CN103820094B - Mixed surfactant and preparation method thereof - Google Patents
Mixed surfactant and preparation method thereof Download PDFInfo
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- CN103820094B CN103820094B CN201310640963.3A CN201310640963A CN103820094B CN 103820094 B CN103820094 B CN 103820094B CN 201310640963 A CN201310640963 A CN 201310640963A CN 103820094 B CN103820094 B CN 103820094B
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- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
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Abstract
<b> the present invention relates to technical field of surfactant, it is a kind of mixed surfactant and preparation method thereof, the raw materials by weight portion meter of this mixed surfactant comprises dodecyl phenol 22</b><bGreatT.G reaT.GT part to 45</b><bGreatT.G reaT.GT part, Sodium Nitrite 2</b><bGreatT.Gr eaT.GT part is to 6</b><bGreatT.Gr eaT.GT part, calcium chloride 2</b><bGreatT.Gr eaT.GT part is to 9</b><bGreatT.Gr eaT.GT part, potassium hydroxide 0.1</b><bGreatT. GreaT.GT part is to 0.6</b><bGreatT. GreaT.GT part, oxyethane 28</b><bGreatT.G reaT.GT part is to 45</b><bGreatT.G reaT.GT part, 1-3</b><bGreatT. GreaT.GT propylene diamine 4</b><bGreatT.Gr eaT.GT part is to 36</b><bGreatT.G reaT.GT part, Witco 1298 Soft Acid 15</b><bGreatT.G reaT.GT part is to 55</b><bGreatT.G reaT.GT part, thanomin 10</b><bGreatT.G reaT.GT part is to 45</b><bGreatT.G reaT.GT part and dehydrated alcohol 2</b><bGreatT.Gr eaT.GT part to 20</b><bGreatT.G reaT.GT part.Mixed surfactant in the present invention is to oil field oil water strong adaptability; alkaline agent need not be added; just can improve water displacing oil effect; current existing tensio-active agent can be replaced completely; and do not need to add alkaline agent; to meet the requirement of oil field development, and energy protection of the environment, be a kind of environmentally friendly additive.</b>
Description
Technical field
the present invention relates to technical field of surfactant, is a kind of mixed surfactant and preparation method thereof.
Background technology
the sulfonated α-olefin that current oil field uses, heavy alkylbenzene sulfonate type, mahogany acid salt form, the non-ionic type of sulphur hydrocarbylation, the tensio-active agents such as the alkyl phenolic resin of hydrocarbylation weak effect when being used alone, need the alkaline agent of additional 0.1% to 2%, just low surface tension can be reached, the promoting agent that ultra low interfacial tension instrument TX500C measures above-mentioned tensio-active agent and alkaline agent compound is dripped with rotating, when the concentration adding tensio-active agent is 0.2% to 1%, low oil water interfacial tension < 5 × 10-2mN/m can be formed, the requirement of oil field development could be met.But add alkaline agent in tensio-active agent after, the material in alkaline agent can react with the mineral substance in stratum, easily causes formation scaling, and water-oil interface not easily breakdown of emulsion, the not easily layering formed, great injury is caused to environment.
Summary of the invention
the invention provides a kind of mixed surfactant and preparation method thereof, overcome the deficiency of above-mentioned prior art, it effectively can solve the problem that the tensio-active agent used in current oilfield water extraction process needs to add alkaline agent.
one of technical scheme of the present invention is realized by following measures: a kind of mixed surfactant, and raw materials by weight portion meter comprises dodecyl phenol 22 parts to 45 parts, Sodium Nitrite 2 parts to 6 parts, 2 parts to 9 parts, calcium chloride, 0.1 part to 0.6 part, potassium hydroxide, 28 parts to 45 parts, oxyethane, 1-3 propylene diamine 4 parts to 36 parts, Witco 1298 Soft Acid 15 parts to 55 parts, thanomin 10 parts to 45 parts and dehydrated alcohol 2 parts to 20 parts.
here is the further optimization and/or improvements to one of foregoing invention technical scheme:
above-mentioned mixed surfactant obtains as follows: the first step, by the dodecyl phenol of aequum, Sodium Nitrite, calcium chloride and potassium hydroxide mix and carry out primary first-order equation 50min to 70min under temperature are 40 DEG C to 60 DEG C conditions, after primary first-order equation completes, add the oxyethane of aequum wherein, ensure in adition process that pressure maintains 0.0MPa to 0.6MPa, then it is 40 DEG C to 60 DEG C in temperature, pressure is carry out secondary reaction 6h to 10h under 0.0MPa to 0.6MPa condition, after secondary reaction completes, add the 1-3 propylene diamine of aequum wherein, then under temperature is 130 DEG C to 160 DEG C conditions, third-order reaction 5h to 8h is carried out, non-positive active agent is obtained after third-order reaction completes, and non-positive active agent is cooled to 40 DEG C to 60 DEG C, second step, obtains quaternary ammonium salt after the Witco 1298 Soft Acid of aequum and thanomin being mixed under temperature is 40 DEG C to 60 DEG C conditions, 3rd step, adds the non-positive active agent that quality is quaternary ammonium salt quality 25% to 55% in quaternary ammonium salt, reaction 10min to 25min after, then the dehydrated alcohol adding aequum wherein mix after obtain mixed surfactant.
in a first step above-mentioned, primary first-order equation, secondary reaction and third-order reaction all carry out under whipped state, and stir speed (S.S.) is 150r/min to 200r/min.
the reaction of above-mentioned 3rd step is carried out under whipped state, and stir speed (S.S.) is 150r/min to 200r/min.
two of technical scheme of the present invention is realized by following measures: a kind of preparation method of mixed surfactant, carry out in the steps below: the first step, by the dodecyl phenol of aequum, Sodium Nitrite, calcium chloride and potassium hydroxide mix and carry out primary first-order equation 50min to 70min under temperature are 40 DEG C to 60 DEG C conditions, after primary first-order equation completes, add the oxyethane of aequum wherein, ensure in adition process that pressure maintains 0.0MPa to 0.6MPa, then it is 40 DEG C to 60 DEG C in temperature, pressure is carry out secondary reaction 6h to 10h under 0.0MPa to 0.6MPa condition, after secondary reaction completes, add the 1-3 propylene diamine of aequum wherein, then under temperature is 130 DEG C to 160 DEG C conditions, third-order reaction 5h to 8h is carried out, non-positive active agent is obtained after third-order reaction completes, and non-positive active agent is cooled to 40 DEG C to 60 DEG C, second step, obtains quaternary ammonium salt after the Witco 1298 Soft Acid of aequum and thanomin being mixed under temperature is 40 DEG C to 60 DEG C conditions, 3rd step, adds the non-positive active agent that quality is quaternary ammonium salt quality 25% to 55% in quaternary ammonium salt, reaction 10min to 25min after, then the dehydrated alcohol adding aequum wherein mix after obtain mixed surfactant, wherein, raw materials by weight portion meter comprises dodecyl phenol 22 parts to 45 parts, Sodium Nitrite 2 parts to 6 parts, 2 parts to 9 parts, calcium chloride, 0.1 part to 0.6 part, potassium hydroxide, 28 parts to 45 parts, oxyethane, 1-3 propylene diamine 4 parts to 36 parts, Witco 1298 Soft Acid 15 parts to 55 parts, thanomin 10 parts to 45 parts and dehydrated alcohol 2 parts to 20 parts.
here is the further optimization and/or improvements to foregoing invention technical scheme two:
in a first step above-mentioned, primary first-order equation, secondary reaction and third-order reaction all carry out under whipped state, and stir speed (S.S.) is 150r/min to 200r/min.
the reaction of above-mentioned 3rd step is carried out under whipped state, and stir speed (S.S.) is 150r/min to 200r/min.
mixed surfactant in the present invention is to oil field oil water strong adaptability; alkaline agent need not be added; just can improve water displacing oil effect; current existing tensio-active agent can be replaced completely; and do not need to add alkaline agent; to meet the requirement of oil field development, and energy protection of the environment, be a kind of environmentally friendly additive.
Embodiment
the present invention by the restriction of following embodiment, can not determine concrete embodiment according to technical scheme of the present invention and practical situation.
below in conjunction with embodiment, the invention will be further described:
embodiment 1, the raw materials by weight portion meter of this mixed surfactant comprises dodecyl phenol 22 parts to 45 parts, Sodium Nitrite 2 parts to 6 parts, 2 parts to 9 parts, calcium chloride, 0.1 part to 0.6 part, potassium hydroxide, 28 parts to 45 parts, oxyethane, 1-3 propylene diamine 4 parts to 36 parts, Witco 1298 Soft Acid 15 parts to 55 parts, thanomin 10 parts to 45 parts and dehydrated alcohol 2 parts to 20 parts.
embodiment 2, the raw materials by weight portion meter of this mixed surfactant comprises dodecyl phenol 22 parts or 45 parts, Sodium Nitrite 2 parts or 6 parts, 2 parts, calcium chloride or 9 parts, 0.1 part, potassium hydroxide or 0.6 part, 28 parts, oxyethane or 45 parts, 1-3 propylene diamine 4 parts or 36 parts, Witco 1298 Soft Acid 15 parts or 55 parts, thanomin 10 parts or 45 parts and dehydrated alcohol 2 parts or 20 parts.
embodiment 3, be with the difference of embodiment 1 and embodiment 2, this mixed surfactant obtains by following preparation method: the first step, by the dodecyl phenol of aequum, Sodium Nitrite, calcium chloride and potassium hydroxide mix and carry out primary first-order equation 50min to 70min under temperature are 40 DEG C to 60 DEG C conditions, after primary first-order equation completes, add the oxyethane of aequum wherein, ensure in adition process that pressure maintains 0.0MPa to 0.6MPa, then it is 40 DEG C to 60 DEG C in temperature, pressure is carry out secondary reaction 6h to 10h under 0.0MPa to 0.6MPa condition, after secondary reaction completes, add the 1-3 propylene diamine of aequum wherein, then under temperature is 130 DEG C to 160 DEG C conditions, third-order reaction 5h to 8h is carried out, non-positive active agent is obtained after third-order reaction completes, and non-positive active agent is cooled to 40 DEG C to 60 DEG C, second step, obtains quaternary ammonium salt after the Witco 1298 Soft Acid of aequum and thanomin being mixed under temperature is 40 DEG C to 60 DEG C conditions, 3rd step, adds the non-positive active agent that quality is quaternary ammonium salt quality 25% to 55% in quaternary ammonium salt, reaction 10min to 25min after, then the dehydrated alcohol adding aequum wherein mix after obtain mixed surfactant.
embodiment 4, be with the difference of embodiment 1 and embodiment 2, this mixed surfactant obtains by following preparation method: the first step, by the dodecyl phenol of aequum, Sodium Nitrite, calcium chloride and potassium hydroxide mix and carry out primary first-order equation 50min or 70min under temperature are 40 DEG C or 60 DEG C of conditions, after primary first-order equation completes, add the oxyethane of aequum wherein, ensure in adition process that pressure maintains 0.0MPa or 0.6MPa, then it is 40 DEG C or 60 DEG C in temperature, pressure is carry out secondary reaction 6h or 10h under 0.0MPa or 0.6MPa condition, after secondary reaction completes, add the 1-3 propylene diamine of aequum wherein, then under temperature is 130 DEG C or 160 DEG C of conditions, third-order reaction 5h or 8h is carried out, non-positive active agent is obtained after third-order reaction completes, and non-positive active agent is cooled to 40 DEG C or 60 DEG C, second step, obtains quaternary ammonium salt after the Witco 1298 Soft Acid of aequum and thanomin being mixed under temperature is 40 DEG C or 60 DEG C of conditions, 3rd step, adds the non-positive active agent that quality is quaternary ammonium salt quality 25% or 55% in quaternary ammonium salt, reaction 10min or 25min after, then the dehydrated alcohol adding aequum wherein mix after obtain mixed surfactant.
embodiment 5, as the optimization of embodiment 3 and embodiment 4, in a first step, primary first-order equation, secondary reaction and third-order reaction all carry out under whipped state, and stir speed (S.S.) is 150r/min to 200r/min.
embodiment 6, as the optimization of embodiment 3, embodiment 4 and embodiment 5, the reaction of the 3rd step is carried out under whipped state, and stir speed (S.S.) is 150r/min to 200r/min.
the present invention is to oil field oil water strong adaptability, alkaline agent need not be added, just can improve water displacing oil effect, during use, when to add the mixed surfactant concentration obtained according to the embodiment of the present invention be 0.2% to 1%, drip ultra low interfacial tension instrument TX500C with rotation to measure, data show, use the mixed surfactant obtained according to the embodiment of the present invention can form low oil water interfacial tension < 5 × 10-2mN/m, on indoor flooding apparatus, carrying out mensuration by industry (SY/T5277-2000) standard, to obtain displacement of reservoir oil rate mean value be 10% to 23%, and average energy improves the recovery ratio of 18%, this has absolutely proved that the mixed surfactant obtained according to the embodiment of the present invention can replace current existing tensio-active agent completely, and do not need to add alkaline agent, to meet the requirement of oil field development, and energy protection of the environment, be a kind of environmentally friendly additive.
above technical characteristic constitutes embodiments of the invention, and it has stronger adaptability and implementation result, can increase and decrease non-essential technical characteristic according to actual needs, meet the demand of different situations.
Claims (6)
1. a mixed surfactant, it is characterized in that raw materials by weight portion meter comprises dodecyl phenol 22 parts to 45 parts, Sodium Nitrite 2 parts to 6 parts, 2 parts to 9 parts, calcium chloride, 0.1 part to 0.6 part, potassium hydroxide, 28 parts to 45 parts, oxyethane, 1,3-propylene diamine 4 parts to 36 parts, Witco 1298 Soft Acid 15 parts to 55 parts, thanomin 10 parts to 45 parts and dehydrated alcohol 2 parts to 20 parts, wherein: this mixed surfactant obtains as follows: the first step, by the dodecyl phenol of aequum, Sodium Nitrite, calcium chloride and potassium hydroxide mix and carry out primary first-order equation 50min to 70min under temperature are 40 DEG C to 60 DEG C conditions, after primary first-order equation completes, add the oxyethane of aequum wherein, ensure in adition process that pressure maintains 0.0MPa to 0.6MPa, then it is 40 DEG C to 60 DEG C in temperature, pressure is carry out secondary reaction 6h to 10h under 0.0MPa to 0.6MPa condition, after secondary reaction completes, add 1 of aequum wherein, 3-propylene diamine, then under temperature is 130 DEG C to 160 DEG C conditions, third-order reaction 5h to 8h is carried out, non-positive active agent is obtained after third-order reaction completes, and non-positive active agent is cooled to 40 DEG C to 60 DEG C, second step, obtains quaternary ammonium salt after the Witco 1298 Soft Acid of aequum and thanomin being mixed under temperature is 40 DEG C to 60 DEG C conditions, 3rd step, adds the non-positive active agent that quality is quaternary ammonium salt quality 25% to 55% in quaternary ammonium salt, reaction 10min to 25min after, then the dehydrated alcohol adding aequum wherein mix after obtain mixed surfactant.
2. mixed surfactant according to claim 1, is characterized in that in a first step, and primary first-order equation, secondary reaction and third-order reaction all carry out under whipped state, and stir speed (S.S.) is 150r/min to 200r/min.
3. mixed surfactant according to claim 1 and 2, it is characterized in that the reaction of the 3rd step is carried out under whipped state, stir speed (S.S.) is 150r/min to 200r/min.
4. the preparation method of a mixed surfactant according to claim 1, it is characterized in that carrying out in the steps below: the first step, by the dodecyl phenol of aequum, Sodium Nitrite, calcium chloride and potassium hydroxide mix and carry out primary first-order equation 50min to 70min under temperature are 40 DEG C to 60 DEG C conditions, after primary first-order equation completes, add the oxyethane of aequum wherein, ensure in adition process that pressure maintains 0.0MPa to 0.6MPa, then it is 40 DEG C to 60 DEG C in temperature, pressure is carry out secondary reaction 6h to 10h under 0.0MPa to 0.6MPa condition, after secondary reaction completes, add 1 of aequum wherein, 3-propylene diamine, then under temperature is 130 DEG C to 160 DEG C conditions, third-order reaction 5h to 8h is carried out, non-positive active agent is obtained after third-order reaction completes, and non-positive active agent is cooled to 40 DEG C to 60 DEG C, second step, obtains quaternary ammonium salt after the Witco 1298 Soft Acid of aequum and thanomin being mixed under temperature is 40 DEG C to 60 DEG C conditions, 3rd step, adds the non-positive active agent that quality is quaternary ammonium salt quality 25% to 55% in quaternary ammonium salt, reaction 10min to 25min after, then the dehydrated alcohol adding aequum wherein mix after obtain mixed surfactant.
5. the preparation method of mixed surfactant according to claim 4, is characterized in that in a first step, and primary first-order equation, secondary reaction and third-order reaction all carry out under whipped state, and stir speed (S.S.) is 150r/min to 200r/min.
6. the preparation method of the mixed surfactant according to claim 4 or 5, it is characterized in that the reaction of the 3rd step is carried out under whipped state, stir speed (S.S.) is 150r/min to 200r/min.
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CN102206483A (en) * | 2011-04-11 | 2011-10-05 | 西南石油大学 | Surfactant/polymer water repellent identification composite oil displacement agent and preparation method thereof |
CN102604620A (en) * | 2012-02-10 | 2012-07-25 | 胜利油田中胜环保有限公司 | Petroleum sulfonate compounded system for oil displacement and preparation method thereof |
CN102895913A (en) * | 2012-09-28 | 2013-01-30 | 西南石油大学 | Cation type dimeric surfactant containing polyoxyethylene ether and synthetizing method of cation type dimeric surfactant |
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2013
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RU2093670C1 (en) * | 1995-01-10 | 1997-10-20 | Научно-исследовательский институт "Нефтеотдача" | Method of improving efficiency of oil displacement by non-ionogenic oil-soluble surface-active materials |
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CN102206483A (en) * | 2011-04-11 | 2011-10-05 | 西南石油大学 | Surfactant/polymer water repellent identification composite oil displacement agent and preparation method thereof |
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Denomination of invention: Mixed surfactant and its preparation method Effective date of registration: 20210625 Granted publication date: 20160302 Pledgee: Karamay Petroleum Branch of Bank of China Ltd. Pledgor: KARAMAY ZHENGCHENG Co.,Ltd. Registration number: Y2021980005336 |