CN1047189C - 除汞的方法 - Google Patents
除汞的方法 Download PDFInfo
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- CN1047189C CN1047189C CN94192008A CN94192008A CN1047189C CN 1047189 C CN1047189 C CN 1047189C CN 94192008 A CN94192008 A CN 94192008A CN 94192008 A CN94192008 A CN 94192008A CN 1047189 C CN1047189 C CN 1047189C
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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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
-
- 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
- C10G32/00—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
- C10G32/02—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms by electric or magnetic means
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treating Waste Gases (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
- Water Treatment By Sorption (AREA)
- General Preparation And Processing Of Foods (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Fats And Perfumes (AREA)
Abstract
本发明涉及利用吸附剂从裂化器进料中除去汞和/或其它重金属的方法。此方法的特征在于进料也进行磁过滤。
Description
本发明涉及使用吸附剂从裂化器进料中除去汞和/或其它重金属的方法。
在US-A4,950,408中公开了这样的方法,它描述了在含硫吸附剂帮助下如何从非极性有机介质尤其是例如气体冷凝液的裂化器进料中除去汞。除汞是为了减轻或最好避免在裂化过程和裂化产物的精炼过程中由于汞的存在而带来的问题。已知汞可诱发金属(如在裂化产物的进一步精炼中使用的含铝设备)的腐蚀和使后续工序使用的催化剂中毒。另外,汞也特别有毒,这就是为何要尽可能避免人体和/或环境与汞的直接接触。
除汞外,这种裂化器进料还含有其它重金属。例如,从UA-A-4,911,825中可知这种进料可含有许多种重金属杂质,它们一般以有机金属配合物的形式存在。本文可提到的重金属有镍,钒,砷,铬,铅,钴,铜和锌。
一些文献介绍了为除去在裂化器进料中常以低浓度(如10-10000ppb量级)存在的一种或多种重金属而进行的种种努力;例如参见上述两篇专利说明书及其引用文献。
申请人发现借助于吸附剂从裂化器进料中除去汞和/或其它重金属的方法并不总是产生满意的结果,和处理过的进料还含有太高含量的汞和/或其它重金属。
本发明方法为这一问题提出解决方案;其特征在于裂化器进料也要进行磁性过滤处理。
申请人无意于进行科学解释,但估计本发明的结果是由于在裂化器进料中捕获了磁性的和/或可磁化的固体杂质。如果遇到这种情况,被除去的汞或其它重金属似乎至少是部分地粘附在这种固体杂质上和因此吸附剂就不再能有效地除去它们。
而应用磁性过滤可导致除去这样的磁性的和/或可磁化的杂质和因此导致较高的对汞和/或其它重金属的捕获效率。
作为附加的结果,本发明方法通过减小碳质沉积物的形成而减小裂化过程中设备的污染。
通过磁性过滤从水流中除去可磁化杂质是已知的方法。在这方面可参考文章“高磁分离的废水处理(Waste waterprocessing withHGMS)”byR.R.Oder and B.I.Horst,文载于Filtration and SeparationJournal,Julyl/August 1976,pp363-377。
但是参考文献并未指明这一事实,即使用吸附剂从裂化器进料中除去汞和/或其它重金属的低捕效率是由于在这种进料中存在磁性的和/或可磁化的固体杂质所致。
本发明方法最好按下述方式使用,即进料在进行吸附剂处理之前,先进行磁性过滤。
磁过滤的一种可能的实施方案是包括一个用可磁化的或最好是铁磁性的填料(如钢毛,铁海绵等)填充的柱;此填料柱的外面配制有磁铁,最好为电磁铁,正如上述文章所提到的,在本实施方案中可使用特别高的磁场梯度(10-100百万高斯/厘米),磁场强度为0.01-10特斯拉。
为改进对细分散的小固体杂质(粒度在0.1-100μ或更高)的捕获效率,除了磁过滤外最好还使用微过滤。微过滤是本领域已知技术,通常是以膜过滤方式进行。其主要目的是除去小颗粒,由于它们粒度小(0.1-10μ)这些小颗粒只能部分被磁过滤除去。因此,优选地在磁过滤之后进行微过滤。单独使用微过滤也有可能提高除去效率,但它也有一些缺点:
-留下相当大浓度的液流;
-通过膜要施加高压力降;
-需要大的过滤面积。
除去固体杂质的另一可能性,即沉积方法,也有类似的缺点。这种方法使用倾析离心法,可能要连续操作(在这种情况下,是藉助于阿基米德螺旋从鼓上刮去沉积物)。但这些机械的能量消耗很大和维护费也很昂贵。而在磁过滤之后再施加微过滤则可有力地克服上述缺点。
磁过滤器最好通过断开磁场和用气体或液体冲洗来使之周期性地再生(即除去捕获在过滤器上的固体材料)。当消除磁场(可以移去磁铁,或优选地关闭所用的电磁铁)时,捕获的固体材料易于从磁过滤器上除去并收集以供进一步的另外处理。
此方法可施用于任何含有上述有害重金属的裂化器进料。在下例实例中可能提到的有:气体冷凝液(gas condensate),石脑油,LNG(液化天然气)。
视进料种类而定(挥发性和粘度会起作用),方法进行的温度可以在-50和+150℃之间变化,较好在-30至+120℃,更好在0-60℃之间。
原则上本发明方法适用于从裂化器进料中除去汞和/或其它重金属的任何过程。它特别适用于使用含硫吸附剂的场合,此硫是以巯基或多硫基或金属硫化物形式。
在US-A-4,950,408中广泛地描述了使用巯基的吸附方法;例如用多硫基的吸附剂可以从用碱金属(氢)硫化物和元素硫处理强碱性离子交换剂得到(参见US-A-4,843,102)。关于使用金属硫化物作吸附剂,可参考例如US-A-4,094,777,其中使用载体上的硫化铜。在NL-A-7,613,998和US-A-4,911,825中也提到其它含硫吸附剂。这些试剂通常有载体材料,它们可以是聚合材料(如与二乙烯基苯交联的聚苯乙烯)或无机材料(如氧化铝、氧化硅、沸石和活性炭)。在室温下具有高粘度的裂化器进料的情况下最好在升高温度下处理,此时用无机载体材料更有利,它比聚合物载体对温度较不敏感。
如果裂化器进料含有不可磁化的固体,为增加对汞和/或其重金属的除去效率,可向裂化器进料中加入可磁化或磁性组分及同时加入化学絮凝剂(如FeCl3)。
这样,杂质就可以通过磁过滤而被捕获。作为可磁化或磁性组分使用的可以是:如铁酸钴,铁酸钡,磁铁矿,铁酸镍及铁氧体磁铁(ferritemagnets)。最好使用磁铁矿作为可磁化或磁性组分。更详细描述可参考“过滤与分离”中的上述文章。
下述实例和比较实验是用于进一步说明本发明方法;但应强调这只为例示本发明并不能看作是对本发明的限制。
实例1
实验装置由以下元件组成:
a)磁过滤器,由30厘米长,直径1厘米的柱构成,内装有钢毛(直径20-40μm),装填度约为10%。外加磁场为0.2特斯拉。
b)吸附柱,长16厘米、直径2厘米,内装有由Rohm&Haas供货的含巯基吸附剂MAC SMl。
平均含有约350ppb汞和约10000ppb铁的气体冷凝液通过实验装置,条件是温度为室温,流速为0.2升/小时。整个实验期间(50天)汞的平均出口浓度总是低于或等于10ppb。
比较例
在实例1的相同条件下相同的进料仅通过吸附柱。对汞的捕获效率约为65%。
实例2
实验装置增加微过滤器,它由一膜元件构成。膜的筛孔宽度0.5μm和过滤面积28厘米2。此微过滤器置于磁过滤器和吸附柱之间。重复实例1,在75天整个实验期内汞的平均出口浓度低于或等于5ppb。
Claims (6)
1.使用含以巯基、多硫基或金属硫化物形式的硫的吸附剂从作为进料的气体冷凝液、石脑油和液化天然气中除去汞的方法,其特征在于该进料也使用装有铁磁性材料的柱进行磁过滤。
2.根据权利要求1的方法,其特征在于还进行微过滤。
3.根据权利要求1-2中任一项的方法,其特征在于在磁过滤中使用的磁生填料通过断开磁场和用气体或液体冲洗进行周期性再生。
4.根据权利要求1-2中任一项的方法,其特征在于使用温度为-30℃至120℃。
5.根据权利要求1-2中任一项的方法,其特征在于磁性或可磁化组分与化学絮凝剂一起加到进料中。
6.根据权利要求5的方法,其特征在于使用磁铁矿作为磁生或可磁化组分。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE9300453A BE1007049A3 (nl) | 1993-05-05 | 1993-05-05 | Werkwijze voor het verwijderen van kwik. |
BE9300453 | 1993-05-05 |
Publications (2)
Publication Number | Publication Date |
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CN1122608A CN1122608A (zh) | 1996-05-15 |
CN1047189C true CN1047189C (zh) | 1999-12-08 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN94192008A Expired - Fee Related CN1047189C (zh) | 1993-05-05 | 1994-04-29 | 除汞的方法 |
Country Status (19)
Country | Link |
---|---|
US (1) | US5702590A (zh) |
EP (1) | EP0697032B1 (zh) |
JP (1) | JPH08509762A (zh) |
CN (1) | CN1047189C (zh) |
AT (1) | ATE148492T1 (zh) |
AU (1) | AU679070B2 (zh) |
BE (1) | BE1007049A3 (zh) |
BR (1) | BR9406367A (zh) |
CA (1) | CA2162160A1 (zh) |
DE (1) | DE69401654T2 (zh) |
DZ (1) | DZ1776A1 (zh) |
ES (1) | ES2098143T3 (zh) |
FI (1) | FI955292A (zh) |
MX (1) | MX9403283A (zh) |
MY (1) | MY131629A (zh) |
NO (1) | NO954407L (zh) |
SG (1) | SG48157A1 (zh) |
TW (1) | TW268901B (zh) |
WO (1) | WO1994025540A1 (zh) |
Families Citing this family (10)
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US6350372B1 (en) | 1999-05-17 | 2002-02-26 | Mobil Oil Corporation | Mercury removal in petroleum crude using H2S/C |
US6596182B1 (en) * | 2001-02-02 | 2003-07-22 | The Regents Of The University Of California | Magnetic process for removing heavy metals from water employing magnetites |
KR100999683B1 (ko) | 2008-01-25 | 2011-01-14 | 팜메이커 주식회사 | 유황의 정제방법 |
KR101423936B1 (ko) | 2009-03-11 | 2014-07-29 | (주)바이오니아 | 실시간 핵산 분석 통합 장치 및 이를 이용한 타겟 핵산의 검출방법 |
JP5889060B2 (ja) * | 2011-04-04 | 2016-03-22 | アークレイ株式会社 | 金属の回収方法 |
KR101870311B1 (ko) | 2012-03-09 | 2018-06-25 | (주)바이오니아 | 핫스타트 역전사반응 또는 핫스타트 역전사 중합효소 연쇄반응용 조성물 |
KR101545848B1 (ko) | 2012-04-09 | 2015-08-21 | (주)바이오니아 | 핵산중합효소로 핵산을 검출하는데 사용되는 고민감도 핵산준비방법 |
CN105778983A (zh) * | 2016-04-20 | 2016-07-20 | 浙江海洋学院 | 一种焦化蜡油中微量焦粉的去除方法 |
CN105861033A (zh) * | 2016-04-20 | 2016-08-17 | 浙江海洋学院 | 一种基于磁性絮凝剂去除焦化汽油中微量焦粉的方法 |
CN105694951A (zh) * | 2016-04-20 | 2016-06-22 | 浙江海洋学院 | 一种焦化柴油中微量焦粉的去除方法 |
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EP0332526A1 (fr) * | 1988-03-10 | 1989-09-13 | Institut Français du Pétrole | Procédé pour l'élimination du mercure et éventuellement d'arsenic dans les hydrocarbures |
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- 1993-05-05 BE BE9300453A patent/BE1007049A3/nl not_active IP Right Cessation
-
1994
- 1994-04-11 TW TW083103161A patent/TW268901B/zh active
- 1994-04-19 MY MYPI94000943A patent/MY131629A/en unknown
- 1994-04-29 JP JP6524121A patent/JPH08509762A/ja active Pending
- 1994-04-29 AT AT94915707T patent/ATE148492T1/de not_active IP Right Cessation
- 1994-04-29 WO PCT/NL1994/000094 patent/WO1994025540A1/en active IP Right Grant
- 1994-04-29 EP EP94915707A patent/EP0697032B1/en not_active Expired - Lifetime
- 1994-04-29 ES ES94915707T patent/ES2098143T3/es not_active Expired - Lifetime
- 1994-04-29 CA CA002162160A patent/CA2162160A1/en not_active Abandoned
- 1994-04-29 DE DE69401654T patent/DE69401654T2/de not_active Expired - Fee Related
- 1994-04-29 BR BR9406367A patent/BR9406367A/pt not_active Application Discontinuation
- 1994-04-29 CN CN94192008A patent/CN1047189C/zh not_active Expired - Fee Related
- 1994-04-29 AU AU67618/94A patent/AU679070B2/en not_active Ceased
- 1994-04-29 SG SG1996007445A patent/SG48157A1/en unknown
- 1994-05-04 MX MX9403283A patent/MX9403283A/es not_active IP Right Cessation
- 1994-05-04 DZ DZ940042A patent/DZ1776A1/fr active
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1995
- 1995-11-03 NO NO954407A patent/NO954407L/no not_active Application Discontinuation
- 1995-11-03 US US08/552,978 patent/US5702590A/en not_active Expired - Fee Related
- 1995-11-03 FI FI955292A patent/FI955292A/fi unknown
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EP0319615A1 (en) * | 1987-12-11 | 1989-06-14 | Dsm N.V. | Process for removing mercury from organic media |
EP0332526A1 (fr) * | 1988-03-10 | 1989-09-13 | Institut Français du Pétrole | Procédé pour l'élimination du mercure et éventuellement d'arsenic dans les hydrocarbures |
Also Published As
Publication number | Publication date |
---|---|
ATE148492T1 (de) | 1997-02-15 |
FI955292A0 (fi) | 1995-11-03 |
MX9403283A (es) | 1995-01-31 |
CA2162160A1 (en) | 1994-11-10 |
US5702590A (en) | 1997-12-30 |
BR9406367A (pt) | 1996-02-27 |
TW268901B (zh) | 1996-01-21 |
AU679070B2 (en) | 1997-06-19 |
AU6761894A (en) | 1994-11-21 |
DE69401654D1 (de) | 1997-03-13 |
FI955292A (fi) | 1995-11-03 |
CN1122608A (zh) | 1996-05-15 |
SG48157A1 (en) | 1998-04-17 |
WO1994025540A1 (en) | 1994-11-10 |
NO954407D0 (no) | 1995-11-03 |
MY131629A (en) | 2007-08-30 |
ES2098143T3 (es) | 1997-04-16 |
EP0697032B1 (en) | 1997-01-29 |
DE69401654T2 (de) | 1997-09-04 |
NO954407L (no) | 1995-11-03 |
DZ1776A1 (fr) | 2002-02-17 |
BE1007049A3 (nl) | 1995-02-28 |
EP0697032A1 (en) | 1996-02-21 |
JPH08509762A (ja) | 1996-10-15 |
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