CN1326589C - Demulsifier with inorganic-polymer compound structure and its preparing method - Google Patents
Demulsifier with inorganic-polymer compound structure and its preparing method Download PDFInfo
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- CN1326589C CN1326589C CNB2004100098398A CN200410009839A CN1326589C CN 1326589 C CN1326589 C CN 1326589C CN B2004100098398 A CNB2004100098398 A CN B2004100098398A CN 200410009839 A CN200410009839 A CN 200410009839A CN 1326589 C CN1326589 C CN 1326589C
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Abstract
The present invention relates to a demulsifier with an inorganic-polymer compound structure and a preparation method thereof. In the method, an organic high molecular weight demulsifier and an inorganic nanometer oxide are processed by in-situ synthesis, i.e. the inorganic nanometer oxide is coated or grafted by the organic high molecular weight demulsifier during the generating process of the nanometer level oxide to obtain a high efficiency demulsifier having an inorganic-polymer compound structure. During the preparation process of the in-situ synthesizing method, the weight ratios of all the materrials for preparing an organic high molecular weight demulsifier solution are: 10 portions of organic high molecular weight demulsifier, 2 portions of ethanol and 3 portions of deionized water; the molar ratio of inorganic nanometer oxide precursors of the prepared inorganic nanometer oxide precursor solution to water is 0.023:1, and the pH value of the mixed solution is about 7. The demulsifier comprises constituent content with the weight percentage: 18 to 54% of organic high molecular weight demulsifier, 2 to 6% of inorganic nanometer oxide and 40 to 80% of other constituents. The demulsifier has the advantages of simpleness, mild reacting condition, easy raw material obtainment, high efficiency, low price and good demulsifying effect.
Description
Technical field
The present invention relates to a kind of demulsifier and preparation method thereof, be applicable to crude oil emulsion is carried out breakdown of emulsion.
Background technology
Crude oil demulsifier is a kind of chemical agent of extensive use on petroleum industry, though because the crude oil that formed in 1 years is water-oil separating in the stratum, but owing to the turbulent motion of crude oil and water, they are through mixing the crude oil emulsion that has formed different stability consumingly in exploitation, the defeated process of collection.Crude oil emulsion can produce very big influence to the collection of crude oil is defeated, so oil extraction must carry out breakdown of emulsion to crude oil emulsion after coming out, and the demulsifier of (1914) is the patent of Barnichel the earliest, and suggestion is with the FeSO of concentration 0.1%
4Solution carries out breakdown of emulsion to crude oil emulsion under 35～60 ℃, counting demulsifier has thenceforth had the history in 90 years, in this history in 90 years, a variety of demulsifiers has appearred, experienced inorganic salts, organic molecule class, organic polymer class demulsifier three phases.The demulsifier of present stage mainly is based on non-ionic polyoxyethylene polyoxypropylene block polymer, the development of demulsifier is mainly concentrated on traditional demulsifier is satisfied new demand to demulsifier by method modifications such as " change head, change tail, add bone, chain extension, grafting, crosslinked, composite ".But above-mentioned demulsifier and method of modifying still exist the preparation component too much, a series of shortcomings such as complicated process of preparation, modified condition harshness or demulsification be undesirable.
Summary of the invention
Technical problem to be solved by this invention is, existing demulsifier and method of modifying exist the preparation component too much, complicated process of preparation, modified condition harshness or the unfavorable shortcoming of demulsification.
Technical scheme of the present invention:
A kind of inorganic-preparation method of polymer complex structure demulsifier, it is synthetic that this method employing organic polymer demulsifier and inorganic nanometer oxide carry out original position, promptly in the generative process of nano-scale oxide, the organic polymer demulsifier coats inorganic nanometer oxide or grafting, obtains inorganic-polymer complex structure demulsifier.
Organic polymer demulsifier and inorganic nanometer oxide carry out original position when synthetic, and each material proportioning is in the organic polymer demulsifier solution of preparation: the mass ratio of organic polymer demulsifier, ethanol, deionized water is 10: 2: 3.The ratio of each component is in the inorganic nanometer oxide mother solution of preparation: the mol ratio of inorganic nanometer oxide parent and water is 0.023: 1.The pH that regulates organic polymer demulsifier solution and inorganic nanometer oxide mother solution mixed liquor is about 7.
A kind of inorganic-preparation method of polymer complex structure demulsifier:
The first step at normal temperatures, is 10: 2: 3 preparation organic polymer demulsifier solution by the mass ratio of polyoxyethylene polyoxypropylene phenolic aldehyde polyethylene polyamine block copolymer TA-1031, ethanol, deionized water;
At normal temperatures, be 0.023: 1 by the mol ratio of inorganic nanometer oxide parent aluminum sulfate and water, preparation aluminum sulfate Al
2(SO
4)
3Solution;
In second step, the above-mentioned two kinds of solution of measuring by the percentage by weight of oxypropylene polyoxyethylene phenolic aldehyde polyethylene polyamine block copolymer TA-1031 and nano aluminium oxide in the product mix at normal temperatures, are about to generate the aluminum sulfate Al of nano aluminium oxide
2(SO
4)
3Solution slowly is added drop-wise in the organic polymer demulsifier solution, after treating fully to mix, surveys the pH value of this moment;
In the 3rd step, the pH value of regulating mixed liquor dropping ammonia lentamente in mixed solution has good mobility according to the flowability interpolation deionized water of reaction back system with the maintenance system, and the pH value of whole system is adjusted to about 7;
The 4th step kept whole system to react under condition of stirring 6～8 hours, obtained inorganic-polymer complex structure demulsifier.
A kind of inorganic-the polymer complex structure demulsifier, each constituent content in this demulsifier is as follows:
Weight percentages of components (%)
Polyoxyethylene polyoxypropylene phenolic aldehyde polyethylene polyamine block copolymer TA-1031 18～54;
Nano aluminium oxide 2～6;
The salt 40～80 that water and ethanol and a small amount of reaction generate.
The present invention compares the beneficial effect that has with prior art: the preparation method is simple, the reaction condition gentleness, raw material are easy to obtain, inexpensive effect is high, show through the crude oil demulsification test: this demulsifier improves 20～30% than the dehydration rate of existing conventional demulsifier, oil-water interfaces are also more neat, and it is also more clear to deviate from water.A large amount of experiments prove that fully the demulsifier of this new structure has inexpensive, characteristics of high efficiency.
Description of drawings
Fig. 1 contains Si demulsifier shape appearance figure.
Fig. 2 contains Al demulsifier shape appearance figure.
The specific embodiment
The present invention adopts polyoxyethylene polyoxypropylene phenolic aldehyde polyethylene polyamine block copolymer TA-1031 as the organic polymer demulsifier, and its structural formula is as follows:
M=(C
3H
6O)
x(C
2H
4O)
yH x, y are the degree of polymerization
The parent of inorganic nanometer oxide adopts aluminum sulfate Al
2(SO
4)
3For embodiment is described further this method.
Preparation process is as follows:
1. in the ethanolic solution of TA-1031, add small quantity of deionized water, stir; The mass ratio of TA-1031, ethanol, ionized water is 10: 2: 3.
2. prepare inorganic nanometer oxide mother solution---aluminum sulfate Al
2(SO
4)
3Solution.
Aluminum sulfate Al
2(SO
4)
3With the mol ratio of water be 0.023: 1
3. at normal temperatures with the aluminum sulfate Al for preparing
2(SO
4)
3Solution slowly drips in the TA-1031 solution, after treating fully to mix, surveys the pH value of this moment.
4. regulate the pH value of mixed solution.
In mixed solution drips, add ammoniacal liquor, in the process of dropping ammonia, will drip slowly, and with the maintenance system good mobility is arranged, add ammoniacal liquor and regulate about the pH value to 7 of whole system according to the flowability interpolation deionized water of reaction back system.
5. keep whole system to react under condition of stirring 6～8 hours, in the generative process of alumina in Nano level, the organic polymer demulsifier obtains inorganic-polymer complex structure demulsifier with its coating or grafting.
Each constituent content in the demulsifier of gained nanostructure-containing is as follows:
Weight percentages of components (%)
Polyoxyethylene polyoxypropylene phenolic aldehyde polyethylene polyamine block copolymer TA-1031 18～54;
Nano aluminium oxide 2～6;
The salt 40～80 that water and ethanol and a small amount of reaction generate.
Reaction condition gentleness of the present invention at room temperature just can react, and raw material are simple and easy to, and do not have " three wastes " to produce in process of production.
Described organic polymer demulsifier comprises: suitability for industrialized production and be applied to the non-ionic polyoxyethylene polyoxypropylene block polymer series organic polymer demulsifier of crude oil demulsification.
The parent of inorganic nanometer oxide also can adopt: sodium metasilicate (Na
2SiO
3), butyl titanate Ti (OC
4H
9)
4Deng.
The transmission electron microscope (TEM) that utilizes the demulsifier of gained of the present invention is as Fig. 1 and Fig. 2.
From the TEM figure as can be seen, the nano inorganic oxide particle is surrounded by organic polymer and has formed coating or Grafting Structure, and the connection by organic molecule, nano inorganic oxide that each is coated and organic polymer have formed the network structure of highly branched chain together.
Evaluation to these two kinds of demulsifiers:
With crude oil demulsification result such as the following table of demulsifier of the present invention to Shengli Oil Field lonely eastern
| The demulsifier title | The dehydration rate (%) of different breakdown of emulsion times | The oil-water interfaces situation | Deviate from water colour | ||||
| 15min | 30min | 60min | 90min | 120min | |||
| No demulsifier | 0 | 0 | 1.3 | 5.5 | 10.2 | Neater | Clearly |
| TA-1031 | 0.00 | 19.35 | 41.29 | 52.26 | 70.42 | Neater | Clearly |
| Contain the Al demulsifier | 35.48 | 77.42 | 83.87 | 87.10 | 91.61 | Together | Clearly |
| Contain the Si demulsifier | 9.68 | 32.26 | 41.94 | 45.16 | 90.32 | Together | Clearly |
From to the evaluation of these several demulsifiers as can be seen, the composite demulsifying agent that contains inorganic-polymer complex structure exceeds about 20% than the dewatering efficiency of demulsifier commonly used at present, and its oil-water interfaces are also more neat.
Claims (3)
1. inorganic-polymer complex structure demulsifier, it is characterized in that: each constituent content in this demulsifier is as follows:
Weight percentages of components (%)
Polyoxyethylene polyoxypropylene phenolic aldehyde polyethylene polyamine block copolymer TA-1031 18～54;
Nano aluminium oxide 2～6;
The salt 40～80 that water and ethanol and a small amount of reaction generate.
2. the preparation method of inorganic-polymer complex structure demulsifier is characterized in that, its preparation process is:
The first step at normal temperatures, is 10: 2: 3 preparation organic polymer demulsifier solution by the mass ratio of polyoxyethylene polyoxypropylene phenolic aldehyde polyethylene polyamine block copolymer TA-1031, ethanol, deionized water;
At normal temperatures, be 0.023: 1 by the mol ratio of inorganic nanometer oxide parent aluminum sulfate and water, preparation aluminum sulfate Al
2(SO
4)
3Solution;
Second step, by the percentage by weight of polyoxyethylene polyoxypropylene phenolic aldehyde polyethylene polyamine block copolymer TA-1031 in the product be 18%～54% and the percentage by weight of nano aluminium oxide be 2%～6% the above-mentioned two kinds of solution of measuring, mix at normal temperatures, be about to generate the aluminum sulfate Al of nano aluminium oxide
2(SO
4)
3Solution slowly is added drop-wise in the organic polymer demulsifier solution, after treating fully to mix, surveys the pH value of this moment;
In the 3rd step, the pH value of regulating mixed liquor dropping ammonia lentamente in mixed solution has good mobility according to the flowability interpolation deionized water of reaction back system with the maintenance system, and the pH value of whole system is adjusted to about 7;
The 4th step kept whole system to react under condition of stirring 6～8 hours, obtained inorganic-polymer complex structure demulsifier.
3. according to claim 2 a kind of inorganic-preparation method of polymer composite demulsifying agent, it is characterized in that: described inorganic nanometer oxide parent comprises aluminum sulfate Al
2(SO
4)
3, sodium metasilicate Na
2SiO
3Perhaps butyl titanate Ti (OC
4H
9)
4
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| CNB2004100098398A CN1326589C (en) | 2004-11-23 | 2004-11-23 | Demulsifier with inorganic-polymer compound structure and its preparing method |
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|---|---|---|---|
| CNB2004100098398A CN1326589C (en) | 2004-11-23 | 2004-11-23 | Demulsifier with inorganic-polymer compound structure and its preparing method |
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|---|---|
| CN1631483A CN1631483A (en) | 2005-06-29 |
| CN1326589C true CN1326589C (en) | 2007-07-18 |
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| US9623346B2 (en) * | 2010-08-02 | 2017-04-18 | Momentive Performance Materials Inc. | Compositions and methods for separating emulsions using the same |
| CN108048255A (en) * | 2017-12-28 | 2018-05-18 | 长沙善道新材料科技有限公司 | A kind of ageing oil cleaning agent and preparation method thereof |
| CN108641792B (en) * | 2018-06-11 | 2021-07-06 | 冠仕(上海)新能源科技有限公司 | Ultralow-temperature ash-free anti-wear flame-retardant ester hydraulic oil, production process and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5433863A (en) * | 1993-11-17 | 1995-07-18 | Nalco Chemical Company | Method for clarifying wastewater containing surfactants |
| US5560832A (en) * | 1995-05-08 | 1996-10-01 | Nalco Chemical Company | Demulsification of oily waste waters using silicon containing polymers |
| CN1253984A (en) * | 1998-11-13 | 2000-05-24 | 中国石油化工集团公司 | Multicomponent crude oil demulsification dehydration additive |
| CN1544117A (en) * | 2003-11-27 | 2004-11-10 | 胜利油田胜利工程设计咨询有限责任公 | Demulsifying agent of nanometer microparticle texture |
-
2004
- 2004-11-23 CN CNB2004100098398A patent/CN1326589C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5433863A (en) * | 1993-11-17 | 1995-07-18 | Nalco Chemical Company | Method for clarifying wastewater containing surfactants |
| US5560832A (en) * | 1995-05-08 | 1996-10-01 | Nalco Chemical Company | Demulsification of oily waste waters using silicon containing polymers |
| CN1253984A (en) * | 1998-11-13 | 2000-05-24 | 中国石油化工集团公司 | Multicomponent crude oil demulsification dehydration additive |
| CN1544117A (en) * | 2003-11-27 | 2004-11-10 | 胜利油田胜利工程设计咨询有限责任公 | Demulsifying agent of nanometer microparticle texture |
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