂可以通过将三种组分以任意顺序组合并形成成型制品而制备。不希望受到任何特定理论限制,认为金属组分(Madd)降低了沸石和/或氧化铝组分的酸度。因此,吸附剂的酸度/碱度可以随着金属组分(Madd)的量和类型而变化。例如具有更多金属组分(Madd)和/或使用提供更多碱性金属氧化物的金属如钾和铯会提高碱度,即降低吸附剂的酸度。如果足以加速烯烃的双键转移反应,则金属组分(Madd)的过量可以为决定性的。
在一个方法中,使氧化铝、沸石和所需金属化合物的水溶液混合并形成成型制品。例如可以使γ-氧化铝、沸石X和乙酸钠溶液组合为捏塑体,然后通过本领域熟知的方式挤出或形成成型制品如粒料、丸剂、片剂或球体(例如通过油滴法)。形成基本圆形的形状或形体的优选方法包括使用盘式球化机。该技术使用旋转盘或盘式球化机,将氧化铝组分、沸石组分和金属组分的溶液供入其上,由此形成基本圆形的颗粒。
形成成型制品的另外的方法为使氧化铝、沸石和金属化合物的粉末混合,随后形成粒料、丸剂等。第三种方法为使氧化铝和沸石组分(粉末)组合,使其形成成型制品,然后用金属化合物的水溶液浸渍成型制品。形成步骤通过任意以上列举的方法进行。
在制备所需金属化合物的溶液中,可以将pH调节为7-14的值。在一个实施方案中,pH为9-13.5。溶液的pH可以通过加入适量的所需金属氢氧化物而控制。例如,如果钠为所需金属,则乙酸钠可用于形成水溶液且可以使用氢氧化钠调节pH。
获得成型制品后,将它们在环境温度至200℃下固化或干燥5分钟至25小时。可以将成型制品分批(例如仓库或塔盘中)固化,或者使用常规设备(如移动带式烘箱或旋转窑)在连续方法中固化。一旦成型制品固化,就通过将固化的制品在275-600℃的温度下加热5-70分钟而将其活化。加热可以使制品在移动盘式或移动带式烘箱或旋转窑中进行,其中制品可以直接烧制或间接烧制以提供完成的固态吸附剂。
三种组分的相对量可以在宽范围内显著变化。氧化铝的量通常为吸附剂的40-90重量%。在一个实施方案中,吸附剂中氧化铝组分与沸石组分的质量比为18∶1-2∶3;并且可以为9∶1-2∶3。沸石的量可以为吸附剂的5-60重量%。金属组分Madd的量也可以显著变化,但是必须以等于存在于沸石的交换位置的金属阳离子M的化学计量量的至少10%的量存在。出于实践原因,Madd的最大量应不超过M的化学计量量的50%。以绝对术语,优选Madd的量以0.015-0.08摩尔Madd/100克吸附剂存在。以金属的氧化物如Na2O报道或表示M和Madd的量。
使要提纯的烃进料料流与上述吸附剂在氮除去条件下接触以降低烃料流的氮含量。该方法产生的流出物烃料流具有相对于烃进料料流氮含量较低的氮含量。氮除去条件通常包括25-300℃的温度和34.5-4136.9kPa(g)的压力。在实施方案中,温度为50℃-200℃;且温度可以为75-175℃。然后可以将来自吸附区域的流出物烃料流引入下游加工单元如烷基化区域或烷基转移区域。
可希望将烷基化区域或烷基转移区域的第一床用作吸附剂区域以除去氮。在该情况下,应分开间隔吸附剂和烷基化或烷基转移催化剂。烷基化剂(例如烯烃)应绕过吸附区域且传输至床间空间以与离开吸附区域的经脱氮的烃料流混合。然而,可优选在分离的容器中含有氮吸附区域和烷基化区域。
在实施方案中,本发明从烃进料料流中除去以相对百分数为基础大于除去的不饱和脂族化合物的量的氮。相对百分数基础由烃进料和流出物料流的氮含量和溴指数确定。溴指数常用于评价烃混合物的烯烃含量(包括二烯烃)。即在该实施方案中,在烃进料和流出物料流之间的以质量百分数为基础的氮含量的百分数降低大于溴指数的百分数降低。例如如果烃进料料流含有4ppm-wt氮和300的溴指数且烃流出物料流含有1ppm-wt氮和150的溴指数,则氮含量降低75%((4-1)/4)且溴指数降低50%((300-150)/300)。因此在该实例中,该方法的除去的氮与不饱和脂族化合物之比以相对百分数为基础为1.5(75%/50%)。由于除去的氮与不饱和脂族化合物之比大于1,从烃进料料流中除去的氮的量以相对百分数为基础大于从烃进料料流中除去的不饱和脂族化合物的量。在另外的实施方案中,除去的氮与不饱和脂族化合物之比以相对百分数为基础为至少1.5,并且除去的氮与不饱和脂族化合物之比以相对百分数为基础可以为至少2。在再一实施方案中,除去的氮与不饱和脂族化合物之比以相对百分数为基础为至少2.5,且除去的氮与不饱和脂族化合物之比以相对百分数为基础可以为至少3。
在一个实施方案中,本发明从烃进料料流中除去以相对质量百分数为基础大于从烃进料料流中除去的二烯烃化合物的量的氮。即在该实施方案中,在烃进料和流出物料流之间以质量百分数为基础的氮含量的百分数的降低大于以质量百分数为基础的二烯烃含量的百分数的降低,即除去的氮与二烯烃之比以相对质量百分数为基础大于1。在另外的实施方案中,除去的氮与二烯烃之比以相对质量百分数为基础为至少1.5;且除去的氮与二烯烃之比以相对质量百分数为基础可以为至少2。在再一实施方案中,除去的氮与二烯烃之比以相对质量百分数为基础为至少2.5;且除去的氮与二烯烃之比以相对质量百分数为基础可以为至少3。
不饱和脂族化合物如烯烃和/或二烯烃化合物的除去可以由各种机理(包括吸附和反应)进行。进入吸附区域的烃进料料流和来自吸附区域的流出物料流的氮含量可以取决于氮浓度由标准实验室方法如UOP269或ASTM D5762或ASTM D4629测定。同样该料流的二烯烃含量可以由方法UOP980测定,且该料流的溴指数可以使用方法UOP304测定。除非另有说明,本文所用分析方法如ASTM D5762和UOP980可以由ASTMInternational,100 Barr Harbor Drive,West Conshohocken,PA,USA得到。
在另外的实施方案中,将以元素为基础为至少50重量%的氮从烃进料料流中除去;且本发明可以除去烃进料料流中的以元素为基础为至少70重量%的氮。在另外的实施方案中,将以元素为基础为至少80重量%的氮从烃进料料流中除去,即来自接触步骤的烃流出物料流的氮含量不超过烃进料料流的氮含量的20%。
在再一实施方案中,来自接触步骤的烃流出物料流的二烯烃含量为烃进料料流二烯烃含量的至少30%,且烃流出物料流二烯烃含量可以为烃进料料流二烯烃含量的至少50%。在另外的实施方案中,烃流出物料流二烯烃含量为烃进料料流二烯烃含量的至少70%。
在另外的实施方案中,来自接触步骤的烃流出物料流的氮含量不超过烃进料料流氮含量的50%,且烃流出物料流二烯烃含量为烃进料料流二烯烃含量的至少30%。在再一实施方案中,来自接触步骤的烃流出物料流氮含量不超过烃进料料流氮含量的50%,且烃流出物料流二烯烃含量为烃进料料流二烯烃含量的至少50%。来自接触步骤的烃流出物料流氮含量可以不超过烃进料料流氮含量的30%,且烃流出物料流二烯烃含量可以为烃进料料流二烯烃含量的至少30%。来自接触步骤的烃流出物料流氮含量可以不超过烃进料料流氮含量的30%,且烃流出物料流二烯烃含量可以为烃进料料流二烯烃含量的至少50%。
实施例1
按照US 7,115,154的实施例2制备本发明吸附剂。测得所得吸附剂具有总共0.142摩尔的Na2O/100g吸附剂。总摩尔数包括0.036摩尔的Na2O/100g吸附剂加入的金属组分(Madd)。
实施例2
市售经酸处理的粘土由Sud-Chemie以产品名称TONSIL CO 630G得到以用作比较吸附剂。
实施例3
使Y-74沸石的样品在15重量%NH4NO3水溶液中淤浆化并使该溶液温度达到75℃(167°F)。Y-74沸石为稳定的钠Y沸石,其中本体Si/Al2之比为5.2,晶胞尺寸为24.53且钠含量基于干燥状态以Na2O计算为2.7重量%。Y-74沸石由钠Y沸石制备,其中本体Si/Al2之比为4.9,晶胞尺寸为24.67且钠含量基于干燥状态以Na2O计算为9.4重量%,其与铵交换以除去75%Na,然后通常按照US 5,324,877的第4栏第47行至第5栏第2行中所述程序的步骤(1)和(2)在600℃(1112°F)下蒸气脱铝。在75℃(167°F)下接触1小时之后,过滤淤浆并用过量温热去离子水洗涤滤饼。再重复这些NH4+离子交换、过滤和水洗涤步骤2次并且所得滤饼具有的本体Si/Al2之比为5.2,钠含量基于干燥状态以Na2O计算为0.13重量%,晶胞尺寸为且根据X射线衍射测定的绝对强度为96。将所得滤饼干燥至适当的潮湿水平,与HNO3胶溶的Pural SB氧化铝混合而得到基于干燥状态为80重量份沸石和20重量份Al2O3粘合剂的混合物,然后挤成1.6mm直径的圆柱形挤出物。使挤出物干燥并在流动的空气中在600℃下锻烧1小时。该催化剂为现有技术的代表。该催化剂的晶胞尺寸为XRD绝对强度为61.1且改性Y沸石中铝的百分数为57.2%骨架铝。
实施例4
将含有烯烃、二烯烃和含氮化合物的工业苯再循环料流(>99重量%苯)样品用作烃进料以评价实施例1-3的吸附剂除去氮和不饱和物的有效性。进料的分析报道在表1中,其中分析来自各测试的流出物或产物。不饱和脂族,即总烯烃含量通过UOP304测定。氮含量通过D4629测定且二烯烃含量通过经修改以改善该方法对探测较低水平的二烯烃的灵敏度的UOP980测定。按照UOP980,不同的是样品大小改变且在本领域熟练技术人员已知的校准仪器以改善探测样品中较低浓度的二烯烃的过程中使用较低浓度的标准溶液。UOP980的修改没有改变不同样品之间的相对测量,但改善和/或能够定量浓度小于500ppm-wt,尤其是小于100ppm-wt的二烯烃。
在测试之前,将吸附剂在250℃下在流动的氮气中预干燥4小时。吸附试验在高压釜中进行,将该高压釜首先用氮气冲洗,然后加入0.6g吸附剂和30g烃进料。然后使高压釜加压至400psig并升温至表1中对各测试所列的温度。高压釜包括设定为100rpm的混合器。当达到规定的温度时,将高压釜在混合下在该温度下保持1小时。此后,除去热以使高压釜冷却至室温并停止混合。将用废的吸附剂从液体产物或流出物中分离,从其取样并分析。
表1
本发明实施例1在使烯烃和二烯烃化合物相对完整的同时显示出除去氮的出乎意料的有效性。相对于烯烃组分选择性吸附氮组分的能力使吸附剂尤其可用于工业应用,其中两种类型的污染物存在于芳族化合物料流中。通过使烯烃的吸附和/或反应最小,预期较高的氮容量和更长的吸附剂寿命。
Claims (10)
1.一种从包含芳族化合物、有机含氮化合物和二烯烃化合物的烃进料料流中除去氮的方法,所述方法包括使烃进料料流与吸附剂在氮除去条件下接触以产生相对于烃进料料流具有较低氮含量的烃流出物料流;其中吸附剂包含沸石组分、氧化铝组分和金属组分(Madd);氧化铝组分的量为吸附剂的约40-约90重量%且金属组分的量为每100g吸附剂约0.015-0.08摩尔呈氧化物状态的金属。
2.根据权利要求1的方法,其中所述沸石组分包含X沸石。
3.根据权利要求1的方法,其中氧化铝组分与沸石组分在吸附剂中的质量比为约18∶1至约2∶3。
4.根据权利要求1的方法,其中所述金属组分(Madd)为选自由钠、钾、锂、铷、铯及其混合物组成的群组的碱金属。
5.根据权利要求1的方法,其中所述有机含氮化合物选自由碱性含氮化合物、弱碱性腈类及其组合组成的群组;任选地,有机含氮化合物以烃进料料流的约30ppb-wt至约1摩尔%的量存在。
6.根据权利要求1的方法,其中所述二烯烃化合物包含C4二烯烃、C5二烯烃和C6二烯烃中的至少一种;且所述二烯烃化合物以烃进料料流的约30ppb-wt至约3000ppm-wt的量存在。
7.根据权利要求1的方法,其中所述氮除去条件包括约25℃至约300℃的温度和约34.5kPa(g)至约4136.9kPa(g)的压力。
8.根据权利要求1的方法,其中除去的氮与不饱和脂族化合物之比以相对百分数为基础大于1,或除去的氮与二烯烃之比以相对质量百分数为基础大于1。
9.根据权利要求1的方法,其中将以元素为基础为至少约50wt%的氮从烃进料料流中除去,或烃流出物料流二烯烃含量为烃进料料流二烯烃含量的至少30%。
10.根据权利要求1的方法,其中烃流出物料流氮含量不超过烃进料料流氮含量的约50%且烃流出物料流二烯烃含量为烃进料料流二烯烃含量的至少30%。
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Application publication date: 20120704 |