CN1560178A - Anti-salt type thicking oil reducing viscosity agent and preparation process thereof - Google Patents
Anti-salt type thicking oil reducing viscosity agent and preparation process thereof Download PDFInfo
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- CN1560178A CN1560178A CNA2004100236152A CN200410023615A CN1560178A CN 1560178 A CN1560178 A CN 1560178A CN A2004100236152 A CNA2004100236152 A CN A2004100236152A CN 200410023615 A CN200410023615 A CN 200410023615A CN 1560178 A CN1560178 A CN 1560178A
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Abstract
The invention provides a salt-resistant crude oil viscosity reductant and its preparing method, and it is polyoxyethylene ether hydroxy propanesulfonate synthesized by using a nonionic surfactant containing special oxyethylene chain segment as raw material and the preparing method includes 1, making polyoxyethylene ether nonionic surfactant react with epoxy chloropropane to obtain polyoxyethylene ether chlorohydroxy propane; 2, making the product in step 1 reacts with NaOH to obtain polyoxyethylene ether epoxy propane; 3, sulfonating the product in step 2 with sodium disulfite to obtain it. Its character: by selecting polyoxyethylene alkyl alcohol (phenol) ether nonionic surfactant of different oxyethylene chain segments as raw materials, it can prepare crude oil viscosity reductants of different salt resisting properties.
Description
Technical field:
The present invention relates to a kind of oilfield chemistry with agent especially anti-salt type heavy crude thinner and preparation method thereof.
Background technology:
Viscous crude is that viscosity is big, colloid and the high quasi-oil of asphalt content.Because oil is thick, the oil pumper load is big, the current consumption height, and mechanical accident is frequent, so the key of heavy oil development is reduction viscosity, improves liquidity.The heavy oil wells viscosity reducing method that proposes both at home and abroad mainly contains hot method (comprising accompanying-heat cable, electrically heated sucker rod, heat-conducting oil heating method etc.), light oil dilution method, reducing viscosity by emulsifying method etc. at present.In these methods, hot method viscosity reduction technology comparative maturity, effect are better, but power consumption is big, cost is high; Mix the thin oil method to extraction liquid aftertreatment do not have influence, but caused the waste of thin oil resource; The construction of reducing viscosity by emulsifying method is simple, running cost is lower, is the viscosity reducing technology of present widespread use.The key of this technology is to develop emulsifying agent efficiently.Emulsifying agent commonly used has alkyl carboxylate's (naphthenate), sulfonated petro-leum, OP, peregal etc., based on this, has formed GY heavy crude thinner, BL heavy crude thinner, HEA heavy crude thinner etc.These heavy crude thinners have played vital role to the exploitation of common heavy oil reservoir.
To mix with local water in the viscosity-depression agent use.Usually contain a certain amount of inorganic salt in the local water, as sodium-chlor, magnesium chloride, calcium chloride etc., the local water saltiness of some special oil reservoirs is then high especially, and as the LG15-2 well of system in Tahe Oilfield, formation water salinity is 2.26 * 10
5Mg/L, wherein ρ (Ca
2+)=1.3 * 10
4Mg/L, ρ (Mg
2+)=800mg/L; The ST7-H1 well in mulberry tower wood oil field, formation water salinity is 2.33 * 10
5Mg/L, wherein ρ (Ca
2+)=1.13 * 10
4Mg/L, ρ (Mg
2+)=921mg/L; The ST5-H1 well in mulberry tower wood oil field, formation water salinity is 2.13 * 10
5Mg/L, wherein ρ (Ca
2+)=1.19 * 10
4Mg/L, ρ (Mg
2+)=1067mg/L.Because local water saltiness height, cause conventional viscosity-depression agent that the reducing thick oil viscosity ability of this class oil reservoir is reduced (the effective viscosity reduction massfraction that shows as viscosity-depression agent increases substantially) even disappearance, therefore develop salt tolerant type heavy crude thinner, significant for high salinity, the particularly exploitation of the heavy crude reservoir of high contents of calcium and magnesium ion content.
Heavy crude thinner is tensio-active agent normally.The tensio-active agent that can be used as heavy crude thinner mainly contains nonionogenic tenside, anion surfactant, amphoterics, wherein the anion surfactant salt resistance ability is not high, so salt tolerant type heavy crude thinner mainly is nonionogenic tenside, amphoterics and both compounds thereof.
US4265264 has reported with polyoxyethylated alkyl alcohol sulfuric acid and polyoxyethylene polyoxypropylene block polyether and has made salt tolerant type heavy crude thinner, but used local water saltiness only is 4720mg/L.
US4333488 has reported with the adipic acid ester of polyoxyethylene polyoxypropylene block polyether and has made salt tolerant type heavy crude thinner that used local water saltiness is 1.2 * 10
4Mg/L (ρ (Ca wherein
2+)=600mg/L, ρ (Mg
2+During)=130mg/L), still have viscosity reducing effect preferably.
US4127678, US4781207 have reported with polyoxyethylated alkyl alcohol acetate, polyoxyethylated alkyl alcohol ethyl sulfonate etc. and have made salt tolerant type heavy crude thinner, but its salt resistance ability do not described.
US4355651 has reported with the polyoxyethylene polyoxypropylene phosphate ester salt and has made salt tolerant type heavy crude thinner that used local water saltiness is up to 4.6 * 10
4Mg/L (ρ (Ca wherein
2+, Mg
2+)=2100mg/L) still has viscosity reducing effect preferably.
The Peng Piao of Beijing Petroleum Chemical Engineering Institute, Qin Bing etc. have reported then with the Soxylat A 25-7 type nonionogenic tenside of aryl end socket and the aromatic acid of replacement or the condenses of aromatic sulfonic acid type anion surfactant and have made salt tolerant type heavy crude thinner that used local water saltiness is up to 5.0 * 10
4Mg/L, wherein ρ (Ca
2+, Mg
2+)=750mg/L, to the viscosity break ratio of the special viscous crude of the super viscous crude in Dan Jia temple, Xinjiang common heavy oil, the Liaohe River greater than more than 95%.
But make a general survey of domestic and international reducing thick oil viscosity technology, for being adapted to the local water saltiness up to 2.0 * 10
5The salt tolerant viscosity-depression agent of the special heavy crude reservoir of mg/L, then do not appear in the newspapers to.
Summary of the invention:
The purpose of this invention is to provide a class and have heavy crude thinner of higher salt resistance ability and preparation method thereof.
The object of the present invention is achieved like this, and the heavy crude thinner that is proposed is to be raw material synthetic Soxylat A 25-7 hydroxy-propanesulfonic acid salt with the nonionogenic tenside that contains certain oxygen ethene chain link, and its general structure is:
Molecular weight 522～1062.
The preparation method of heavy crude thinner of the present invention mainly comprised for three steps: the first step by Soxylat A 25-7 type nonionogenic tenside and epichlorohydrin reaction, obtains Soxylat A 25-7 chloro hydroxy propane; In second step, product Soxylat A 25-7 chloro hydroxy propane and NaOH reaction obtain the Soxylat A 25-7 propylene oxide; In the 3rd step, Soxylat A 25-7 propylene oxide and sodium bisulfite carry out sulfonation reaction, obtain Soxylat A 25-7 hydroxy-propanesulfonic acid salt.The equation of reaction is as follows:
Said Soxylat A 25-7 type nonionogenic tenside is selected from Soxylat A 25-7 alkyl ethoxylated or polyethenoxy alkylphenols etc., also can be their mixture.
In the formula: R represents alkyl or alkylbenzene, and R generally contains 12～16 carbon;
N is the chain number of oxygen ethene, and generally selecting n is 4～20.
By regulating the chain number of oxygen ethene, can make Soxylat A 25-7 hydroxy-propanesulfonic acid salt have different salt resistances, thereby obtain having the heavy crude thinner of different salt resistance abilities.When n was 4～8, the gained viscosity-depression agent can anti-10
5The sodium-chlor of mg/L or 3.0 * 10
4The calcium chloride of mg/L; When n is 10～20, then can forms and be adapted to local water inorganic salt mass concentration up to 2.26 * 10
5The viscosity-depression agent of the high salt heavy crude reservoir of mg/L.
Embodiment:
Specify anti-salt type heavy crude thinner of the present invention and preparation method thereof below by embodiment.
Anti-salt type heavy crude thinner of the present invention is to be raw material synthetic Soxylat A 25-7 hydroxy-propanesulfonic acid salt with the nonionogenic tenside that contains certain oxygen ethene chain link, and its general structure is:
Molecular weight 522～1062.
Embodiment 1:
The preparation of main explanation polyoxyethylene nonylphenol ether hydroxypropionate sodium-15.
Add 0.1mol polyoxyethylene nonylphenol ether-15 in there-necked flask, add the 1.2g tin tetrachloride again, oil bath is heated to 100 ℃, splashes into the 0.15mol epoxy chloropropane by funnel while stirring.Reacted again 0.5 hour after dripping off epoxy chloropropane, can get intermediate product Soxylat A 25-7 chloro hydroxy propane-15.Add 0.11mol sodium hydroxide in above-mentioned product, 70 ℃ were reacted 0.5 hour, and can get intermediate product Soxylat A 25-7 propylene oxide-15.Add 0.2mol sodium bisulfite, 0.1mol S-WAT at last, be warmed up to 140 ℃ the reaction 4 hours, get final product polyoxyethylene nonylphenol ether hydroxypropionate sodium-15, overall yield is 65%.Add the water of 3 times of quality, make heavy crude thinner 1.
Embodiment 2:
Make raw material with polyoxyethylene nonylphenol ether-8, add 0.1mol polyoxyethylene nonylphenol ether-8 in there-necked flask, add the 1.2g tin tetrachloride again, oil bath is heated to 100 ℃, splashes into the 0.15mol epoxy chloropropane by funnel while stirring.Reacted again 0.5 hour after dripping off epoxy chloropropane, can get intermediate product polyoxyethylene nonylphenol ether chloro hydroxy propane-8.Add 0.11mol sodium hydroxide in above-mentioned product, 70 ℃ were reacted 0.5 hour, and can get intermediate product polyoxyethylene nonylphenol ether ring Ethylene Oxide-8.Add 0.2mol sodium bisulfite, 0.1mol S-WAT at last, be warmed up to 140 ℃ of reactions 4 hours, synthetic polyoxyethylene nonylphenol ether hydroxypropionate sodium-8, overall yield is 67%.Add the water of 3 times of quality, make heavy crude thinner 2.
Characteristics of the present invention:
Make raw material by the Soxylat A 25-7 nonionogenic tenside of selecting different oxygen ethene chain links, can prepare the heavy crude thinner with different salt resistant characters: with polyoxyethylene nonylphenol ether hydroxypropionate sodium-8 is the viscosity-depression agent of main component, viscous crude to Liaohe Oil Field, Shengli Oil Field all has viscosity-reducing performance preferably, can anti-10
5The sodium-chlor of mg/L or 3 * 10
4The calcium chloride of mg/L; With polyoxyethylene nonylphenol ether hydroxypropionate sodium-15 is the viscosity-depression agent of main component, and salt resistance ability is up to 2.26 * 10
5Mg/L can be used as the viscosity-depression agent of high salinity reservoir viscous crude.
Claims (3)
1. an anti-salt type heavy crude thinner is characterized in that the nonionogenic tenside to contain aerobic ethylene chain joint is a raw material synthetic Soxylat A 25-7 hydroxy-propanesulfonic acid salt, and its general structure is:
Molecular weight 522～1062.
2. the preparation method of an anti-salt type heavy crude thinner is characterized in that mainly comprising three steps:
The first step by Soxylat A 25-7 type nonionogenic tenside and epichlorohydrin reaction, obtains Soxylat A 25-7 chloro hydroxy propane;
In second step, product Soxylat A 25-7 chloro hydroxy propane and NaOH reaction obtain the Soxylat A 25-7 propylene oxide;
In the 3rd step, Soxylat A 25-7 propylene oxide and sodium bisulfite carry out sulfonation reaction, obtain Soxylat A 25-7 hydroxy-propanesulfonic acid salt, and the equation of reaction is as follows:
In the formula: R represents alkyl or alkylbenzene, and R contains 12～16 carbon; N is the chain number of oxygen ethene, and selecting n is 4～20.
3. according to the preparation method of the described anti-salt type heavy crude thinner of claim 2, it is characterized in that said Soxylat A 25-7 type nonionogenic tenside is selected from polyoxyethylated alkyl alcohol or polyethenoxy alkylphenols, also can be their mixture.
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| CNA2004100236152A CN1560178A (en) | 2004-02-25 | 2004-02-25 | Anti-salt type thicking oil reducing viscosity agent and preparation process thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004100236152A CN1560178A (en) | 2004-02-25 | 2004-02-25 | Anti-salt type thicking oil reducing viscosity agent and preparation process thereof |
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| CN1560178A true CN1560178A (en) | 2005-01-05 |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280182B (en) * | 2007-04-04 | 2010-10-06 | 中国石油化工股份有限公司 | Surfactant composition and use thereof |
| CN101280180B (en) * | 2007-04-04 | 2011-02-09 | 中国石油化工股份有限公司 | Surfactant composition and use thereof |
| CN101280181B (en) * | 2007-04-04 | 2011-02-09 | 中国石油化工股份有限公司 | Surfactant composition and use thereof |
| CN101280179B (en) * | 2007-04-04 | 2011-02-09 | 中国石油化工股份有限公司 | Surfactant composition and use thereof |
| CN103058895A (en) * | 2012-12-21 | 2013-04-24 | 江苏美思德化学股份有限公司 | Heat resistance and salt tolerance type polyether sulfonic acid salt and synthetic method thereof |
| CN103540297A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Composite oil-based emulsifier containing fatty alcohol polyoxyethylene polypropylene oxide ether carboxylate and preparation method thereof |
| CN103897172A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | Phenol ether sulfonate oil-based emulsifier and preparation method thereof |
| CN103897677A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | Oil-based drilling fluid adopting phenol ether sulfonate composite oil-based emulsifier, and preparation method thereof |
| CN104147977A (en) * | 2014-07-09 | 2014-11-19 | 华南理工大学 | Lignin-based anion-cation type high-molecular surface active agent and preparation method thereof |
| CN104277808A (en) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Oil-displacement surfactant and preparation method thereof |
| CN104277812A (en) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Tertiary oil recovery surfactant and preparation method thereof |
| CN104277811A (en) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Preparation method for enhanced oil recovery surfactant |
| CN105273704A (en) * | 2014-07-11 | 2016-01-27 | 中国石油化工股份有限公司 | Salt-resistant oil-displacing surfactant and preparation method thereof |
| CN105273705A (en) * | 2014-07-11 | 2016-01-27 | 中国石油化工股份有限公司 | Salt-resistant oil-displacing composition and preparation method thereof |
| CN106590584A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Oil-displacement surfactant for high-salt oil reservoirs |
| CN105315980B (en) * | 2014-07-24 | 2018-08-17 | 中国石油化工股份有限公司 | Displacement composition and preparation method thereof |
| CN109135703A (en) * | 2018-09-17 | 2019-01-04 | 佛山市禅城区诺高环保科技有限公司 | A kind of preparation method of heavy crude thinner |
-
2004
- 2004-02-25 CN CNA2004100236152A patent/CN1560178A/en active Pending
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101280180B (en) * | 2007-04-04 | 2011-02-09 | 中国石油化工股份有限公司 | Surfactant composition and use thereof |
| CN101280181B (en) * | 2007-04-04 | 2011-02-09 | 中国石油化工股份有限公司 | Surfactant composition and use thereof |
| CN101280179B (en) * | 2007-04-04 | 2011-02-09 | 中国石油化工股份有限公司 | Surfactant composition and use thereof |
| CN101280182B (en) * | 2007-04-04 | 2010-10-06 | 中国石油化工股份有限公司 | Surfactant composition and use thereof |
| CN103540297A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Composite oil-based emulsifier containing fatty alcohol polyoxyethylene polypropylene oxide ether carboxylate and preparation method thereof |
| CN103540297B (en) * | 2012-07-12 | 2017-04-19 | 中国石油化工股份有限公司 | Composite oil-based emulsifier containing fatty alcohol polyoxyethylene polypropylene oxide ether carboxylate and preparation method thereof |
| CN103058895A (en) * | 2012-12-21 | 2013-04-24 | 江苏美思德化学股份有限公司 | Heat resistance and salt tolerance type polyether sulfonic acid salt and synthetic method thereof |
| CN103897172B (en) * | 2012-12-27 | 2016-09-07 | 中国石油化工股份有限公司 | 2, 2-Oxydiphenol sulfonate oil base emulsifying agent and preparation method |
| CN103897172A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | Phenol ether sulfonate oil-based emulsifier and preparation method thereof |
| CN103897677A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | Oil-based drilling fluid adopting phenol ether sulfonate composite oil-based emulsifier, and preparation method thereof |
| CN104277812B (en) * | 2013-07-09 | 2017-05-17 | 中国石油化工股份有限公司 | Tertiary oil recovery surfactant and preparation method thereof |
| CN104277811B (en) * | 2013-07-09 | 2017-07-14 | 中国石油化工股份有限公司 | The preparation method of intensified oil reduction surfactant |
| CN104277811A (en) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Preparation method for enhanced oil recovery surfactant |
| CN104277812A (en) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Tertiary oil recovery surfactant and preparation method thereof |
| CN104277808A (en) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Oil-displacement surfactant and preparation method thereof |
| CN104277808B (en) * | 2013-07-09 | 2017-06-20 | 中国石油化工股份有限公司 | Surfactant oil displacement and preparation method thereof |
| CN104147977A (en) * | 2014-07-09 | 2014-11-19 | 华南理工大学 | Lignin-based anion-cation type high-molecular surface active agent and preparation method thereof |
| CN104147977B (en) * | 2014-07-09 | 2015-10-28 | 华南理工大学 | A kind of lignin-base anion and cation high molecular surfactant and preparation method thereof |
| CN105273705A (en) * | 2014-07-11 | 2016-01-27 | 中国石油化工股份有限公司 | Salt-resistant oil-displacing composition and preparation method thereof |
| CN105273704A (en) * | 2014-07-11 | 2016-01-27 | 中国石油化工股份有限公司 | Salt-resistant oil-displacing surfactant and preparation method thereof |
| CN105273705B (en) * | 2014-07-11 | 2018-04-06 | 中国石油化工股份有限公司 | Salt tolerant displacement composition and preparation method thereof |
| CN105273704B (en) * | 2014-07-11 | 2018-05-11 | 中国石油化工股份有限公司 | Salt tolerant oil displacement surfactant and preparation method thereof |
| CN105315980B (en) * | 2014-07-24 | 2018-08-17 | 中国石油化工股份有限公司 | Displacement composition and preparation method thereof |
| CN106590584A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Oil-displacement surfactant for high-salt oil reservoirs |
| CN106590584B (en) * | 2015-10-20 | 2019-05-14 | 中国石油化工股份有限公司 | Oil displacement surfactant for high salinity reservoir |
| CN109135703A (en) * | 2018-09-17 | 2019-01-04 | 佛山市禅城区诺高环保科技有限公司 | A kind of preparation method of heavy crude thinner |
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