CN1106442C - 从原油中除钙的方法 - Google Patents

从原油中除钙的方法 Download PDF

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CN1106442C
CN1106442C CN97198517A CN97198517A CN1106442C CN 1106442 C CN1106442 C CN 1106442C CN 97198517 A CN97198517 A CN 97198517A CN 97198517 A CN97198517 A CN 97198517A CN 1106442 C CN1106442 C CN 1106442C
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resin
metal
electrically charged
acid
charged metal
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CN1232437A (zh
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G·萨托里
D·W·萨瓦吉
S·C·布鲁姆
B·H·巴林格
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ExxonMobil Technology and Engineering Co
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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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/06—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil
    • 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

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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)
  • Dispersion Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明提供了一种从石油原料中除去带2价正电荷的金属的方法。该方法包括使原料与一种树脂接触，所述树脂包含羧基、磺酸基和/或磷酸基。在优选的实施方案中，金属为第II族金属，特别是钙。

Description

从原油中除钙的方法
发明背景
本发明涉及一种从原油中除去某些金属的方法。具体而言，金属为钙。
存在于原油中的钙会导致加热器和换热器结垢，并使得原油加工中采用的催化剂中毒。因而，与低钙原油相比，高钙原油价值较低。除钙的方法可增加这种原油的价值。本发明对于在耐腐蚀环境下加工高钙原油显得更有价值，其中，在实施本发明的方法时酸度增加不构成一种缺陷。
发明概述
本发明提供了一种从石油原料中除去带2价正电荷的金属的方法。该方法包括使原料与一种树脂接触，所述树脂包含羧基、磺酸基和/或膦酸基。在优选的实施方案中，金属为第II族金属，特别是钙。发明详述
本发明提供了一种从石油原料中除去带2价正电荷的金属的方法。这些金属包括：钙、镁、锰和锌。钙是特别重要的。本发明的方法包括使原料与一种树脂接触，所述树脂包含羧基、磺酸基和/或膦酸基。这些金属可以是以下的几种形式，包括环烷酸盐、酚盐、氯化物或硫酸盐。
树脂可包含羧基、磺酸基和/或膦酸基。优选所述树脂为交联树脂，因而其不溶于原油中。适宜的树脂为磺化的苯乙烯-二乙烯基苯共聚物、甲基丙烯酸-二乙烯基苯共聚物、聚丙烯酸、聚乙烯基磺酸、磷酸化苯乙烯-二乙烯基苯共聚物、聚甲基丙烯酸和连接有亚氨基二乙酸基团的苯乙烯-二乙烯基苯共聚物。
树脂可以是所述石油原料通过其的树脂床形式；或者，树脂可悬浮于原油中，并在处理的最后阶段通过过滤或离心进行分离。处理过程的温度应足够高以降低原油的粘度，但应足够低以避免树脂分解。通常温度在50-150℃是令人满意的。
使用后，树脂可通过酸处理进行再生。
下述实施例用于对本发明进行阐明，但它们并不构成对本发明的限定。实施例1
反应装置为备有搅拌器和回流冷凝器的玻璃容器，该装置被浸在油浴中。向反应器中加入50g的Kome 6/1原油，其包含930ppm的钙、42ppm的锰和2.6ppm的锌。再向反应器中加入15.6g的磺化苯乙烯-二乙烯基苯共聚物，其商业名称为Amberlite IR-120，其容量为1.9毫当量/ml。
将混合物在70℃下搅拌7小时。然后，通过离心分离出固体，将处理过的原油中的金属进行分析。钙、锰和锌的含量分别降至107、4.9和0.9ppm。
红外光谱表明，在1708cm-1处相应于羧基的谱带的强度比未处理过的原油强，而在1600cm-1处相应于环烷酸盐的谱带的强度比未处理过的原油弱。这表明，金属为羧酸盐形式，金属除去后游离出羧酸。
我们相信发生了下述反应： 实施例2
反应装置与实施例1相同，向反应器中加入50g的Kome 6/1原油。再向反应器中加入2.15g的甲基丙烯酸与二乙烯基苯的共聚物，其商业名称为Amberlite IRP-64，其容量为10毫当量/g。
将混合物在70℃下搅拌6小时。然后，通过离心分离出固体，对原油进行分析。钙、锰和锌的含量分别降至66、2.2和0.7ppm。
我们相信发生了下述反应：
Figure C9719851700061
实施例3
反应装置与实施例1相同，向反应器中加入50g的Kome 6/1原油。再向反应器中加入7.6g的磺化苯乙烯-二乙烯基苯共聚物，其容量为3.3毫当量/g，公知的商品名为Amberlyst XN 1010。
将混合物在70℃下搅拌7小时。离心分离出固体后，油包含147ppm的钙、9ppm的锰和0.7ppm的锌，即远小于未处理的Kome 6/1。

Claims (12)

1、一种除去溶解于石油原料油相中带2价正电荷的金属的方法，该方法包括(a)使原料与一种油不溶性树脂接触，所述树脂包含选自羧基、磺酸基和膦酸基的基团和其组合的基团和(b)从所述石油原料中分离所述树脂，从而降低在所述石油原油中的金属浓度。
2、根据权利要求1的方法，其中，所述的树脂为交联树脂。
3、根据权利要求1的方法，其中，所述的树脂包括磺化的苯乙烯-二乙烯基苯共聚物、甲基丙烯酸-二乙烯基苯共聚物、聚丙烯酸、聚乙烯基磺酸、磷酸化苯乙烯-二乙烯基苯共聚物、聚甲基丙烯酸和连接有亚氨基二乙酸基团的苯乙烯-二乙烯基苯共聚物。
4、根据权利要求1的方法，其中，所述的带电荷金属为第II族金属。
5、根据权利要求1的方法，其中，所述的带电荷金属为钙。
6、根据权利要求1的方法，其中，所述的树脂为所述石油原料通过其的树脂床形式。
7、根据权利要求1的方法，其中，所述的树脂悬浮于原油中，并在处理的最后阶段通过过滤或离心进行分离。
8、根据权利要求1的方法，其中，所述的方法在50-150℃下进行。
9、根据权利要求1的方法，其中，所述的带电荷金属为环烷酸盐形式。
10、根据权利要求1的方法，其中，所述的带电荷金属为酚盐形式。
11、根据权利要求1的方法，其中，所述的带电荷金属为氯化物形式。
12、根据权利要求1的方法，其中，所述的带电荷金属为硫酸盐形式。
CN97198517A 1996-10-04 1997-10-03 从原油中除钙的方法 Expired - Fee Related CN1106442C (zh)

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US6187175B1 (en) * 1996-10-04 2001-02-13 Exxonmobil Research And Engineering Company Co2 treatment to remove organically bound metal ions from crude
GB0013086D0 (en) * 2000-05-30 2000-07-19 Bp Exploration Operating Process for removing metal ions from crude oil
GB0107908D0 (en) * 2001-03-29 2001-05-23 Bp Oil Int Decolourisation method
US20050004415A1 (en) * 2003-07-02 2005-01-06 Chevron U.S.A. Inc. Ion exchange methods of treating a Fischer-Tropsch derived hydrocarbon stream
WO2007086661A1 (en) * 2006-01-25 2007-08-02 Sk Energy Co., Ltd. Method of removing the calcium from hydrocarbonaceous oil
CN101440300B (zh) * 2007-11-22 2012-06-27 中国石油化工股份有限公司 一种含酸高钙原油的加工方法
WO2010003504A1 (en) * 2008-07-10 2010-01-14 Infineum International Limited Removal of metal from diesel fuel
US9214248B2 (en) 2010-12-15 2015-12-15 Electric Power Research Institute, Inc. Capture and removal of radioactive species from an aqueous solution
US9589690B2 (en) 2010-12-15 2017-03-07 Electric Power Research Institute, Inc. Light water reactor primary coolant activity cleanup
US8975340B2 (en) 2010-12-15 2015-03-10 Electric Power Research Institute, Inc. Synthesis of sequestration resins for water treatment in light water reactors
GB2548525B (en) 2014-12-23 2021-03-31 Equinor Energy As Process for removing metal naphthenate from crude hydrocarbon mixtures

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US5976358A (en) 1999-11-02
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EP0931021B1 (en) 2009-11-18
DE69739659D1 (de) 2009-12-31
CN1232437A (zh) 1999-10-20
CA2266433A1 (en) 1998-04-09
AU730026B2 (en) 2001-02-22
EP0931021A1 (en) 1999-07-28
EP0931021A4 (en) 2000-11-15
WO1998014402A1 (en) 1998-04-09
NO991628L (no) 1999-04-06
NO991628D0 (no) 1999-04-06
CA2266433C (en) 2007-01-30

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