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CN100379843C - 用吸附剂从烃流中脱AsH3的方法 - Google Patents

用吸附剂从烃流中脱AsH3的方法 Download PDF

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CN100379843C
CN100379843C CNB038075830A CN03807583A CN100379843C CN 100379843 C CN100379843 C CN 100379843C CN B038075830 A CNB038075830 A CN B038075830A CN 03807583 A CN03807583 A CN 03807583A CN 100379843 C CN100379843 C CN 100379843C
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hydrocarbon stream
carrier
ash
sulphur
arsine
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CN1646666A (zh
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L·H·波斯特马
A·科维斯
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SABIC Hydrocarbons BV
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    • 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
    • C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
    • C10G70/04—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Separation Of Gases By Adsorption (AREA)

Abstract

一种从常压沸点低于约0℃的烃流中脱AsH3的方法，该方法通过使烃流与含有沉积在载体上的元素硫的吸附剂相接触进行。硫的含量为硫和载体总量的5-25wt%。除了AsH3之外，也可将汞从烃流中脱除。

Description

用吸附剂从烃流中脱AsH3的方法
本发明涉及一种用吸附剂从烃流中脱AsH3的方法。
J.A.Reid在1997年3月7日于休斯顿召开的AlChE EPC胂研讨会上，在“脱胂和脱含砷化合物的方法介绍”中总结了脱AsH3方法。
在烃流中存在AsH3是个问题，这是因为AsH3会使进一步处理该烃流所用的催化剂中毒，例如氢化催化剂。对于主要含有如大于70vol.％的含1-3个碳原子的烃的物料来说，AsH3的存在是一个特殊问题。这些烃流的常压沸点低于约0℃。该物流可能含有AsH3，但不含烷基胂，如单-、二-和三烷基胂。
本发明的目的是提供一种从常压沸点低于0℃的烃流中脱AsH3的方法。
本发明所述方法的特征在于，该烃流同吸附剂相接触，所述吸附剂含有沉积在载体材料上的元素硫。
在一般条件下(常压，室温)，常压沸点低于0℃的烃流是气态的。但是，根据所采用的温度和压力的不同，该烃流也可能是液态的。
该烃流可以含有某些化合物如丙烷、丙烯、乙烷、乙烯、甲烷和/或乙炔。该烃流可以含有如至少70vol.％的丙烯和/或乙烯。
吸附柱含有沉积在载体上的元素硫，所述载体如硅石、氧化铝、硅石/氧化铝、二氧化钛、沸石、活性炭和/或氧化镁。
根据本发明的一个优选实施方案，该载体为活性炭，这是因为活性炭具有一个优点，即同其它载体相比，它的单位体积表面积较大，而且活性炭不含有酸性或碱性部位，这种部位会触发烃流中的化合物发生所不希望的聚合反应。
将元素硫施加在载体上，可以通过如下方法，如用硫溶液浸渍或喷射该载体、或用熔融态硫浸渍该载体、或用升华法将硫负载到载体上。
一般来说，硫的含量少于硫和载体总量的35wt％。
本发明的一个优选实施方案是硫的含量为2-25wt％。
使该烃流通过含有沉积在载体上的元素硫的吸附柱。本发明所述方法可以通过任意适合的方式进行，并且该吸附柱可以具有任意合乎需要的形状和体积。该吸附柱优选是一固定床。该烃流可以以向上流或向下流通过。
一般来说，压力范围在常压至2.5MPa之间。该选择取决于烃流通过过程中的温度，该压力优选为能使该烃流保持气态。
一般来说，温度范围在15℃-100℃。温度高于100℃时，能显著地从吸附柱中升华硫。这是不希望的，因为硫会使处理烃流所用的催化剂中毒。
本发明所述的方法中，气体时空速度(GHSV)一般在1000-50000h-1，其中GHSV定义为[每小时的气体Nm3数]/[m3吸附剂]。
除AsH3之外，烃流还会含有其它杂质，如重金属、特别是汞。本发明所述方法也能从烃流中脱汞。
相对于本发明旨在脱AsH3而言，EP-A-488235公开了一种脱三烷基胂的方法。利用含无机载体和元素硫的固体吸附剂从流体中脱除三烷基胂。在EP-A-488235所述的方法中，使用被负载的CuO-ZnO材料或PbO/Al2O3的防护床从进料中脱除AsH3和/或H2S。在第二步中，使流体同所述固体吸附剂接触，从而脱除流体中的三烷基胂。因此，EP-A-488235没有教导和提示使用含有沉积在载体上的元素硫的吸附剂来脱AsH3。
通过下面的实施例将详细阐述本发明，但本发明的保护范围并不限于这些实施例。
实施例I-III
实施例I-III在固定床设备中进行，使用下述吸附剂A、B和C：
A：六偏磷酸钠HGR，沉积在活性炭上的硫；硫含量10-18wt％，
B：Süd Chemie MIS-2，沉积在活性炭上的硫；硫含量15wt％，以及
C：Norit RBHG-3，沉积在活性炭上的硫；硫含量大约10wt％，
上述实施例在30℃、常压、气体时空速度(GHSV)为1700h-1的条件下进行7天试验。
物料由烃流组成，该烃流含有93vol.％丙烯、3.5vol.％丙烷和3.5vol.％的残余物如甲基乙炔和丙二烯。该物料含有250mg/kgAsH3和2000mg/kgHg。
在试验过程中，从该物料和已处理的气体中取样。通过电感耦合等离子体质谱(ICP-MS)技术对气体试样进行分析。
实施例I
表I
  吸附剂   时间(小时)   脱除的AsH<sub>3</sub>(％)   脱除的汞(％)
  A   33   100   100
  49   100   99
  98   100   96
  121   100   89
  143   100   92
实施例2
表II
  吸附剂   时间(小时)   脱除的AsH<sub>3</sub>(％)   脱除的汞(％)
  B   1   100   98
  32   100   88
  72   100   79
  102   100   79
  125   100   80
实施例3
表III
  吸附剂   时间(小时)   脱除的AsH<sub>3</sub>(％)   脱除的汞(％)
  C   3   100   100
  22   100   100
  46   100   99
  97   100   92
  148   100   86

Claims (5)

1.一种从常压沸点低于0℃的烃流中脱AsH3的方法，所述烃流不含烷基胂，该方法通过使烃流与含有沉积在载体上的元素硫的吸附剂相接触而进行，其中所述吸附剂中硫的含量为硫和载体总量的2-25wt％。
2.如权利要求1所述的方法，其特征在于该烃流包含丙烷、丙烯、乙烷、乙烯、甲烷和/或乙炔。
3.如权利要求1或2所述的方法，其特征在于该载体为硅石、氧化铝、硅石/氧化铝、二氧化钛、沸石、活性炭和/或氧化镁。
4.如权利要求1或2所述的方法，其特征在于该载体为活性炭。
5.如权利要求1或2所述的方法，其特征在于除了AsH3之外，汞也被从烃流中脱除。
CNB038075830A 2002-04-03 2003-03-28 用吸附剂从烃流中脱AsH3的方法 Expired - Fee Related CN100379843C (zh)

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CN107298986B (zh) * 2016-04-14 2019-05-21 中国石油化工股份有限公司 一种吸收稳定工艺方法
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CN107298987B (zh) * 2016-04-14 2019-03-19 中国石油化工股份有限公司 吸收稳定工艺及系统
CN107298989B (zh) * 2016-04-14 2019-03-19 中国石油化工股份有限公司 一种吸收稳定工艺及系统
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