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WO2008000115A1 - A procss for removing polymer and zooglea from crude oil - Google Patents

A procss for removing polymer and zooglea from crude oil Download PDF

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Publication number
WO2008000115A1
WO2008000115A1 PCT/CN2006/003272 CN2006003272W WO2008000115A1 WO 2008000115 A1 WO2008000115 A1 WO 2008000115A1 CN 2006003272 W CN2006003272 W CN 2006003272W WO 2008000115 A1 WO2008000115 A1 WO 2008000115A1
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Prior art keywords
crude oil
polymer
micelles
demulsification
separated
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English (en)
French (fr)
Inventor
Shuhai Guo
Gang Li
Hanfeng Ye
Fengmei Li
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Institute of Applied Ecology of CAS
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Institute of Applied Ecology of CAS
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G53/00Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/14Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D17/00Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02Separation of non-miscible liquids
    • B01D17/04Breaking emulsions
    • B01D17/041Breaking emulsions with moving devices
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D17/00Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02Separation of non-miscible liquids
    • B01D17/04Breaking emulsions
    • B01D17/047Breaking emulsions with separation aids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G27/00Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G33/00Dewatering or demulsification of hydrocarbon oils
    • C10G33/04Dewatering or demulsification of hydrocarbon oils with chemical means

Definitions

  • the invention relates to a method for treating crude oil, in particular to a method for removing polymers and bacterial micelles in crude oil. Background technique
  • Polymer flooding technology began in the United States in the late 1950s. From the 1970s to 1985, the United States conducted a total of 183 polymer flooding field tests, with a maximum recovery rate of 8.6%. In addition, in the former Soviet Union's Louisiana and Arlan fields, Canada's Horsefly Lake field and Courtenay test area, and Germany, Oman, etc., also carried out polymer flooding industrial tests, generally improve oil recovery 6-17% .
  • Demulsification-gravity separation A demulsifier is added to the crude oil to be treated for treatment, and then sent to a purified oil settling tank. After dehydration, it is sent to the crude oil receiving tank.
  • the main advantage of this treatment process is that the technology is simple and the energy consumption is low.
  • the disadvantage is that this method cannot remove the polymer, the micelles, the gums, the asphaltenes and the like, and the dewatering of the treated crude oil is still difficult and cannot meet the process requirements.
  • Demulsification-swirl separation “When the crude oil to be treated is broken, the two-phase separation is carried out by using a swirling technique, and the purpose of dehydration can be achieved, but the polymer and the micelle in the crude oil cannot be removed.
  • An object of the present invention is to provide a method for removing polymer and bacterial gum in crude oil to smoothly perform electric dehydration.
  • the oxidative demulsification is to oxidize and demulsifie the crude oil by adding the demulsification agent at a concentration of 100-300 ppm under the condition of stirring speed of 75-150 r/min and heating temperature of 45-75 °C.
  • the residence time is 10-25min;
  • the three-phase separation is a high-factor three-phase separation technique with a separation factor of 9000-14000 for oil, water, and solid three-phase separation of oxidized and demulsified crude oil, wherein more than 85% of the polymers cause electrical dehydration
  • the fungal micelles are separated from the crude oil by the solid phase, and ions which are not conducive to electrical dehydration are separated from the crude oil by the aqueous phase.
  • the demulsification agent is an amine and an epoxide block polyether.
  • the method of the present invention adds an oxidative demulsification agent to the crude oil to be treated, and fully oxidizes and demulsifies the crude oil to effectively separate the polymer and the micelles from the crude oil.
  • the separation technology used in the method for removing polymer and bacterial gum in crude oil is high-factor three-phase separation, and the removal rate of polymer and bacterial micelle in the separated crude oil is as high as 85% or more, and the quality of crude oil is greatly improved. , can be smoothly dehydrated.
  • the recovered crude oil recovery rate is in compliance with the output standard and the processing cost is low.
  • Fig. 2 is a graph showing the electric dehydration of crude oil after the treatment of Example 2.
  • Figure 3 shows the polymer and fungal mass solids separated in a three-phase separator.
  • Figure 4 shows the polymer and the micelle o solid phase separated in the three-phase separator.
  • the raw materials are as follows: polymer containing polymer and fungal group 0. 15-0. 25%, water containing 10-30% crude oil (this example takes crude oil from Daqing Oilfield), the specific implementation method is as follows (see Table 1):
  • the crude oil to be treated is introduced into the reaction tank and heated to 60 ° C; at the same time, the mixture is stirred at a low speed, and the stirring speed is 90 r / min.
  • a demulsification agent having a concentration of 150 ⁇ and 250 ppm, respectively: a fatty amine polyoxypropylene polyoxyethylene block polyether.
  • the crude oil stays in the reaction tank for about 15 minutes, and fully acts with the demulsification agent.
  • Figure 1 shows the current-voltage curve at a concentration of 150 ppm and a separation factor of 10,000. It can be seen from the figure that the current of the electric off-system is within the normal range, which can ensure the normal operation of the electric dehydrator. After treatment, the crude oil has a water content of less than 1.8% and can be exported to the outside by electrohydration. ,
  • the raw material is 0. 3-0. 5 %
  • the demulsifier is: polyethene polyamine poly Oxyethylene polyoxypropylene ether.
  • the polymer and the micelles are separated from the crude oil by solid phase (see Figure 4), and the separated crude oil is subjected to electrical dehydration.
  • Figure 2 shows the current-voltage curve at a concentration of 300 ppm and a separation factor of 14,000. It can be seen from the figure that the current of the electric off-system is within the normal range, which can ensure the normal operation of the electric dehydrator.
  • the water content of the crude oil after processing is less than 0.9%. , reach the standard directly outside the loss.
  • the raw material is 0. 05-0. 1%
  • the water containing 30-40% of the crude oil and the demulsifier is: phenolamine resin Polyoxyethylene polyoxypropylene ether.
  • the polymer and the micelles are separated from the crude oil by the solid phase, and the separated crude oil is subjected to electrical dehydration.
  • the current of the electric off system is within the normal range, which can ensure the normal operation of the electric dehydrator.
  • the crude oil has a water content of less than 2.7%, and can be exported to the outside by electrohydration.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Description

一种去除原油中聚合物及菌胶团的方法 技术领域
本发明涉及原油的处理方法, 具体的说是一种去除原油中聚合物及菌胶团的方法。 背景技术
由于一次采油 (依靠地层天然压力)和二次采油 (注水补压) 已不能提供充分的石 油储备以满足日益增加的原油资源消耗的需要, 为满足国民经济发展对石油产量的需 求, 努力提高已开发油田的采收率, 积极进行三次采油。三次采油技术中很重要的一种 手段就是聚合物驱油技术。聚合物驱油适用于温度适中、原油粘度中等(5— lOOmPa · s)、 非均质比较严重的油藏。
聚合物驱油技术在美国始于 20世纪 50年代末。从 70年代到 1985年, 美国共进行 聚合物驱油矿场试验 183次, 采收率最高提髙到 8. 6%。 此外, 在前苏联的奥尔良油田 和阿尔兰油田、 加拿大的 Horsefly Lake油田和 Courtenay试验区及德国、 阿曼等, 也 都进行了聚合物驱油工业性试验, 一般提高原油采收率 6— 17%。
国内的聚合物驱油技术在 20世纪 90年代发展很快。聚合物驱油技术首先在大庆油 田取得了成功, 从 1987年开始聚合物驱的现场试验, 到 1997年聚合物增产原油产量占 当年原油产量的 1/10, 成为稳产的重要技术手段。继这之后, 胜利、大港、河南、辽河 等油田也都进行了先导性试验, 并取得了成功。
随着聚合物驱油技术的普遍应用, 遇到的问题也逐渐增多。生产过程中投加的大量 聚合物, 与菌胶团、 石油胶质、 沥青质等胶合在一起, 共同构成水 /油型稳定胶体, 导 致脱水困难, 引起电脱水系统的保护性断电, 干扰了集输系统的正常运行。 因此, 含有 聚合物及菌胶团的原油不能进入脱水系统, 无法外输而成为废弃物, 已经逐渐成为制约 油田安全平稳生产和环境保护的重要限制因子。
目前国内外对原油中聚合物及菌胶团的处理技术主要集中在:
1、 采取措施减少聚合物使用量以减轻聚合物对原油性质的影响。 但就目前采油现 状来看, 随着聚合物驱油技术的快速发展, 对聚合物使用量会越来越大, 因此, 难以从 根本上解决这个问题。
2、 破乳脱水方法
( 1 )破乳-重力分离: 向待处理原油中加入破乳剂进行处理, 然后送入净化油沉降 罐。 脱水后, 送入原油接收罐。 该处理工艺主要优点是技术简单、 能耗低; 而缺点是这 种方式不能去除聚合物、 菌胶团及胶质、 沥青质等物质, 处理后的原油脱水依然困难, 不能满足工艺要求。
(2)破乳-水洗-重力分离: 该方法与上述方法相比, 增加了水洗工艺, 可提高水 溶性化合物和离子的去除率, 但不能去除原油中的聚合物和菌胶团。
(3)破乳-旋流分离:》将待处理原油破乳后, 利用旋流技术进行二相分离,·可达到 脱水目的, 但也不能脱除原油中的聚合物和菌胶团。
以上方法都无法去除原油中的聚'合物及菌胶团, 以致不能顺利完成电脱水。
由此可见, 现有技术中未见到能够去除原油中聚合物及菌胶团, 从而顺利完成电脱 水的报道。
发明内容
本发明的目的在于提供一种去除原油中聚合物及菌胶团,从而顺利完成电脱水的方 法。
为实现上述目的, 本发明采用的技术方案为:
以原油为原料, 将其氧化破乳, 然后进行三相分离去除原油中的聚合物及菌胶团; 其中, 所述的氧化破乳是将原料在搅拌速度为 75— 150r/min、 加热温度为 45— 75°C的 条件下, 加入浓度为 100— 300ppm破乳药剂对原油进行氧化破乳, 反应停留时间为 10 —25min;
其中:所述三相分离是利用分离因数为 9000— 14000的高因素三相分离技术对氧化 破乳后的原油进行油、 水、 固三相分离, 其中 85%以上导致电脱水困难的聚合物及菌 胶团随固相与原油分离, 同时不利于电脱水的离子随水相与原油分离。所述破乳药剂为 胺和环氧化物嵌段聚醚。
目 m
本发明的技术优点:
' 1.本发明方法在待处理原油中加入氧化破乳药剂, 对原油进行充分氧化破乳, 使聚 合物及菌胶团与原油能够得到有效分离。
2.本发明方法去除原油中聚合物及菌胶团采用的分离技术为高因数三相分离,分离 后的原油中聚合物及菌胶团去除率高达 85%以上, 原油品质得到极大改善, 可顺利进行 电脱水。 处理后的原油回收率髙, 符合输出标准, 并且处理成本低。
附图说明
图 实施例 1处理后原 脱水曲 o
1 为 油电 线 o图。
图 2 为实施例 2处理后原油电脱水曲线图。
图 3 为三相分离器中分离出的聚合物及菌胶团固相物。
图 4为三相分离器中分离出的聚合物及菌胶团 o固相物。
具体实施方式
下面结合实施例对本发明作进一步详细说明。
实施例 1
所取原料为含聚合物及菌胶团 0. 15-0. 25%, 含水 10- 30%的原油(本实施例取大庆 油田的原油), 具体实施方法如下 (参见表 1 ):
( 1 )向反应槽中通入待处理原油,加热至 60°C;同时低速搅混,搅拌速度为 90r/min。 (2)在恒温加热、 定速搅拌的条件下, 加入浓度分别为 150ρρπι和 250ppm的破乳 药剂: 脂肪胺聚氧丙烯聚氧乙烯嵌段聚醚。将原油在反应槽中停留 15min左右, 与破乳 药剂充分作用。
(3) 将破乳后的原油在三相分离器中分离, 其分离因数分别为 10000和 13000。 原油经高效分离方法分离成油、 水、 固三相, 聚合物及菌胶团随固相从原油中分离(参 见图 3), 大部分离子随水相分离, 分离后的原油进行电脱水。
图 1表示浓度为 150ppm,分离因数为 10000时的电流一电压曲线。 由图可知, 电脱 系统电流均在正常范围内, 能够保证电脱水器正常运行。处理后原油含水低于 1. 8%, 经 电脱水后可达标外输。 ,
表 1 原油中聚合物 ^菌胶团去除结果
60 搅拌速度 (r/min) 90 反应停留时间 (rain) 15 加药浓度 (KM) ■ 150 250 分 离 因 数 10000 13000
Figure imgf000004_0001
实施例 2
与实施例 1不同之处在于参见表 2, 所取原料为含聚合物及菌胶团 0. 3-0. 5 % , 含 水小于 10%的原油, 所加破乳剂为: 多乙烯多胺聚氧乙烯聚氧丙烯醚。 聚合物及菌胶团 通过固相从原油中分离 (参见图 4), 分离后的原油进行电脱水。
图 2表示浓度为 300ppm,分离因数为 14000时的电流一电压曲线。 由图可知, 电脱 系统电流均在正常范围内, 能够保证电脱水器正常运行。 处理后原油含水低于 0. 9%。, 可达标直接外输。
原油中聚合物及菌胶团去除结果
Figure imgf000004_0002
实施例 3
与实施例 1不同之处在于参见表 3, 所取原料为含聚合物及菌胶团 0. 05-0. 1 %, 含 水 30- 40%的原油,所加破乳剂为: 酚胺醛树脂聚氧乙烯聚氧丙烯醚。聚合物及菌胶团通 过固相从原油中分离, 分离后的原油进行电脱水。 电脱系统电流均在正常范围内, 能够 保证电脱水器正常运行。 处理后原油含水低于 2. 7 %, 经电脱水后可达标外输。
原油中聚合物及菌胶团去除结果 温 度 ( c ) 45 搅拌速度 (r/min) 75 反应停留时间 (min) 10 加药浓度 (P 1) 100 200 分离 因 数 9000 12000 9000 12000 聚合物及菌胶团去除率
85. 5 90. 1 88. 6 92. 4
( % )

Claims

权利要求书
1. 一种去除原油中聚合物及菌胶团的方法, 其特征在于: 以原油为原料, 将其氧 化破乳, 然后进行三相分离去除原油中的聚合物及菌胶团; 其中, 所述的氧化破乳是将 原料在搅拌速度为 75— 150r/min、 加热温度为 45— 75°C的条件下, 加入浓度为 100— 300ρρπι破乳药剂对原油进行氧化破乳, 反应停留时间为 10— 25niin。
2. 按照权利要求 1所述去除原油中聚合物及菌胶团的方法, 其特征在于: 所述三 相分离是利用分离因数为 9000— 14000的高因素三相分离技术对氧化破乳后的原袖进行 油、 水、 固三相分离, 其中 85 %以上导致电脱水困难的聚合物及菌胶团随固相与原油 分离, 同时不利于电脱水的离子随水相与原油分离。
3. 按照权利要求 1所述去除原油中聚合物及菌胶团的方法, 其特征在于: 破乳药 剂为胺和环氧化物嵌段聚醚。
PCT/CN2006/003272 2006-06-21 2006-12-04 A procss for removing polymer and zooglea from crude oil Ceased WO2008000115A1 (en)

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CN103160448B (zh) * 2011-12-13 2014-06-11 中国科学院沈阳应用生态研究所 适合于电场条件下的石油烃降解菌及其应用

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CN115161068A (zh) * 2022-08-03 2022-10-11 东北石油大学 应用于含酸化返排液原油的电脱水装置

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